Electronic Supplementary Material (ESI) for Chemical Science.

This journal is © The Royal Society of Chemistry 2016

The Influence of Acceptor Nucleophilicity on the Glycosylation Reaction

Mechanism

S. van der Vorm, T. Hansen, H. S. Overkleeft, G. A. van der Marel, J. D. C. Codée

Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands

Supplementary Information

General experimental procedures S1

General procedure for Tf2O/Ph2SO mediated glycosylations S1

General computational procedure S1

Preparation of donor 1 S2

Preparation of donor 2 S3

Preparation of donor 3 S5

Preparation of acceptor 10 S7

Preparation of acceptor 11 S8

Preparation of acceptor 12 S9

Preparation of acceptor 13 S11

Preparation of acceptor 14 S13

Glycosylation data for donor 1 S14

Glycosylation data for donor 2 S21

Glycosylation data for donor 3 S28

NMR spectra of new compounds S36

Methyl 2,3,4-tri-O-methyl mannopyranosyl uronate oxocarbenium ion S110

3 4
atom coordinates and energies of the H4, H3, B2,5 conformations
General experimental procedures: All chemicals (Acros, Aldrich, Alfa Aesar, Fluka, Merck) were of commercial grade and
used as received unless stated otherwise. DCM was stored over activated 4 Å molecular sieves (beads, 8-12 mesh, Sigma-
Aldrich) for at least 24 h before use. Tri-tert-butylpyrimidine (TTBP) was synthesized as described by Crich et al.1 All non-
glycoside acceptors were stored in stock solutions (DCM, 0.5 M) over activated 4 Å molecular sieves. Glycoside acceptors
were diluted to 0.5 M in DCM prior to use. Trifluoromethanesulfonic anhydride (Tf2O) was distilled over P2O5 and stored at -
20°C under an argon atmosphere. Triethylamine (Et3N) was distilled over CaH2 and stored over KOH pellets. Overnight
temperature control was achieved by a FT902 Immersion Cooler (Julabo). Flash column chromatography was performed on
silica gel 60 Å (0.04 – 0.063 mm, Screening Devices B.V.). Size exclusion chromatography was performed on SephadexTM
(LH-20, GE Healthcare Life Sciences) by isocratic elution with DCM/MeOH (1/1, v/v). TLC-analysis was conducted on TLC
Silica gel 60 (Kieselgel 60 F254, Merck) with UV detection by (254 nm) and by spraying with 20% sulfuric acid in ethanol
followed by charring at ±150 °C or by spraying with a solution of (NH4)6Mo7O24·H2O (25 g/L) and (NH4)4Ce(SO4)4·2H2O (10
g/L) in 10% sulfuric acid in water followed by charring at ±150 °C. TLC-MS analysis was performed on a Camag TLC-MS
Interface combined with an API165 (SCIEX) mass spectrometer (eluted with tert-butylmethylether/EtOAc/MeOH, 5/4/1, v/v/v
+ 0.1% formic acid, flow rate 0.12 mL/min). LC-MS analysis was conducted on a Finnigan LCQ Advantage Max mass
spectrometer with a Finnigan Surveyor HPLC system eluted with a gradient solvent (8 min, 1 mL/min, 10%-90% CH3CN in
H2O + 1% TFA, total sample run 12 min). High-resolution mass spectra were recorded on a Thermo Finnigan LTQ Orbitrap
mass spectrometer equipped with an electrospray ion source in positive mode (source voltage 3.5 kV, sheath gas flow 10,
capillary temperature 275 ⁰C) with resolution R=60.000 at m/z=400 (mass range = 150-4000). 1H, 2H and 13C NMR spectra
were recorded on a Bruker AV-400 NMR instrument (400, 61 and 101 MHz respectively), or a Bruker DMX-400 NMR
instrument. For samples measured in CDCl3 chemical shifts (δ) are given in ppm relative to tetramethylsilane as internal
standard or the residual signal of the deuterated solvent. Coupling constants (J) are given in Hz. All given 13C-APT spectra are
proton decoupled. NMR peak assignments were made using COSY and HSQC. If necessary additional NOESY, HMBC and
(HMBC-)GATED experiments were used to further elucidate the structure. The anomeric product ratios were based on careful
analysis of the crude reaction mixture and the purified reaction product by integration of representative 1H NMR signals. IR
spectra were recorded on a Shimadzu FTIR-8300 IR spectrometer and are reported in cm-1. Specific rotations were measured
on a Propol automatic polarimeter in CHCl3 (10 mg/ml) at 589 nm unless otherwise stated.

General procedure for Tf2O/Ph2SO mediated glycosylations: Donor (0.1 mmol), Ph2SO (26 mg, 0.13 mmol, 1.3 eq.) and
TTBP (62 mg, 0.25 mmol, 2.5 eq.) were coevaporated twice with dry toluene (4 Å molecular sieves) and dissolved in DCM (2
mL, 0.05 M donor). Activated 3Å molecular sieves (rods, size 1/16 in.) were added and the reaction mixture stirred for 30 min
at room temperature. The solution was cooled to -78°C and Tf2O (22 μl, 0.13 mmol, 1.3 eq.) was slowly added. The reaction
mixture was allowed to warm to -60°C in approximately 45 min, followed by recooling to -78°C and addition of the acceptor
(0.2 mmol, 2 eq.) in DCM (0.4 mL, 0.5 M). The reaction mixture was allowed to warm to -40°C in approximately 60 min and
stirred for an additional 0-18 h depending on the acceptor. The reaction was quenched with Et3N (0.1 mL, 0.72 mmol, 5.5 eq.)
at -40 ⁰C and diluted with DCM. The solution was transferred to a separatory funnel and water was added, the layers were
separated and the water phase extracted once more with DCM. The combined organic layers were dried over MgSO 4, filtered,
and concentrated in vacuo. Purification by silica gel flash column chromatography and when needed, sephadexTM LH-20 size
exclusion chromatography yielded the glycosylation product as a mixture of anomers.

General computational procedure: Density functional theory (DFT) ab initio calculations were performed with the B3LYP
model. Conformations were generated from a conformer distribution search option included in the Spartan 04 program2 in the
gas phase at the 6-31G* basis set level. All generated geometries were further optimized with Gaussian 03 3 at the 6-311G**
level, their zero-point energy corrections calculated and further optimized with incorporated polarizable continuum model
(PCM) to correct for solvation in dichloromethane.

S1
Preparation of donor 1

Scheme S-1: Mannose donor 1 synthesis. Reagents and conditions: a) i. Ac2O, HClO4; ii. HBr, AcOH; iii. PhSH, NaH, DMF,
S1: 65% (three steps); b) NaOMe, MeOH, S2: 99%; c) i. PhCH(OMe)2, CSA; ii. BnBr, NaH, DMF, 1: 51% (two steps).

Phenyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-mannopyranoside (S1)

To a mixture of HBr (33 wt% in AcOH, 35 mL, 200 mmol, 1 eq.) and Ac2O (93 mL, 1020 mmol, 5.1 eq.) and 10 drops of 70%
aq. HClO4 , D-mannose (36.0 g, 200 mmol) was added portion wise at 0 ⁰C. After 20 minutes an additional amount of HBr (33
wt% in AcOH, 70 mL, 400 mmol, 2 eq.) was added. After stirring for 16 h at r.t. the reaction mixture was concentrated in vacuo
at 30 ⁰C. The resulting black oil was co-evaporated with toluene until neutral pH was reached and was used in the following
step without further purification. To a solution of the crude product in DMF (400 mL), thiophenol (21.5 mL, 210 mmol, 1.05
eq.) was added. The reaction mixture was cooled to 0 ⁰C and NaH (60% dispersion in mineral oil, 8.4 g, 210 mmol, 1.05 eq.)
was added portion wise. After 2 h stirring at r.t. the reaction was quenched by the addition of aq. HCl (1 M). To the resulting
black suspension, 4 L of water was added and extracted 10 times with Et 2O. The combined organic layers were washed with
water, dried with MgSO4 and concentrated in vacuo. Flash column chromatography (9/1 to 7/3 pentane/EtOAc) afforded the
title compound as an orange oil (57.3 g, 130 mmol, 65%). Rf: 0.70 (1/1 pentane/EtOAc). Spectroscopic data were in accord
with those previously reported.4,5 [α]26 1
D = -44.4° (c = 0.5, CHCl3); IR (neat): 1047, 1213, 1368, 1742; H NMR (400 MHz,

CDCl3, HH-COSY, HSQC): δ 7.56 – 7.47 (m, 2H, CHarom SPh), 7.34 – 7.30 (m, 3H, CHarom SPh), 5.66 (dd, 1H, J = 3.5, 0.8 Hz,
H-2), 5.28 (t, 1H, J = 10.0 Hz, H-4), 5.07 (dd, 1H, J = 10.1, 3.5 Hz, H-3), 4.94 (d, 1H, J = 1.0 Hz, H-1), 4.29 (dd, 1H, J = 12.2,
6.5 Hz, H-6), 4.17 (dd, 1H, J = 12.2, 2.4 Hz, H-6), 3.72 (ddd, 1H, J = 10.0, 6.4, 2.5 Hz, H-5), 2.20 (s, 3H, CH3 OAc), 2.09 (s,
3H, CH3 OAc), 2.04 (s, 3H, CH3 OAc), 1.98 (s, 3H CH3, OAc); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 170.5, 170.1,
167.0, 169.6 (C=O Ac), 133.2 (Cq SPh), 131.9, 129.1, 128.1 (CHarom SPh), 85.5 (C-1), 76.4 (C-5), 71.8 (C-3), 70.6 (C-2), 65.8
(C-4), 62.8 (C-6), 20.7, 20.7, 20.6, 20.6 (CH3 Ac); 13C-GATED NMR (101 MHz, CDCl3): δ 85.5 (JC1,H1 = 153 Hz, C-1 β);
HRMS: [M+Na]+ calcd for C20H24O9SNa 463.10332, found 463.10305.

Phenyl 1-thio-β-D-mannopyranoside (S2)

To a solution of S1 (24.9 g, 56.5 mmol) in MeOH (280 mL), NaOMe (0.31 g, 5.7 mmol, 0.1 eq.) was added. The reaction
mixture was stirred for 16 h. Amberlite IR120 H+ was added until pH 6 was reached and the mixture was filtered and
concentrated in vacuo. This afforded the title compound (15.3 g, 56.4 mmol, 99%) as a white foam. Rf: 0.20 (9/1 DCM/MeOH).
Spectroscopic data were in accord with those previously reported.6,7 IR (neat, cm-1): 880, 1085, 1636, 2974, 3312; 1H NMR
(400 MHz, MeOD, HH-COSY, HSQC): δ 7.53 – 7.46 (m, 2H, CHarom SPh), 7.34 – 7.17 (m, 3H, CHarom SPh), 5.00 (s, 1H, H-
1), 4.05 (dd, 1H, J = 3.4, 1.0 Hz, H-2), 3.88 (dd, 1H, J = 11.9, 2.4 Hz, H-6), 3.73 (dd, 1H, J = 12.1, 5.7 Hz, H-6), 3.63 (t, 1H,
J = 9.5 Hz, H-4), 3.51 (dd, 1H, J = 9.5, 3.4 Hz, H-3), 3.29 (m, 1H, J = 5.8 Hz, H-5); 13C-APT NMR (101 MHz, MeOD, HSQC):

S2
δ 131.0, 130.0, 127.7 (CHarom SPh), 88.8 (C-1), 82.4 (C-5), 76.2 (C-3), 74.3 (C-2), 68.3 (C-4), 62.9 (C-6); HRMS: [M+Na]+
calcd for C12H16O5SNa 295.06107, found 295.06107.

Phenyl 2,3-di-O-benzyl-4,6-O-benzylidene-1-thio-β-D-mannopyranoside (1)

To a solution of S2 (1.36 g, 5 mmol) in DMF (50 mL), benzaldehyde dimethyl acetal (3.0 mL, 20 mmol, 4 eq.) and CSA (0.25
g, 1 mmol, 0.2 eq.) were added. After the solution was stirred for 16 h, benzyl bromide (2.4 mL, 20 mmol, 4 eq.) and NaH
(60% dispersion in mineral oil, 0.48 g, 20 mmol, 4 eq.) were added at 0 ⁰C. The suspension was allowed to warm up until r.t.
and stirred for an additional 2 h. The reaction mixture was quenched with MeOH, followed by the addition of DCM (250 mL)
and ice water (500 mL). The water layer was extracted once with DCM and the combined organic layers were washed with
water and brine. The combined organic layers were dried over MgSO4, filtered and concentrated under reduced pressure. Flash
column chromatography (1/0 to 9/1 pentane/EtOAc) and subsequent recrystallization from EtOAc and pentane afforded the
title compound as a white solid (1.38 g, 2.56 mmol, 51% over 2 steps). Rf: 0.27 (9/1 pentane/EtOAc). Spectroscopic data were
in accord with those previously reported.8 IR (neat): 733, 1026, 1069, 1452, 2864; 1H NMR (400 MHz, CDCl3, HH-COSY,
HSQC, HMBC): δ 7.64 – 7.14 (m, 20H, CHarom), 5.64 (s, 1H, CHPh), 5.12 (d, 1H, J = 11.1 Hz, CHH Bn), 4.89 (d, 1H, J = 12.3
Hz, CHH Bn), 4.86 (d, 1H, J = 11.1 Hz, CHH Bn), 4.85 (d, 1H, J = 1.3 Hz, H-1), 4.74 (d, 1H, J = 12.3 Hz, CHH Bn), 4.36 –
4.26 (m, 2H, H-4, H-6), 4.18 (dd, 1H, J = 3.1, 1.3 Hz, H-2), 3.95 (t, 1H, J = 10.3 Hz, H-6), 3.74 (dd, 1H, J = 9.8, 3.1 Hz, H-3),
3.42 (td, 1H, J = 9.7, 4.9 Hz, H-5); 13C-APT NMR (101 MHz, CDCl3, HSQC, HMBC): δ 138.1, 137.6, 135.1 (Cq), 131.2, 129.1,
129.1, 128.8, 128.6, 128.4, 127.9, 127.9, 127.8, 127.6, 126.2 (CHarom), 101.6 (CHPh), 89.2 (C-1), 79.9 (C-3), 79.1 (C-2), 78.8
(C-4), 76.0, 73.3 (CH2 Bn), 71.8 (C-5), 68.6 (C-6); 13C-GATED NMR (101 MHz, CDCl3) δ 89.2 (JC1,H1 = 152 Hz, C-1 β);
HRMS: [M+NH4]+ calcd for C33H36NO5S 558.23087, found 558.23071.

Preparation of donor 2

Scheme S-2: Glucose donor 2 synthesis. Reagents and conditions: a) Ac2O, NaOAc, S3: 89%; b) PhSH, BF3•OEt2, DCM, S4:
75%; c) NaOMe, MeOH, S5: 85%; d) PhCH(OMe)2, p-TsOH•H2O, S6: 94%; e) BnBr, NaH, DMF, 2: 86%.

1,2,3,4,6-Penta-O-acetyl-α/β-D-glucopyranoside (S3)

S3
To a 140°C solution of NaOAc (8.2 g, 100 mmol, 0.5 eq) in Ac2O (190 mL, 2 mol, 10 eq.) D-glucose was added portionwise
and the reaction mixture was refluxed for an additional 15 min. The solution was cooled to r.t. and poured over crushed ice.
The product was filtered, taken up in DCM, concentrated in vacuo and recrystallized from hot EtOH (750 mL) to give the
product as a white solid (69.4 g, 178 mmol, 89%). Spectroscopic data were in accord with those previously reported.9,10 Data
for the β-anomer: 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 5.72 (d, 1H, J = 8.3 Hz, H-1), 5.26 (t, 1H, J = 9.4 Hz, H-
3), 5.19 – 5.08 (m, 2H, H-2, H-4), 4.30 (dd, 1H, J = 12.7, 3.8 Hz, H-6), 4.15 – 4.08 (m, 1H, H-6), 3.88 – 3.81 (m, 1H, H-5),
2.12 (s, 3H, CH3 OAc), 2.09 (s, 3H, CH3 OAc), 2.04 (s, 6H, 2xCH3 OAc), 2.02 (s, 3H, CH3 OAc); 13C-APT NMR (CDCl3, 101
MHz, HSQC): δ 170.7, 170.2, 169.5, 169.4, 169.1 (C q OAc), 91.8 (C-1), 72.9, 72.8 (C-3, C-5), 70.3, 67.9 (C-2, C-4), 61.6 (C-
6), 21.0, 20.8, 20.7 (CH3 OAc);

Phenyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranoside (S4)

D-glucose pentaacetate S3 (20 g, 51 mmol) was dissolved in DCM (100 mL) and cooled to 0°C. Thiophenol (7.8 mL, 76.5
mmol, 1.5 eq.) was added followed by addition of boron trifluoride diethyl etherate (10.9 mL, 76.5 mmol, 1.5 eq.) and the
mixture was refluxed overnight. Sat. aq. NaHCO3 (300 mL) and Et2O (100 mL) were added and the mixture was extracted
three times with Et2O. The organic layer was washed with brine, dried with MgSO4, filtered and concentrated under reduced
pressure. The crude product was purified by crystallization from EtOAc/hexane (1/10) to obtain the title compound as a white
solid. (16.8 g, 38.2 mmol, 75%). Spectroscopic data were in accord with those previously reported.11–14 1H NMR (CDCl3, 400
MHz, HH-COSY, HSQC): δ 7.50 (dd, 2H, J = 6.6, 3.0 Hz, CHarom), 7.34 – 7.28 (m, 3H, CHarom), 5.24 (t, 1H, J = 9.3 Hz, H-3),
5.04 (t, 1H, J = 9.8 Hz, H-4), 4.97 (t, 1H, J = 9.6 Hz, H-2), 4.75 (d, 1H, J = 10.0 Hz, H-1), 4.23 (dd, 1H, J = 12.3, 5.1 Hz, H-
6), 4.17 (dd, 1H, J = 12.3, 2.5 Hz, H-6), 3.76 (ddd, 1H, J = 10.0, 5.1, 2.5 Hz, H-5), 2.07 (s, 3H, CH3 OAc), 2.06 (s, 3H, CH3
OAc), 2.01 (s, 3H, CH3 OAc), 1.98 (s, 3H, CH3 OAc); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 170.2, 169.8, 169.2, 169.0
(C=O Ac), 132.8 (CHarom), 131.5 (Cq), 128.8, 128.2 (CHarom), 85.3 (C-1), 75.5 (C-5), 73.8 (C-3), 69.8 (C-2), 68.1 (C-4), 61.9
(C-6), 20.5, 20.5, 20.4, 20.4 (CH3 Ac);

Phenyl 1-thio-β-D-glucopyranoside (S5)

To a solution of S4 (16.3 g, 37.0 mmol) in MeOH (200 mL) was added Na(s) (89 mg, 3.7 mmol, 0.1 eq) and the reaction was
stirred for 18 h at r.t. The reaction mixture was neutralized with Amberlite H +, filtered and Celite® was added to the filtrate
and the mixture concentrated in vacuo. The residue was purified by flash column chromatography (1% to 12% EtOH in EtOAc)
to obtain a white solid (8.6 g, 31.6 mmol, 85%). Spectroscopic data were in accord with those previously reported. 15 1H NMR
(MeOD, 400 MHz, HH-COSY, HSQC): δ 7.61 – 7.54 (m, 2H, CHarom), 7.33 – 7.24 (m, 3H, CHarom), 4.60 (d, 1H, J = 9.8 Hz,
H-1), 3.87 (dd, 1H, J = 12.1, 1.8 Hz, H-6), 3.67 (dd, 1H, J = 12.2, 5.2 Hz, H-6), 3.39 (t, 1H, J = 8.5 Hz, H-3), 3.35 – 3.26 (m,
2H, H-4, H-5), 3.22 (dd, 1H, J = 9.8, 8.6 Hz, H-2); 13C-APT NMR (MeOD, 101 MHz, HSQC): δ 135.3 (Cq), 132.7, 129.9,
128.3 (CHarom), 89.4 (C-1), 82.0 (C-4), 79.7 (C-3), 73.7 (C-2), 71.3 (C-5), 62.8 (C-6);

S4
Phenyl 4,6-O-benzylidene-1-thio-β-D-glucopyranoside (S6)

To a solution of S5 (12.81 g, 47 mmol) and p-TsOH•H2O (100 mg, 0.5 mmol, 0.01 eq.) in DMF (25 mL) and CH3CN (100
mL) was added benzyldehyde dimethyl acetal (9.9 mL, 65.8 mmol, 1.4 eq.). The reaction was heated to 50°C at 250 mbar for
5 hours and subsequently quenched with Et3N (2 mL) and diluted with EtOAc (250 mL). The solution was washed with H 2O
(2x 100 mL) and brine (100 mL). The organic layer was dried (MgSO4) and concentrated in vacuo. Percipitation from
EtOAc/petroleum ether formed a waxy material (12.0 g, 33.3 mmol) and the remaining mother liquors were purified by column
chromatography (3/1 to 1/3 pentane/EtOAc) to give another batch of product (3.86 g, 10.7 mmol). Total yield 15.9 g, 44 mmol,
94%. Rf: 0.50 (1/2 pentane/EtOAc). Spectroscopic data were in accord with those previously reported.12–14 1H NMR (CDCl3,
400 MHz, HH-COSY, HSQC): δ 7.59 – 7.51 (m, 2H, CHarom), 7.51 – 7.44 (m, 2H, CHarom), 7.40 – 7.31 (m, 6H, CHarom), 5.54
(s, 1H, CHPh), 4.64 (d, 1H, J = 9.8 Hz, H-1), 4.39 (dd, 1H, J = 10.5, 4.4 Hz, H-6), 3.91 – 3.74 (m, 2H, H-4, H-6), 3.59 – 3.43
(m, 3H, H-2, H-3, H-5); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 137.0 (Cq), 133.2 (CHarom), 131.4 (Cq), 129.5, 129.3,
128.7, 128.5, 126.4 (CHarom), 102.1 (CHPh), 88.8 (C-1), 80.4 (C-3), 74.7 (C-4), 72.7 (C-2), 70.7 (C-5), 68.7 (C-6);

Phenyl 2,3-di-O-benzyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside (2)

Diol S6 (7.21 g, 20 mmol) was dissolved in DMF (100 mL) and cooled to 0°C. Benzyl bromide (5.75 mL, 48 mmol, 2.4 eq.)
and NaH (60% dispersion in mineral oil, 2.4 g, 60 mmol, 3 eq.) were added and the reaction mixture was allowed to stir
overnight. MeOH was added to quench the reaction followed by H2O (500 mL) and EtOAc (300 mL). The organic layer was
washed with brine and dried with MgSO4. After concentration of the organic layer under reduced pressure, the crude product
was crystallized from EtOAc (50 mL) and hexane (100 mL) to obtain the title compound as a white solid (9.49 g, 17.4 mmol,
86%). Spectroscopic data were in accord with those previously reported.12–14,16 1H NMR (CDCl3, 400 MHz, HH-COSY,
HSQC): δ 7.56 – 7.51 (m, 2H, CHarom), 7.51 – 7.46 (m, 2H, CHarom), 7.42 – 7.26 (m, 16H, CHarom), 5.59 (s, 1H, CHPh), 4.94
(d, 1H, J = 11.1 Hz, CHH Bn), 4.86 (d, 1H, J = 10.2 Hz, CHH Bn), 4.81 (d, 1H, J = 10.3 Hz, CHH Bn), 4.80 – 4.73 (m, 2H,
CHH Bn, H-1), 4.39 (dd, 1H, J = 10.5, 5.0 Hz, H-6), 3.84 (dd, 1H, J = 9.3, 8.3 Hz, H-3), 3.80 (t, 1H, J = 10.3 Hz, H-6), 3.71
(t, 1H, J = 9.3 Hz, H-4), 3.56 – 3.42 (m, 2H, H-2, H-5); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 138.4, 138.1, 137.4,
133.2 (Cq-arom), 132.5, 129.1, 129.1, 128.5, 128.5, 128.4, 128.3, 128.2, 128.0, 128.0, 127.9, 126.1 (CH arom), 101.3 (CHPh), 88.4
(C-1), 83.1 (C-3), 81.6 (C-4), 80.6 (C-2), 76.0, 75.5 (CH2 Bn), 70.4 (C-5), 68.8 (C-6); HRMS: [M+H]+ calcd for C33H33O5S
541.20432, found 541.20392.

Preparation of donor 3

Scheme S-3: Mannuronic acid ester donor 3 synthesis. Reagents and conditions: a) p-TsOH•H2O, MeOH, S7: 93%; b) i.
TEMPO, BAIB, DCM, H2O, AcOH; ii. MeI, K2CO3, DMF, S8: 63% (two steps); c) Ac2O, pyridine, 3: 92%.

S5
Phenyl 2,3-di-O-benzyl-1-thio-β-D-mannopyranoside (S7)

To a solution of 2 (1.62 g, 3 mmol) in MeOH (30 mL), p-TsOH·H2O (60 mg, 0.3 mmol, 0.1 eq.) was added. The suspension
was stirred for 1 h at 50 ⁰C and subsequently quenched with Et3N. After concentration in vacuo the resulting product was
purified by flash column chromatography (9/1 to 1/1 pentane/EtOAc) to yield the title compound as a colourless foam (1.26 g,
2.78 mmol, 93%). Rf: 0.10 (4/1 pentane/EtOAc). Spectroscopic data were in accord with those previously reported.17 [α]26
D =-

62.4° (c = 0.5, CHCl3); IR (neat): 734, 1026, 1119, 1454, 924, 3391; 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.54
– 7.19 (m, 15H, CHarom), 4.97 (d, 1H, J = 11.3 Hz, CHH Bn), 4.85 (s, 1H, H-1), 4.85 (d, 1H, J = 11.3 Hz, CHH Bn), 4.75 (d,
1H, J = 11.7 Hz, CHH Bn), 4.53 (d, 1H, J = 11.7 Hz, CHH Bn), 4.20 (d, 1H, J = 2.1 Hz, H-2), 4.05 (td, 1H, J = 9.5, 2.3 Hz, H-
4), 3.93 (ddd, 1H, J = 11.0, 7.2, 3.6 Hz, H-6), 3.82 (dt, 1H, J = 12.1, 6.3 Hz, H-6), 3.46 (dd, 1H, J = 9.5, 2.8 Hz, H-3), 3.38
(ddd, 1H, J = 9.5, 6.0, 3.6 Hz, H-5), 2.33 (s, 1H, 4-OH), 2.14 (t, 1H, J = 6.4 Hz, 6-OH); 13C-APT NMR (101 MHz, CDCl3,
HSQC): δ 138.0, 137.6, 135.1 (Cq), 130.7, 129.2, 128.8, 128.5, 128.4, 128.3, 127.9, 127.9, 127.5 (CHarom), 87.9 (C-1), 83.6 (C-
3), 80.1 (C-5), 76.7 (C-2), 75.3, 72.3 (CH2 Bn), 67.5 (C-4), 63.1 (C-6); 13C-GATED NMR (101 MHz, CDCl3): δ 87.9 (J = 152
Hz, C-1 β); HRMS: [M+Na]+ calcd for C26H28O5SNa 475.15497, found 475.15430.

Methyl (phenyl 2,3-di-O-benzyl-1-thio-β-D-mannopyranosyl uronate) (S8)

To a two phase system of S7 (1.25 g, 2.76 mmol) in DCM (10 mL) and H2O (5 mL), TEMPO (86 mg, 0.55 mmol, 0.2 eq.),
BAIB (2.22 g, 6.9 mmol, 2.5 eq.) and AcOH (50 μL) were added. The reaction mixture was stirred for 6 h and was quenched
with sat. aq. Na2S2O3. The resulting suspension was concentrated under reduced pressure and co-evaporated three times with
toluene. The formed solid was dissolved in DMF (15 mL), K2CO3 (1.14 g, 8.28 mmol, 3 eq.) and methyl iodide (0.52 mL, 8.28
mmol, 3 eq.) were added. The suspension was stirred for 16 h at r.t. and followed by the addition of H 2O (150 mL). The aqueous
layer was extracted three times with Et2O and subsequently washed with sat. aq. NaHCO3 and brine. The combined organic
layers were dried over MgSO4, filtered and concentrated under reduced pressure. Flash column chromatography (1/0 to 3/1
pentane/EtOAc) followed by recrystallization in EtOAc and pentane afforded the title compound as a white solid (0.48 g, 1.75
mmol, 63% over 2 steps). Rf: 0.70 (1/1 pentane/EtOAc). Spectroscopic data were in accord with those previously reported. 17
[α]26 1
D = -72,0° (c = 0.5, CHCl3); IR (neat): 696, 735, 1026, 1064, 1123, 1429, 1454, 1744, 2855, 2924, 3462; H NMR (400

MHz, CDCl3, HH-COSY, HSQC): δ 7.51 – 7.25 (m, 20H, CHarom), 5.02 (d, 1H, J = 11.4 Hz, CHH Bn), 4.86 (d, 1H, J = 11.3
Hz, CHH Bn), 4.79 – 4.74 (m, 3H, CHH Bn, CHH Bn, H-1), 4.41 (td, 1H, J = 9.5, 2.1 Hz, H-4), 4.12 (dd, 1H, J = 3.0, 1.0 Hz,
H-2), 3.84 – 3.77 (m, 4H, H-5, CH3 CO2Me), 3.50 (dd, 1H, J = 9.5, 2.9 Hz, H-3), 3.11 (d, 1H, J = 2.3 Hz, 4-OH); 13C-APT
NMR (101 MHz, CDCl3, HSQC): δ 138.0, 135.1 (Cq), 131.3, 129.1, 128.7, 128.6, 128.3, 128.1, 127.9, 127.9, 127.6 (CH arom),
89.0 (C-1), 82.4 (C-3), 78.3 (C-5), 77.0 (C-2), 75.4, 73.1 (CH2 Bn), 68.6 (C-4), 52.9 (CH3 CO2Me); 13C- GATED NMR (101
MHz, CDCl3): δ 89.0 (JC1,H1 = 154 Hz, C-1 β). HRMS: [M+H]+ calcd for C27H29O6S 481,16794, found 481,16812.

Methyl (phenyl 4-O-acetyl-2,3-di-O-benzyl-thio-β-D-mannopyranosyl uronate) (3)

S6
To a suspension of S8 (1.20 g, 2.5 mmol) in pyridine (3.0 mL, 37.5 mmol, 15 eq.), Ac2O (0.30 mL, 3.1 mmol, 1.25 eq.) was
added. After stirring for 16 h at r.t., the reaction mixture was quenched with H 2O (25 mL). To the quenched reaction mixture,
EtOAc was added and the layers were separated. The water layer was extracted for an additional 2 times with EtOAc. The
combined organic layers were washed with sat. aq. NaHCO3 and brine. The resulting organic layer was dried over MgSO4,
filtered and concentrated under reduced pressure. Flash column chromatography (9/1 to 7/3 pentane/EtOAc) afforded the title
compound as a white solid (1.2 g, 2.3 mmol, 92%). Rf: 0.42 (7/3 pentane/EtOAc). [α]26
D = -84.0° (c = 0.5, CHCl3); IR (neat):

733, 1024, 1053, 1089, 1746, 2870; 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.50 – 7.23 (m, 15H, CHarom), 5.61 (t,
1H, J = 9.6 Hz, H-4), 5.03 (d, 1H, J = 11.6 Hz, CHH Bn), 4.85 (d, 1H, J = 11.6 Hz, CHH Bn), 4.78 (d, 1H, J = 1.1 Hz, H-1),
4.67 (d, 1H, J = 12.2 Hz, CHH Bn), 4.57 (d, 1H, J = 12.2 Hz, CHH Bn), 4.15 (dd, 1H, J = 2.8, 1.0 Hz, H-2), 3.88 (d, 1H, J =
9.6 Hz, H-5), 3.74 (s, 3H, CH3 CO2Me), 3.61 (dd, 1H, J = 9.7, 2.9 Hz, H-3), 2.01 (s, 3H, CH3 OAc); 13C-APT NMR (101 MHz,
CDCl3, HSQC): δ 169.7, 167.8 (C=O CO2Me, Ac), 137.9, 137.7, 135.1 (Cq), 131.3, 129.1, 128.7, 128.6, 128.3, 128.1, 127.9,
127.7, 127.7 (CHarom), 88.7 (C-1), 80.4 (C-3), 77.3 (C-5), 76.4 (C-2), 75.1, 72.6 (CH2 Bn), 68.9 (C-4), 52.8 (CH3 CO2Me), 21.0
(CH3 Ac); 13C-GATED NMR (101 MHz, CDCl3): δ 88.7 (JC1,H1 = 152 Hz, C-1 β); HRMS: [M+NH4]+ calcd for C29H34NO7S
540.20505, found 540.20515.

Preparation of acceptor 10

Scheme S-4: Glucose acceptor 10 synthesis. Reagents and conditions: a) TrtCl, Et3N, DMAP, DMF; b) BnBr, NaH, DMF; c)
p-TsOH•H2O, MeOH, 10: 78% (three steps).

Methyl 2,3,4-tri-O-benzyl-α-D-glucopyranoside (10)

To a solution of methyl-α-D-glucopyranoside in DMF (50 mL), trityl chloride (3.1 g, 11 mmol, 1.1 eq.), Et3N (2.1 mL, 15 mmol,
1.5 eq.) and DMAP (0.12 g, 1 mmol, 0.1 eq.) were added. After stirring for 6 h at 60 ⁰C the reaction was cooled to 0 ⁰C and
followed by the addition of benzyl bromide (4.8 mL, 40 mmol, 4 eq.), NaH (2 g, 50 mmol, 5 eq.). The suspension was stirred
for 16 h at r.t. and subsequently quenched with MeOH. The reaction mixture was concentrated under reduced pressure and the
remaining oil was transferred to a separation funnel. Et2O and H2O were added and the layers were separated. The water layer
was extracted three more times with Et2O. The combined organic layers were washed with water, sat. aq. NaHCO3 and brine.
The resulting organic layer was dried over MgSO4, filtered and concentrated under reduced pressure. The crude product S9
was suspended in MeOH (100 mL) followed by the addition of p-TsOH·H2O (0.19 g, 1 mmol, 0.1 eq.). After stirring for 1 h at
50 ⁰C the reaction mixture was quenched with sat. aq. NaHCO3 and concentrated in vacuo. Flash column chromatography (1/0
to 7/3 pentane/EtOAc) afforded the title compound as a waxy solid (3.6 g, 7.7 mmol, 78% over 3 steps). Spectroscopic data
were in accord with those previously reported.11,18 Rf: 0.57 (7/3 pentane/EtOAc). IR (neat): 880, 1043, 1086, 1381, 1636, 2893,
2974, 3312; 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.42 – 7.24 (m, 15H, CHarom), 4.99 (d, 1H, J = 10.8 Hz, CHH
Bn), 4.92 – 4.77 (m, 3H, CHH Bn, CHH Bn, CHH Bn), 4.72 – 4.60 (m, 2H, CHH Bn, CHH Bn), 4.56 (d, 1H, J = 3.5 Hz, H-

S7
1), 4.01 (t, 1H, J = 9.3 Hz, H-4), 3.82 – 3.73 (m, 1H, H-6), 3.73 – 3.61 (m, 2H, H-6, H-5), 3.58 – 3.45 (m, 2H, H-6, H-2, H-3),
3.37 (s, 3H, CH3 OMe), 1.61 (dd, 1H, J = 7.3, 5.4 Hz, 6-OH); 13C-APT NMR (101 MHz, CDCl3, HSQC, HMBC): δ 138.8,
138.2 (Cq), 128.6, 128.6, 128.6, 128.3, 128.2, 128.1, 128.1, 128.0, 127.8 (CH arom), 98.3 (C-1), 82.1 (C-4), 80.0 (C-2), 77.4 (C-
3), 75.9, 75.2, 73.6 (CH2 Bn), 70.7 (C-5), 62.0 (C-6), 55.3 (CH3 OMe); 13C-GATED NMR (101 MHz, CDCl3): δ 98.3 (JC1,H1 =
164 Hz, C-1 α); HRMS: [M+Na]+ calcd for C28H32O6Na 487.20911, found 487.20851.

Preparation of acceptor 11

Scheme S-5: Glucose acceptor 11 synthesis. Reagents and conditions: a) PhCH(OMe)2, p-TsOH•H2O, S10: 87%; b) BnBr,
NaH, DMF, S11: 87%; c) NaCNBH3, THF, HCl, dioxane, 11: 87%.

Methyl 4,6-O-benzylidene-α-D-glucopyranoside (S10)

To a solution of methyl α-D-glucopyranoside (38.8 g, 200 mmol) in acetonitrile (800 mL) was added PhCH(OMe) 2 (36 mL,
240 mmol, 1.2 eq.) and p-TsOH•H2O (3.8 g, 20 mmol, 0.1 eq.). The solution was stirred overnight at ambient temperature
followed by concentration in vacuo (60°C, 600 mbar, 1.5 h) to a quarter of its original volume. The reaction mixture was treated
with Et3N (3 mL), diluted with EtOAc (500 mL) and subsequently washed with H2O (2x 150 mL), sat. aq. NaHCO3 (50 mL)
and brine (2x 100 mL). The organic layer was dried (MgSO4), filtered and concentrated in vacuo. The resulting crude residue
was crystalized from EtOAc/petroleum ether to give the title product in two crops (49.2 g, 174 mmol, 87%, white solid).
Spectroscopic data were in accord with those previously reported.11,19 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 7.51
– 7.45 (m, 2H, CHarom), 7.36 (dd, 3H, J = 5.1, 2.0 Hz, CHarom), 5.51 (s, 1H, CHPh), 4.75 (d, 1H, J = 3.8 Hz, H-1), 4.28 (dd, 1H,
J = 9.6, 4.3 Hz, H-6), 3.91 (t, 1H, J = 9.2 Hz, H-3), 3.84 – 3.68 (m, 2H, H-5, H-6), 3.60 (dd, 1H, J = 9.2, 3.9 Hz, H-2), 3.47 (t,
1H, J = 9.3 Hz, H-4), 3.43 (s, 3H, CH3 OMe), 2.87 (bs, 2H, OH); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 137.2 (Cq),
129.4, 128.4, 126.4 (CHarom), 102.0 (CHPh), 99.9 (C-1), 81.1 (C-4), 72.9 (C-2), 71.7 (C-3), 69.0 (C-6), 62.5 (C-5), 55.7 (OMe);

Methyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside (S11)

Benzyl bromide (10.5 mL, 88 mmol, 2.2 eq.) and sodium hydride (60% dispersion, 4.16 g, 104 mmol, 2.6 eq.) were added to a
0°C solution of diol S10 (11.29 g, 40 mmol) in DMF (200 mL) and the solution was stirred overnight. The reaction mixture
was quenched by slow addition of MeOH, diluted with EtOAc (500 mL) and washed with H 2O (200 mL) and brine (200 mL).
The organic layer was dried with MgSO4, filtered and concentrated in vacuo. The solid residue was recrystallization from
EtOAc/pentane to yield the title compound as a white solid (16.0 g, 34.6 mmol, 87%). R f: 0.57 (4/1 pentane/EtOAc).

S8
Spectroscopic data were in accord with those previously reported.11,16 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 7.52
– 7.46 (m, 2H, CHarom), 7.41 – 7.25 (m, 13H, CHarom), 5.55 (s, 1H, CHPh), 4.92 (d, 1H, J = 11.3 Hz, CHH Bn), 4.85 (d, 1H, J
= 12.1 Hz, CHH Bn), 4.84 (d, 1H, J = 11.3 Hz, CHH Bn), 4.70 (d, 1H, J = 12.1 Hz, CHH Bn), 4.59 (d, 1H, J = 3.7 Hz, H-1),
4.26 (dd, 1H, J = 10.1, 4.7 Hz H-6), 4.05 (t, 1H, J = 9.3 Hz, H-3), 3.83 (td, 1H, J = 9.9, 4.7 Hz, H-5), 3.70 (t, 1H, J = 10.2 Hz,
H-6), 3.60 (t, 1H, J = 9.4 Hz, H-4), 3.56 (dd, 1H, J = 9.3, 3.7 Hz, H-2), 3.40 (s, 3H, CH3 OMe); 13C-APT NMR (CDCl3, 101
MHz, HSQC): δ 138.8, 138.3, 137.5 (Cq), 129.0, 128.6, 128.4, 128.3, 128.2, 128.1, 128.0, 127.7, 126.1 (CH arom), 101.4 (CHPh),
99.3 (C-1), 82.2 (C-4), 79.3 (C-2), 78.7 (C-3), 75.5, 73.9 (CH2 Bn), 69.2 (C-6), 62.4 (C-5), 55.5 (OMe);

Methyl 2,3,6-tri-O-benzyl-α-D-glucopyranoside (11)

Fully protected compound S11 (3.24 g, 7.0 mmol) was dissolved in THF (100 mL) and NaCNBH3 (4.0 g, 63 mmol, 9 eq.) was
added. To this solution 4.0 M HCl in 1,4-dioxane (18 mL, 72 mmol, 10.3 eq.) was slowly added and the reaction was stirred
for an additional hour. Ice cold H2O (300 mL) was added and the mixture extracted with DCM (2x 120 mL). The combined
organic layers were washed with sat. aq. NaHCO3 (100 mL) and brine (100 mL), dried with MgSO4 and concentrated in vacuo.
Flash column chromatography (6/1 to 4/1 pentane/EtOAc,) gave the title compound as a colorless oil (2.7 g, 5.85 mmol, 87%).
Rf: 0.37 (4/1 pentane/EtOAc). Spectroscopic data were in accord with those previously reported. 11 IR (neat): 695, 732, 1027,
1047, 1453, 2910, 3477; 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 7.41 – 7.23 (m, 15H, CHarom), 4.99 (d, 1H, J =
11.4 Hz, CHH Bn), 4.75 (d, 1H, J = 12.1 Hz, CHH Bn), 4.73 (d, 1H, J = 11.4 Hz, CHH Bn), 4.68 – 4.60 (m, 2H, CHH Bn, H-
1), 4.57 (d, 1H, J = 12.1 Hz, CHH Bn), 4.52 (d, 1H, J = 12.2 Hz, CHH Bn), 3.78 (dd, 1H, J = 9.6, 8.8 Hz, H-3), 3.74 – 3.63 (m,
3H, H-5, H-6, H-6), 3.59 (t, 1H, J = 9.2 Hz, H-4), 3.52 (dd, 1H, J = 9.6, 3.5 Hz, H-2), 3.37 (s, 3H, CH3 OMe), 2.44 (bs, 1H, 4-
OH); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 138.8, 138.1, 138.0 (Cq), 128.6, 128.5, 128.4, 128.1, 128.0, 128.0, 127.8,
127.6, 127.6 (CHarom), 98.2 (C-1), 81.5 (C-3), 79.6 (C-2), 75.4, 73.6, 73.1 (CH2 Bn), 70.7 (C-4), 69.9 (C-5), 69.5 (C-6), 55.2
(OMe); HRMS: [M+NH4]+ calcd for C28H36NO6 482.25371, found 482.25357.

Preparation of acceptor 12

Scheme S-6: Glucuronic acid ester acceptor 12 synthesis. Reagents and conditions: a) p-TsOH•H2O, MeOH, S12: 99%; b) i.
TEMPO, BAIB, DCM, H2O, AcOH; ii. MeI, K2CO3, DMF, 12: 52% (two steps).

Methyl 2,3-di-O-benzyl-α-D-glucopyranoside (S12)

S9
Fully protected S11 (9.25 g, 20 mmol) and p-TsOH•H2O (380 mg, 2 mmol, 0.1 eq.) were added to MeOH (100 mL) and heated
at 60°C for 15 min after all solids were dissolved and TLC analysis showed full conversion to a lower running spot. The reaction
mixture was quenched with Et3N (1 mL) and concentrated in vacuo. The crude product was purified by flash column
chromatography (8/1 to 3/2 pentane/acetone) to give the tile compound as a white solid (7.4 g, 19.8 mmol, 99%) as a white
solid. Rf: 0.33 (2/1 pentane/acetone). Spectroscopic data were in accord with those previously reported. 11,20 1H NMR (CDCl3,
400 MHz, HH-COSY, HSQC): δ 7.37 – 7.26 (m, 10H, CHarom), 5.00 (d, 1H, J = 11.4 Hz, CHH Bn), 4.75 (d, 1H, J = 12.2 Hz,
CHH Bn), 4.71 (d, 1H, J = 11.5 Hz, CHH Bn), 4.64 (d, 1H, J = 12.1 Hz, CHH Bn), 4.59 (d, 1H, J = 3.5 Hz, H-1), 3.78 (dd, 1H,
J = 9.6, 8.6 Hz, H-3), 3.78 – 3.69 (m, 2H, H-6), 3.61 – 3.56 (m, 1H, H-5), 3.51 (dd, 1H, J = 9.8, 8.6 Hz, H-4), 3.48 (dd, 1H, J
= 9.5, 3.5 Hz, H-2), 3.36 (s, 3H, CH3 OMe), 2.46 (bs, 2H, OH); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 138.8, 138.1 (Cq-
arom), 128.7, 128.6, 128.2, 128.1, 128.0, 127.9 (CH arom), 98.2 (C-1), 81.4 (C-3), 79.9 (C-2), 75.5, 73.2 (CH2 Bn), 70.8 (C-5),
70.3 (C-4), 62.3 (C-6), 55.3 (OMe);

Methyl (methyl 2,3-di-O-benzyl-α-D-glucopyranosyl uronate) (12)

To a solution of diol S12 (6.95 g, 18.6 mmol) in DCM (70 mL) and AcOH (0.1 mL) was added BAIB (14.95 g, 46.4 mmol,
2.5 eq.), TEMPO (580 mg, 3.7 mmol, 0.2 eq.) and H2O (30 mL). The solution was stirred vigorously for 2.5 hours at room
temperature, quenched by the addition of Na2S2SO3 (10% aq.) and this suspension stirred for 15 min. The mixture was extracted
two times with EtOAc and the combined organic fractions were dried (MgSO 4), filtered, concentrated in vacuo and
coevaporated with toluene once. The crude carboxylic acid was dissolved in DMF (75 mL) and cooled to 0°C. K 2CO3 (7.7 g,
55.7 mmol, 3 eq.) and MeI (3.5 mL, 55.7 mmol, 3 eq.) were added and the reaction mixture stirred overnight. H 2O was added
and the reaction mixture was extracted twice with EtOAc. The combined organic layers where dried (MgSO 4), filtered and
concentrated in vacuo. Purification by flash column chromatography (1/0 to 9/1 toluene/acetone) followed by recrystallization
from DCM/EtOAc/petroleum ether (1/1/23) gave the title product as white needles (3.84 g, 9.54 mmol, 52%, 2 steps).
30
Spectroscopic data were in accord with those previously reported.21 [α]23
D = +19.0° (c=1.0, CHCl3), lit.: [α]D = +17.9° (c=0.5,

CHCl3)21 ; IR: 700, 738, 1040, 1061, 1738, 2918, 3532; 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 7.39 – 7.26 (m,
10H, CHarom), 4.92 (d, 1H, J = 11.3 Hz, CHH Bn), 4.81 (d, 1H, J = 11.4 Hz, CHH Bn), 4.79 (d, 1H, J = 12.1 Hz, CHH Bn),
4.67 – 4.62 (m, 2H, CHH Bn, H-1), 4.15 (d, 1H, J = 8.9 Hz, H-5), 3.87 – 3.76 (m, 5H, H-3, H-4, CH3 CO2Me), 3.53 (dd, 1H,
J = 8.9, 3.4 Hz, H-2), 3.42 (s, 3H, CH3 OMe), 2.89 (bs, 1H, 4-OH); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 170.8 (C=O
CO2Me), 138.7, 138.0 (Cq-arom), 128.6, 128.3, 128.1, 128.0, 127.9 (CHarom), 98.8 (C-1), 80.5 (C-3), 78.6 (C-2), 75.6, 73.7 (CH2
Bn), 71.9 (C-4), 70.6 (C-5), 56.0 (OMe), 52.8 (CO2Me); HRMS: [M+Na]+ calcd for C22H26O7Na 425.15707, found 425.15649.

S10
Preparation of acceptor 13

Scheme S-7: Galactose acceptor 13 synthesis. Reagents and conditions: a) i. Ac2O, HClO4; ii. HBr, AcOH; iii. I2, MeOH, S13:
48% (three steps); b) NaOMe, MeOH; c) PhCH(OMe)2, p-TsOH•H2O, S15: 61% (two steps); d) BnBr, NaH, DMF, S16: 75%;
e) NaCNBH3, THF, HCl, dioxane, 13: 74%.

Methyl 2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside (S13)

Following the procedure of Kartha et al.22 D-galactose (4.5 g, 25 mmol) was portionwise added to a mixture of 70% aq. HClO4
(cat., 5 drops) and Ac2O (14.2 mL, 150 mmol, 6 eq.). After stirring overnight a 33 wt% solution of HBr in AcOH (13.1 mL, 75
mmol, 3 eq.) was added and the reaction stirred at r.t. for 5 h. Solvents were evaporated by a water aspirator and the crude
product was dissolved in EtOAc and washed with cold [Link]. NaHCO3 and brine. The organic phase was dried Na2SO4 and
concentrated in vacuo. The crude bromide was dissolved in MeOH (100 mL) and cooled to 0°C. Iodine (3.17 g, 12.5 mmol,
0.5 eq.) was added and the reaction was stirred for 2 h. The reaction mixture was quenched by sat. aq. Na2S2O4 and extracted
with Et2O twice. The organic layer was washed with sat. aq. NaHCO3 and brine, dried (MgSO4), filtered, and concentrated in
vacuo. Flash column chromatography (8/1 to 1/1 pentane/EtOAc) gave the methyl galactoside as an anomerically pure yellow
oil (4.31 g, 11.9 mmol, 48% over three steps). Spectroscopic data were in accord with those previously reported. 23,24 1H NMR
(CDCl3, 400 MHz, HH-COSY, HSQC): δ 5.40 (dd, 1H, J = 3.4, 1.2 Hz, H-4), 5.20 (dd, 1H, J = 10.5, 7.9 Hz, H-2), 5.03 (dd,
1H, J = 10.5, 3.4 Hz, H-3), 4.42 (d, 1H, J = 7.9 Hz, H-1), 4.25 – 4.11 (m, 2H, H-6), 3.93 (td, 1H, J = 6.7, 1.2 Hz, H-5), 3.52 (s,
13C-APT
3H, CH3 OMe), 2.16 (s, 3H, CH3 Ac), 2.07 (s, 3H, CH3 Ac), 2.06 (s, 3H, CH3 Ac), 1.99 (s, 3H, CH3 Ac); NMR
(CDCl3, 101 MHz, HSQC): δ 170.4, 170.2, 170.1, 169.5 (C=O Ac), 102.0 (C-1), 71.0 (C-3), 70.6 (C-5), 68.8 (C-2), 67.1 (C-
4), 61.3 (C-6), 57.0 (OMe), 20.8, 20.7, 20.7, 20.6 (CH3 Ac);

Methyl β-D-galactopyranoside (S14)

Acetylated S13 (4.31 g, 11.9 mmol) was dissolved in MeOH (50 mL) and NaOMe (325 mg, 6.0 mmol, 0.5 eq.) was added.
After 30 min Amberlite H+ was added until neutral pH was achieved and the resin was subsequently filtered off. The solution

S11
was concentrated in vacuo to give the crude tetra-ol. Spectroscopic data were in accord with those previously reported.25 1H
NMR (D2O, 400 MHz, HSQC): δ 4.79 (bs, 4H, OH), 4.30 (d, 1H, J = 7.9 Hz, H-1), 3.90 (d, 1H, J = 3.5 Hz, H-4), 3.81 – 3.73
(m, 2H, H-6), 3.75 – 3.64 (m, 1H, H-5), 3.63 (dd, 1H, J = 9.9, 3.5 Hz, H-3), 3.55 (s, 3H, CH3 OMe), 3.48 (dd, 1H, J = 9.9, 7.9
Hz, H-2); 13C NMR (D2O, 101 MHz, HSQC): δ 103.8 (C-1), 75.2 (C-5), 72.8 (C-3), 70.8 (C-2), 68.7 (C-4), 61.0 (C-6), 57.2
(OMe);

Methyl 4,6-O-benzylidene-β-D-galactopyranoside (S15)

Crude S14 (1.94 g, 10 mmol) and p-TsOH•H2O were dissolved in CH3CN (50 mL) and DMF (15 mL) and the poorly soluble
reaction mixture was stirred at 60°C, 350 mbar for 3 h. Et3N (0.8 mL) was added and the reaction mixture was portioned
between EtOAc and H2O. The organic layer did not contain observable product, therefore the water layer was evaporated to
give the crude product. Column chromatography (1:0 to 9/1 DCM/MeOH) gave the benzylidene protected galactoside as a
waxy solid (1.73 g, 6.1 mmol, 61%). Spectroscopic data were in accord with those previously reported. 11,19,26 1H NMR (CDCl3,
400 MHz): δ 7.55 – 7.46 (m, 2H), 7.40 – 7.34 (m, 3H), 5.55 (s, 1H), 4.36 (dd, 1H, J = 12.5, 1.5 Hz), 4.24 – 4.20 (m, 2H), 4.12
– 4.07 (m, 1H), 3.79 – 3.67 (m, 2H), 3.59 (d, 3H, J = 0.7 Hz), 3.49 (t, 1H, J = 1.6 Hz);

Methyl 2,3-di-O-benzyl-4,6-O-benzylidene-β-D-galactopyranoside (S16)

Compound S15 was coevaporated with dry toluene twice before being dissolved in DMF (30 mL). Benzyl bromide (3.2 mL,
18.4 mmol, 3 eq.) and NaH (60% dispersion in mineral oil, 736 mg, 18.4 mmol, 3 eq.) were added and the reaction mixture
was stirred overnight. H2O was added and the mixture was extracted with EtOAc twice. The organic layer was washed with
brine twice and dried (MgSO4), filtered, and concentrated in vacuo. The crude product was purified by flash column
chromatography (8/1 to 3/1 pentane/EtOAc) to afford the benzylated product (2.11 g, 4.56 mmol, 75%). Rf: 0.63 (3/2
pentane/EtOAc). Spectroscopic data were in accord with those previously reported.11 1H NMR (CDCl3, 400 MHz, HH-COSY,
HSQC): δ 7.59 – 7.53 (m, 2H, CHarom), 7.42 – 7.26 (m, 13H, CHarom), 5.50 (s, 1H, CHPh), 4.91 (d, 1H, J = 10.9 Hz, CHH Bn),
4.81 – 4.71 (m, 3H, CHH Bn, CH2 Bn), 4.36 – 4.27 (m, 2H, H-1, H-6), 4.11 (dd, 1H, J = 3.7, 1.1 Hz, H-4), 4.02 (dd, 1H, J =
12.3, 1.8 Hz, H-6), 3.84 (dd, 1H, J = 9.7, 7.7 Hz, H-2), 3.60 – 3.53 (m, 4H, H-3, CH3 OMe), 3.32 (d, 1H, J = 1.3 Hz, H-5); 13C-
APT NMR (CDCl3, 101 MHz, HSQC): δ 139.0, 138.5, 137.9 (Cq), 129.1, 128.5, 128.4, 128.2, 128.2, 127.9, 127.8, 127.6, 126.7
(CHarom), 104.8 (C-1), 101.5 (CHPh), 79.3 (C-3), 78.6 (C-2), 75.4 (CH2 Bn), 74.1 (C-4), 72.1 (CH2 Bn), 69.4 (C-6), 66.5 (C-
5), 57.2 (OMe);

S12
Methyl 2,3,6-tri-O-benzyl-β-D-galactopyranoside (13)

To a solution of S16 (2.10 g, 4.54 mmol) and NaCNBH3 (1.7 g, 27.2 mmol, 6 eq.) in THF (60 mL), 4.0 M HCl in 1,4-dioxane
(9 mL, 36 mmol, 7.9 eq.) was added. The reaction mixture was stirred for 1 h and then H 2O was added. The solution was
extracted twice with DCM and the organic layer was washed with brine, dried with MgSO4 en concentrated in vacuo. Flash
column chromatography (9/1 to 1/1 pentane/EtOAc) provided the free alcohol as an oil (1.56 g, 3.36 mmol, 74%). Rf: 0.74 (3/2
pentane/EtOAc). Spectroscopic data were in accord with those previously reported.11,27,28 1H NMR (CDCl3, 400 MHz, HH-
COSY, HSQC): δ 7.41 – 7.21 (m, 15H, CHarom), 4.88 (d, 1H, J = 11.1 Hz, CHH Bn), 4.71 (d, 1H, J = 11.0 Hz, CHH Bn), 4.67
(s, 2H, CH2 Bn), 4.56 (s, 2H, CH2 Bn), 4.26 (d, 1H, J = 7.7 Hz, H-1), 3.98 (d, 1H, J = 3.4 Hz, H-4)), 3.79 (dd, 1H, J = 9.9, 5.9
Hz, H-6), 3.72 (dd, 1H, J = 9.9, 6.0 Hz, H-6), 3.64 (dd, 1H, J = 9.4, 7.7 Hz, H-2), 3.59 – 3.50 (m, 4H, H-5, CH3 OMe), 3.46
(dd, 1H, J = 9.4, 3.4 Hz, H-3), 2.70 (s, 1H, 4-OH); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 138.6, 137.9, 137.8 (Cq),
128.4, 128.3, 128.0, 127.8, 127.8, 127.7, 127.7, 127.5 (CH arom), 104.7 (C-1), 80.5 (C-3), 79.0 (C-2), 75.1, 73.6 (CH2 Bn), 73.1
(C-5), 72.3 (CH2 Bn), 69.2 (C-6), 66.8 (C-4), 56.9 (OMe); HRMS: [M+Na]+ calcd for C28H33O6Na 487.20911, found 487.20848.

Preparation of acceptor 14

Scheme S-8: Mannose acceptor 14 synthesis. Reagents and conditions: a) PhCH(OMe)2, p-TsOH•H2O, CH3CN, S17: 80%; b)
LiAlH4, AlCl3, Et2O, DCM, 14: 96%.

Methyl 2,3-exo;4,6-di-O-benzylidene-α-D-mannopyranoside (S17)

To a solution of methyl α-D-mannoside (19.4 g, 100 mmol) in CH3CN (120 mL) was added benzylidene dimethyl acetal (36
mL, 240 mmol, 2.4 eq.) and p-TsOH•H2O (475 mg, 2.5 mmol, 0.025 eq.). The reaction mixture was stirred at 60°C and 500
mbar for 3 h and the volume was reduced by half. Sat. aq. NaHCO3 was added to quench the reaction and the precipitate
collected and washed with cold H2O. The solids were recrystallized from EtOH/EtOAc to obtain two crops of white needles
(total yield: 29.6 g, 80 mmol, 80% exo only). Spectroscopic data were in accord with those previously reported. 29 1H NMR
(CDCl3, 400 MHz, HH-COSY, HSQC): δ 7.55 – 7.51 (m, 2H, CHarom), 7.48 – 7.44 (m, 2H, CHarom), 7.41 – 7.34 (m, 6H,
CHarom), 6.30 (s, 1H, CHPh2,3 exo), 5.64 (s, 1H, CHPh4,6), 5.02 (s, 1H, H-1), 4.63 (dd, 1H, J = 7.8, 5.4 Hz, H-3), 4.40 – 4.32 (m,
1H, H-6), 4.14 (d, 1H, J = 5.4 Hz, H-2), 3.93 – 3.88 (m, 1H, H-4), 3.88 – 3.81 (m, 2H, H-5, H-6), 3.41 (s, 3H, CH3 OMe); 13C-
APT NMR (CDCl3, 101 MHz, HSQC): δ 138.7, 137.3 (Cq), 129.3, 128.5, 128.4, 126.4, 126.2 (CHarom), 103.1 (CHPh2,3 exo),
102.2 (CHPh4,6), 99.0 (C-1), 77.6 (C-4), 75.7 (C-3), 75.4 (C-2), 69.1 (C-6), 60.5 (C-5), 55.4 (OMe);

S13
Methyl 3-O-benzyl-4,6-O-benzylidene-α-D-mannopyranoside (14)

Compound S17 (5.56 g, 15 mmol) was dissolved in 100 mL DCM and 150 mL Et 2O. A solution of LiAlH4 (2.4 M in THF, 8
mL, 19.2 mmol, 1.3 eq.) was added to the reaction mixture at 0°C followed by addition of AlCl 3 (2.2 g, 16.4 mmol, 1.1 eq.).
The reaction mixture was allowed to stir for 3 h at r.t. before being quenched by careful addition of EtOAc and H2O. The
mixture was extracted with EtOAc and the organic phase was washed with brine, dried MgSO4 and concentrated under reduced
pressure. Purification of the crude product by flash column chromatography (6/1 to 1/1 pentane/EtOAc) gave the title compound
as a colorless oil (5.37 g, 14.4 mmol, 96%). Rf: 0.38 (2/1 pentane/EtOAc). Spectroscopic data were in accord with those
previously reported.29–31 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 7.53 – 7.47 (m, 2H, CHarom), 7.41 – 7.27 (m, 8H,
CHarom), 5.60 (s, 1H, CHPh), 4.84 (d, 1H, J = 11.9 Hz, CHH Bn), 4.73 (d, 1H, J = 1.4 Hz, H-1), 4.69 (d, 1H, J = 11.9 Hz, CHH
Bn), 4.27 (dd, 1H, J = 9.4, 4.0 Hz, H-6), 4.09 (t, 1H, J = 9.2 Hz, H-4), 4.01 (dt, 1H, J = 3.3, 1.6 Hz, H-2), 3.93 – 3.75 (m, 3H,
H-3, H-5, H-5), 3.35 (s, 3H, CH3 OMe), 2.82 (d, 1H, J = 1.7 Hz, 2-OH); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 138.1,
137.7 (Cq), 129.0, 128.6, 128.3, 128.0, 127.9, 126.2 (CHarom), 101.7 (CHPh), 101.2 (C-1), 78.9 (C-4), 75.7 (C-3), 73.1 (CH2
Bn), 69.9 (C-2), 69.0 (C-6), 63.3 (C-5), 55.0 (OMe); HRMS: [M+Na]+ calcd for C21H24O6Na 395.14651, found 395.14638

Glycosylations with donor 1

Cyclohexyl 2,3-di-O-benzyl-4,6-O-benzylidene-α/β-D-mannopyranoside (1A).

Donor 1 and cyclohexanol were condensed using the general procedure for Tf2O/Ph2SO mediated and purified by flash column
chromatography (1/0 to 9/1 pentane/EtOAc) to yield glycosylation product 1A (50.9 mg, 51 μmol, 96%, α:β = 1:5). Rf: 0.43
(9/1 pentane/EtOAc). Spectroscopic data were in accord with those previously reported. 32,33 IR (neat): 694, 733, 964, 1026,
1047, 1084, 1361, 1452, 2857, 2857, 2930; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.55 –
7.23 (m, 15H, CHarom), 5.61 (s, 1H, CHPh), 5.02 (d, 1H, J = 12.5 Hz, CHH Bn), 4.91 (d, 1H, J = 12.5 Hz, CHH Bn), 4.67 (d,
1H, J = 12.5 Hz, CHH Bn), 4.58 (s, 1H, H-1), 4.58 (d, 1H, J = 12.5 Hz, CHH Bn), 4.30 (dd, 1H, J = 10.4, 4.9 Hz, H-6), 4.22
(t, 1H, J = 9.6 Hz, H-4), 3.94 (t, 1H, J = 10.3 Hz, H-6), 3.87 (d, 1H, J = 3.0 Hz, H-2), 3.70 (dt, 1H, J = 8.6, 4.7 Hz, CH Cy),
3.58 (dd, 1H, J = 9.9, 3.1 Hz, H-3), 3.31 (td, 1H, J = 9.9, 4.9 Hz, H-5), 2.06 – 0.99 (m, 10H, CH2 Cy); 13C-APT NMR (101
MHz, CDCl3, HSQC): δ 138.68, 138.54, 137.79 (Cq), 129.05, 128.92, 128.85, 128.49, 128.40, 128.28, 128.22, 128.19, 127.84,
127.68, 127.62, 127.60, 127.58, 127.53, 126.18, 126.14, 125.21 (CH arom), 101.48 (CHPh), 100.12 (C-1), 78.76 (C-4), 78.25 (C-
3), 76.84 (CH Cy), 76.31 (C-2), 74.71 (CH2 Bn), 72.39 (CH2 Bn), 68.82 (C-6), 67.68 (C-5), 33.48, 31.57, 25.78, 23.87, 23.72
(CH2 Cy); 13C-GATED NMR (101 MHz, CDCl3): 100.1 (JC1,H1 = 154 Hz, C-1 β); Diagnostic peaks α-anomer: 1H NMR (400
MHz, CDCl3, HH-COSY, HSQC): δ 5.64 (s, 0.20H, CHPh), 4.89 – 4.79 (m, 0.60H, CHH Bn, CHH Bn, C-1), 4.71 (d, 0.20H,
J = 12.3 Hz, CHH Bn), 4.00 (dd, 0.20H, J = 10.0, 3.2 Hz, H-2), 3.78 (dd, 0.20H, J = 3.1, 1.6 Hz, H-3), 3.54 – 3.49 (m, 0.20H,
CH Cy); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 97.41 (C-1), 64.36 (C-5), 33.38, 31.31, 25.69, 25.25, 24.11 (CH2 Cy);
HRMS: [M+Na]+ calcd for C33H38O6Na 553.25606, found 553.25531.

S14
Ethyl 2,3-di-O-benzyl-4,6-O-benzylidene-α/β-D-mannopyranoside (1B).

Donor 1 and ethanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations and purified by
flash column chromatography (1/0 to 9/1 pentane/EtOAc) to yield glycosylation product 1B (33.5 mg, 70 μmol, 70%, α:β =
1:5). Rf: 0.43 (9/1 pentane/EtOAc). IR (neat): 696, 734, 893, 912, 968, 1004, 1049, 1088, 1373, 1452, 2866, 2926; Data for the
β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.53 – 7.28 (m, 15H, CHarom), 5.62 (s, 1H, CHPh), 4.99 (d, 1H,
J = 12.4 Hz, CHH Bn), 4.89 (d, 1H, J = 12.4 Hz, CHH Bn), 4.68 (d, 1H, J = 12.6 Hz, CHH Bn), 4.58 (d, 1H, J = 12.5 Hz, CHH
Bn), 4.46 (s, 1H, H-1), 4.31 (dd, 1H, J = 10.4, 4.9 Hz, H-6), 4.21 (t, 1H, J = 9.6 Hz, H-4), 4.02 – 3.89 (m, 3H, CHHCH3 Et, H-
2, H-6), 3.58 (dd, 1H, J = 9.9, 3.1 Hz, H-3), 3.56 – 3.47 (m, 1H, CHHCH3 Et), 3.36 – 3.28 (m, 1H, H-5), 1.27 (t, 3H, J = 7.0
Hz, CH3 Et); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 138.6, 138.5, 137.8 (Cq), 123.0, 128.9, 128.4, 128.3, 128.2, 127.7,
127.7, 127.6, 126.2, (CHarom) 102.2 (C-1), 101.5 (CHPh), 78.8 (C-4), 78.0 (C-3), 75.9 (C-2), 74.8 (CH2 Bn), 72.5 (CH2 Bn),
68.8 (C-6), 67.7 (C-5), 65.7 (CH2 Et), 15.3 (CH3 Et); 13C-GATED NMR (101 MHz, CDCl3): δ 102.2 (JC1,H1 = 153 Hz, C-1 β);
Diagnostic peaks α-anomer: 1H NMR (400 MHz, CDCl3): δ 5.65 (s, 0.20H), 4.86 – 4.81 (m, 0.40H, CHH Bn, CHH Bn), 4.80
(d, 0.20H, J = 1.5 Hz, H-1), 4.74 (d, 0.20H, J = 12.3 Hz, CHH Bn), 3.74 – 3.66 (m, 0.20H, CHHCH3), 3.46 – 3.39 (m, 0.20H,
CHHCH3 Et); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 128.9, 128.5, 128.4, 128.3, 128.2, 127.9, 127.6, 126.2 (C q), 101.6
(CHPh), 99.3 (C-1), 79.4 (C-3), 76.5 (C-4), 76.4 (C-2), 73.7 (CH2 Bn), 73.3 (CH2 Bn), 69.3 (C-6), 64.3 (C-5) 63.3 (CH2 Et),
15.1 (CH3 Et); HRMS: [M+Na]+ calcd for C29H32O6Na 499.20911, found 499.20846.

2-Fluoroethyl 2,3-di-O-benzyl-4,6-O-benzylidene-α/β-D-mannopyranoside (1C).

Donor 1 and 2-fluoroethanol were condensed using the general procedure for Tf2O/Ph2SO mediated and purified by flash
column chromatography (1/0 to 4/1 pentane/EtOAc) to yield glycosylation product 1C (42.7 mg, 86 μmol, 86%, α:β = 1:5). Rf:
0.18 (9/1 pentane/EtOAc). IR (neat): 696, 738, 802, 887, 1025, 1043, 1066, 1086, 1261, 1371, 1454, 2870; Data for the β-
anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.66 – 7.32 (m, 15H, CHarom), 5.62 (s, 1H, CHPh), 4.99 (d, 1H, J
= 12.3 Hz, CHH Bn), 4.89 (d, 1H, J = 12.3 Hz, CHH Bn), 4.70 – 4.51 (m, 5H, CHH Bn, CHH Bn, H-1, CH2CHHF, CH2CHHF),
4.30 (dd, 1H, J = 10.4, 4.8 Hz, H-6), 4.22 (t, 1H, J = 9.6 Hz, H-4), 4.08 (ddt, 1H, J = 35.7, 12.2, 3.0 Hz, CHHCH2F), 3.98 (d,
1H, J = 2.9 Hz, H-2), 3.92 (t, 1H, J = 10.3 Hz, H-6), 3.80 (dtd, 1H, J = 22.6, 11.9, 7.8, 2.4 Hz, CHHCH2F), 3.59 (dd, 1H, J =
9.9, 3.1 Hz, H-3), 3.33 (td, 1H, J = 9.7, 4.9 Hz, H-5); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 138.4, 138.4, 137.6 (Cq),
131.2, 129.4, 129.0, 128.8, 128.4, 128.3, 128.2, 127.7, 127.7, 126.2, 124.9 (CH arom), 102.3 (C-1), 101.5 (CHPh), 82.8 (d, J =
169.74 Hz, CH2F), 78.6 (C-4), 77.8 (C-3), 75.7 (C-2), 75.0 (CH2 Bn), 72.5 (CH2 Bn), 69.0 (d, J = 19.7 Hz, CH2CH2F), 67.7
(C-6). 13C-GATED NMR (101 MHz, CDCl3): δ 102.3 (JC1,H1 = 156 Hz, C-1 β); Diagnostic peaks α-anomer: 1H NMR (400
MHz, CDCl3, HH-COSY, HSQC): δ 5.62 (s, 0.20H, CHPh), 4.93 – 4.80 (m, 0.60H, CHH Bn, CHH Bn, H-1); 13C-APT NMR
(101 MHz, CDCl3, HSQC): δ 99.7 (C-1), 82.5 (d, J = 170 Hz, CH2F), 79.2 (C-4), 76.5 (C-3), 76.4 (C-2), 73.8 (CH2 Bn), 73.3
(CH2 Bn), 68.9 (C-6), 66.7 (d, J = 19.9 Hz, CH2CH2F), 64.4 (C-5); 13C-GATED NMR (101 MHz, CDCl3): δ 99.7 (JC1,H1 = 170
Hz, C-1 α); HRMS: [M+Na]+ calcd for C29H31FO6Na 517.19969, found 517.19888.

S15
2,2-Difluoroethyl 2,3-di-O-benzyl-4,6-O-benzylidene-α/β-D-mannopyranoside (1D).

Donor 1 and 2,2-difluoroethanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations and
purified by flash column chromatography (1/0 to 4/1 pentane/EtOAc) to yield glycosylation product 1D (46.1 mg, 90 μmol,
90%, α:β = 1:5). Rf: 0.50 (9/1 pentane/EtOAc). IR (neat): 694, 744, 795, 1026, 1094, 1261, 1369, 1454, 2868; Data for the β-
anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.68 – 7.27 (m, 15H, CHarom), 5.90 (dddd, 1H, J = 54.8, 5.1, 2.8,
1.5 Hz, CHF2) 5.62 (s, 1H, CHPh), 4.94 (d, 1H, J = 12.2 Hz, CHH Bn), 4.86 (d, 1H, J = 12.2 Hz, CHH Bn), 4.70 (d, 1H, J =
12.5 Hz, CHH Bn), 4.60 (d, 1H, J = 12.4 Hz, CHH Bn), 4.51 (s, 1H. H-1), 4.31 (dd, 1H, J = 10.4, 4.9 Hz, H-6), 4.22 (t, 1H, J
= 9.6 Hz, H-4), 4.05 (dtd, 1H, J = 20.7, 11.1, 2.9 Hz, CHHCHF2), 3.98 – 3.88 (m, 2H, H-2, H-6), 3.82 – 3.65 (m, 1H, CHHCHF2),
3.59 (dd, 1H, J = 9.9, 3.1 Hz, H-3), 3.33 (td, 1H, J = 9.7, 4.8 Hz, H-5); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 138.3,
138.2, 137.5 (Cq), 128.8, 128.5, 128.3, 127.7, 126.2 (Carom), 115.4 (t, J = 241.9, CHF2), 102.3 (C-1), 101.6 (CHPh), 78.6 (C-4),
77.8 (C-3), 75.5 (C-2), 75.1 (CH2 Bn), 72.6 (CH2 Bn), 68.5 (t, J = 33.0 Hz, CH2CHF2), 68.5 (C-6), 67.8 (C-5); 13C-GATED
NMR (101 MHz, CDCl3): 102.3 (JC1,H1 = 156 Hz, C-1 β); Diagnostic peaks α-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY,
HSQC): δ 5.98 (dt, 0.03 H, J = 5.7, 4.1 Hz, CHF2), 5.84 (dt, 0.10H, J = 5.9, 4.1 Hz, CHF2), 5.70 (dt, 0.03H, J = 6.1, 4.1 Hz,
CHF2), 4.84 (m, 0.34H, C-1, CHH Bn), 4.72 (d, 0.17H, J = 12.1 Hz, CHH Bn), 4.66 (d, 0.17H, J = 12.2 Hz, CHH Bn); 13C-
APT NMR (101 MHz, CDCl3, HSQC): δ 115.4 (t, J = 240.10, CHF2), 101.6 (CHPh), 100.1 (C-1), 79.0 (C-4), 76.3 (C-3), 76.2
(C-2), 73.9 (CH2 Bn), 73.4 (CH2 Bn), 68.5 (C-6), 64.8 (C-5); HRMS: [M+Na]+ calcd for C29H30F2O6Na 535.19027, found
535.18950.

2,2,2-Trifluoroethyl 2,3-di-O-benzyl-4,6-O-benzylidene-α/β-D-mannopyranoside (1E).

Donor 1 and 2,2,2-trifluoroethanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations and
purified by flash column chromatography (1/0 to 9/1 pentane/EtOAc) to yield glycosylation product 1E (41.7 mg, 79 μmol,
79%, α:β = 1:3.4). Rf: 0.60 (9/1 pentane/EtOAc). IR (neat): 696, 737, 1028, 1057, 1085, 1161, 1277, 1454, 2870; Data for the
β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.50 – 7.28 (m, 15H, CHarom) 5.62 (s, 1H, CHPh), 4.96 (d, 1H,
J = 12.2 Hz, CHH Bn), 4.87 (d, 1H, J = 12.1 Hz, CHH Bn), 4.69 (d, 1H, J = 12.5 Hz, CHH Bn), 4.59 (d, 1H, J = 12.5 Hz, CHH
Bn), 4.57 (s, 1H, H-1), 4.31 (dd, 1H, J = 10.4, 4.9 Hz, C-6), 4.28 – 4.17 (m, 2H, C-4, CHHCF3), 4.01 – 3.86 (m, 3H, H-2, H-6,
CHHCF3), 3.59 (dd, 1H, J = 9.9, 3.1 Hz, H-3), 3.34 (td, 1H, J = 9.8, 4.9 Hz, H-5); 13C-APT NMR (101 MHz, CDCl3, HSQC):
δ 138.2, 138.0, 137.5 (Cq), 129.1, 128.9, 128.5, 128.3, 127.9, 127.8, 127.7, 126.2 (C arom), 123.7 (q, J = 277.6 Hz, CF3) 101.9
(C-1), 101.6 (CHPh), 78.4 (C-4), 77.7 (C-3), 77.5 (C-2), 75.1 (CH2 Bn), 75.0 (CH2 Bn), 72.6 (C-6), 68.4 (C-5), 66.2 (q, J =
34.9 Hz, CH2CF3); 13C-GATED NMR (101 MHz, CDCl3): 101.9 (JC1,H1 = 157 Hz, C-1 β); Diagnostic peaks α-anomer: 1H
NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 5.64 (s, 0.29H, CHPh), 4.88 – 4.82 (m, 0.87H, CHH Bn, CHH Bn, H-1), 4.73
– 4.64 (m, 0.58H, CHH Bn, CHH Bn); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 101.6 (CHPh), 100.1 (C-1), 78.9 (C-4),
76.2 (C-3), 76.0 (C-2), 74.1 (CH2 Bn), 73.5 (CH2 Bn), 68.7 (C-6), 65.0 (C-5); HRMS: [M+Na]+ calcd for C29H29F3O6Na
553.18084, found 553.18021.

S16
1,1,1,3,3,3-Hexafluoro-2-propyl 2,3-di-O-benzyl-4,6-O-benzylidene-α/β-D-mannopyranoside (1F).

Donor 1 and 1,1,1,3,3,3-hexafluoro-2-propanol were condensed using the general procedure for Tf2O/Ph2SO mediated
glycosylations (for an additional 120 hours at -40°C) and purified by flash column chromatography (1/0 to 9/1 pentane/EtOAc)
to yield glycosylation product 1F (33.6 mg, 34 μmol, 56%, α:β = 3.3:1). Rf: 0.81 (8/2 pentane/EtOAc). IR (neat): 694, 898,
977, 1058, 1091, 1195, 1217, 1287, 136, 2924; Data for the α-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.54
– 7.27 (m, 15H, CHarom), 5.64 (s, 1H, CHPh), 4.95 (s, 1H, H-1), 4.86 (d, 1H, J = 5.5 Hz, CHH Bn), 4.82 (d, 1H, J = 8.9 Hz,
CHH Bn), 4.69 (d, 1H, J = 2.8 Hz, CHH Bn), 4.65 (d, 1H, J = 7.7 Hz, CHH Bn), 4.38 – 4.19 (m, 3H, H-3, H-6, CH(CF3)2),
3.92 (d, 1H, J = 4.9 Hz, H-4), 3.89 – 3.83 (m, 2H, H-6, H-5); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 138.5, 137.5, 137.4
(Cq), 129.1, 128.7, 128.5, 128.4, 128.3, 127.8, 127.7, 126.1 (CHarom), 121.6 (q, J = 282.7 Hz, CF3), 101.8 (C-1), 101.6 (CHPh),
78.4 (C-3), 76.1 (C-4), 75.5 (C-2), 74.3 (CH2 Bn), 73.8 (CH2 Bn), 72.4 (hept, J = 32.7 Hz, CH(CF3)2), 72.1 (CH2 Bn), 68.3 (C-
6), 65.8 (C-5);13C-GATED NMR (101 MHz, CDCl3): δ 101.8 (JC1,H1 = 175 Hz, C-1 α); Diagnostic peaks β-anomer: 1H NMR
(400 MHz, CDCl3, HH-COSY, HSQC, HMBC): δ 5.61 (s, 0.30H, CHPh), 4.82 (d, 0.60H, J = 11.9 Hz, CHH Bn), 4.79 (s, 0.30H,
H-1,), 4.69 (d, 0.30H, J = 12.9 Hz, CHH Bn), 4.02 (d, 0.30H, J = 2.9 Hz, H-2), 3.61 (dd, 0.30H, J = 9.9, 3.1 Hz, H-3), 3.36 (td,
0.30H, J = 9.9, 4.9 Hz, H-5); 13C-APT NMR (101 MHz, CDCl3, HSQC, HMBC): δ 101.3 (C-1), 72.6 (C-6), 68.2 (C-5); 13C
HMBC-GATED NMR (101 MHz, CDCl3): δ 101.3 (JC1,H1 = 159 Hz, C-1 β); HRMS: [M+Na]+ calcd for C30H28F6O6Na
621.16823, found 621.16790.

1-[2H]-1,5-anhydro-2,3-di-O-benzyl-4,6-O-benzylidene-α-D-mannitol (1G)

Donor 1 and triethylsilane-D were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 24 hours at -40°C) and purified by flash column chromatography (19/1 to 3/1 pentane/Et 2O) to yield glycosylation
product 42 (25.8 mg, 60 μmol, 60%, α:β = < 1:20). Rf: 0.2 (4/1 pentane/Et2O). Spectroscopic data of the non-dueterated
mannitol were in accord with those previously reported.34 [𝛼]22
𝐷 = -27.2° (c = 0.5, CHCl3); IR (neat): 694, 733, 1092, 1119,

1452, 2349, 2866; Data for the β-anomer: 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 7.54 – 7.48 (m, 2H, CHarom),
7.44 – 7.26 (m, 13H, CHarom), 5.65 (s, 1H, CHPh), 4.82 (d, 1H, J = 12.6 Hz, CHH Bn), 4.81 (d, 1H, J = 12.5 Hz, CHH Bn),
4.76 (d, 1H, J = 12.5 Hz, CHH Bn), 4.68 (d, 1H, J = 12.4 Hz, CHH Bn), 4.28 (dd, 1H, J = 11.2, 4.1 Hz, H-6), 4.25 (t, 1H, J =
10.1 Hz, H-4), 3.85 (t, 1H, J = 10.3 Hz, H-6), 3.79 (d, 1H, J = 3.3 Hz, H-2), 3.68 (dd, 1H, J = 9.8, 3.3 Hz, H-3), 3.42 (s, 1H,
H-1), 3.34 (td, 1H, J = 9.7, 4.9 Hz, H-5); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 138.6, 138.3, 137.8 (Cq), 128.9, 128.5,
128.4, 128.3, 128.2, 127.9, 127.7, 127.7, 126.1 (CHarom), 101.5 (CHPh), 79.4 (C-4), 78.6 (C-3), 74.4 (C-2), 72.7 (CH2 Bn), 72.5
(C-5), 72.4 (CH2 Bn), 68.8 (t, J = 22 Hz, C-1), 68.7 (C-6); 2H NMR (CHCl3, 77 MHz): δ 4.08 (D-1); HRMS: [M+H]+ calcd for
C27H28DO5 434.20723, found 434.20691.

Allyl 2,3-di-O-benzyl-4,6-O-benzylidene-1-deoxy-β-D-mannopyranose (1H).

S17
Donor 1 and allyl trimethylsilane were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 96 hours at -40°C) and purified by flash column chromatography (1/0 to 9/1 pentane/EtOAc) to yield glycosylation
product 1H (20.7 mg, 44 μmol, 44%, α:β = < 1:20). Rf: 0.80 (9/1 pentane/EtOAc). Spectroscopic data were in accord with those
previously reported.35 [𝛼]26
𝐷 = -19.6° (c = 0.5, CHCl3); IR (neat): 696, 1028, 1097, 1454, 2860, 2924; Data for the β-anomer:
1H NMR (400 MHz, CDCl3, HH-COSY, HSQC, NOESY): δ 7.52 – 7.26 (m, 15H, CHarom), 5.76 – 5.59 (m, 1H, CHCH2 allyl),
5.64 (s, 1H, CHPh), 5.11 – 4.98 (m, 3H, CHH Bn, CHCH2 allyl), 4.92 (d, 1H, J = 12.3 Hz, CHH Bn), 4.76 (d, 1H, J = 12.3 Hz,
CHH Bn), 4.69 (d, 1H, J = 11.4 Hz, CHH Bn), 4.35 – 4.16 (m, 2H, H-4, H-6), 3.84 (t, 1H, J = 10.3 Hz, H-6), 3.80 (d, 1H, J =
2.2 Hz, H-2), 3.73 (dd, 1H, J = 9.8, 2.9 Hz, H-3), 3.45 (t, 1H, J = 6.8 Hz, H-1), 3.38 (td, 1H, J = 9.8, 4.9 Hz, H-5), 2.46 (dt,
1H, J = 13.5, 6.7 Hz, CHHCH allylic), 2.25 (dt, 1H, J = 14.3, 7.2 Hz, CHHCH allylic); 13C-APT NMR (101 MHz, CDCl3,
HSQC, HMBC): δ 138.8, 138.6, 137.9 (Cq), 134.4 (CHCH2 allyl), 128.9, 128.6, 128.5, 128.4, 128.3, 127.8, 127.7, 127.7, 126.2
(CHarom), 117.6 (CHCH2 allyl), 101.5 (CHPh), 80.9 (C-3), 79.8 (C-1), 79.7 (C-4), 76.6 (C-2), 75.1 (CH2 Bn), 73.3 (CH2 Bn),
72.1 (C-5), 68.8 (C-6), 35.6 (CH2CH allylic); HRMS: [M+H]+ calcd for C30H33O5 473.23225, found 473.23219.

Methyl 6-O-(2,3-di-O-benzyl-4,6-O-benzylidene-α/β-D-mannopyranosyl)-2,3,4-tri-O-benzyl-α-D-glucopyranoside (20).

Donor 1 and acceptor 10 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 20 (86.6mg, 97 μmol, 97%, α:β = 1:10). Rf: 0.67 (7/3 pentane/EtOAc). Spectroscopic data were in accord with those
previously reported.32,36,37 [𝛼]26 26 36 20
𝐷 +5.2° (c = 1, CHCl3, 546 nm), [𝛼]𝐷 0.0° (c = 1, CHCl3, 589 nm), (lit: [𝛼]𝐷 = -1.7° (c = 1.8,

CHCl3), lit:32 [𝛼]27

𝐷 = -5.8° (c = 0.94, CHCl3)); IR (neat): 731, 1026, 1049, 1084, 1452, 2872; Data for the β-anomer: H NMR
1

(400 MHz, CDCl3, HH-COSY, HSQC): δ 7.58 – 7.05 (m, 30H, CHarom), 5.59 (s, 1H, CHPh), 5.03 (d, 1H, J = 10.9 Hz, CHH
Bn), 4.92 (d, 1H, J = 12.3 Hz, CHH Bn), 4.86 – 4.76 (m, 4H, CHH Bn, CHH Bn, CHH Bn, CHH Bn), 4.72 (d, 1H, J = 12.5
Hz, CHH Bn), 4.67 (d, 1H, J = 12.2 Hz, CHH Bn), 4.61 (d, 1H, J = 12.6 Hz, CHH Bn), 4.58 (d, 1H, J = 3.5 Hz, H-1), 4.50 (d,
1H, J = 11.6 Hz, CHH Bn), 4.25 (dd, 1H, J = 10.4, 4.8 Hz, H-6’), 4.18 (t, 1H, J = 9.6 Hz, H-4’), 4.08 (m, 2H, H-1’, H-6), 4.02
(t, 1H, J = 9.3 Hz, H-4), 3.91 (t, 1H, J = 10.3 Hz, H-6’), 3.80 – 3.72 (m, 1H, H-2), 3.69 (d, 1H, J = 2.9 Hz, H-2’), 3.47 (m, 4H,
H-3, H-3’, H-5, H-6), 3.33 (s, 3H, CH3 OMe), 3.22 (td, 1H, J = 9.8, 4.8 Hz, H-5’); 13C-APT NMR (101 MHz, CDCl3): δ 138.9,
138.5, 138.5, 138.5, 138.1, 137.7 (Cq), 129.0, 128.7, 128.6, 128.5, 128.5, 128.5, 128.3, 128.3, 128.2, 128.1, 128.1, 127.8, 127.8,
127.7, 126.1 (CHarom), 102.1 (H-1’), 101.5 (CHPh), 97.9 (C-1), 82.3 (C-4), 79.9 (C-3), 78.8 (C-4), 77.9 (C-3’), 76.8 (C-5), 75.8
(CH2 Bn), 75.7 (C-2’), 74.8 (CH2 Bn), 74.6 (CH2 Bn), 73.5 (CH2 Bn), 72.6 (CH2 Bn), 69.7 (C-2), 68.7 (C-6’), 68.3 (C-6), 67.7
(C-5’), 55.2 (CH3 OMe); HRMS: [M+Na]+ calcd for C55H58O11Na 917.38713, found 917.38729.

Methyl 4-O-(2,3-di-O-benzyl-4,6-O-benzylidene-α/β-D-mannopyranosyl)-2,3,6-tri-O-benzyl-α-D-glucopyranoside (21).

S18
Donor 1 and acceptor 11 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 21 (67.4 mg, 75 μmol, 75%, α:β = 1:9). Rf: 0.67 (7/3 pentane/EtOAc). Spectroscopic data were in accord with those

𝐷 15.8° (c = 1, CHCl3), (lit: [𝛼]𝐷 = –15.5° (c = 0.8, CHCl3)); IR (neat): 735, 1028, 1083,
previously reported.32,36–38 [𝛼]26 38 25

1452, 2862; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.46 – 7.21 (m, 25H, CHarom), 5.51 (s,
1H, CHPh), 5.05 (d, 1H, J = 10.6 Hz, CHH Bn), 4.84 – 4.70 (m, 5H, CHH Bn, CHH Bn, CHH Bn, CHH Bn, CHH Bn), 4.70 –
4.52 (m, 4H, CHH Bn, CHH Bn, CHH Bn, H-1), 4.36 (s, 1H, H-1’), 4.28 (d, 1H, J = 12.1 Hz, CHH Bn), 4.12 – 4.01 (m, 2H,
H-4’, H-6), 3.94 – 3.81 (m, 2H, H-3, H-4), 3.63 (d, 1H, J = 2.9 Hz, H-2’), 3.62 – 3.47 (m, 4H, H-5, H-2, H-6, H-6’, H-6’), 3.47,
3.40 (s, 3H, CH3 OMe), 3.32 (dd, 1H, J = 9.8, 3.0 Hz, H-3’), 3.05 (td, 1H, J = 9.7, 4.8 Hz, H-5’); 13C-APT NMR (101 MHz,
CDCl3, HSQC): δ 139.5, 138.8, 138.7, 138.4, 137.8, 137.6 (C q), 128.9, 128.7, 128.6, 128.5, 128.5, 128.4, 128.3, 128.2, 128.1,
127.9, 127.8, 127.6, 127.6, 127.4, 127.3, 126.2 (CHarom), 101.7 (C-1’), 101.4 (CHPh), 98.5 (C-1), 80.4 (C-4), 79.1 (C-2), 78.8
(C-4’), 78.4 (C-3’), 77.8 (C-3), 77.1 (C-2), 75.4 (CH2 Bn), 75.1 (CH2 Bn), 73.8 (CH2 Bn), 73.7 (CH2 Bn), 72.6 (CH2 Bn), 69.7
(C-5), 68.7 (C-6), 68.4 (C-6’), 67.4 (C-5), 55.5 (CH3 OMe); 13C-GATED NMR (101 MHz, CDCl3): 101.7 (JC1,H1 = 156 Hz, C-
1 β); Diagnostic peaks α-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 5.60 (s, 0.11H, CHPh), 5.30 (d, 0.11H, J
= 1.3 Hz, C-1’); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 101.5 (C-1’), 101.4 (CHPh); HRMS: [M+Na] + calcd for
C55H58O11Na 917.38713, found 917.38706.

Methyl (methyl [4-O-(2,3-di-O-benzyl-4,6-O-benzylidene-α/β-D-mannopyranosyl]-2,3-di-O-benzyl-α-D-glucopyranosyl

uronate) (22).

Donor 1 and acceptor 12 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 48 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 22 (72.8 mg, 87 μmol, 87%, α:β = 1:10). Rf: 0.65 (7/3 pentane/EtOAc); [𝛼]26
𝐷 = -19.2° (c = 1, CHCl3); IR (neat): 735,

1045, 1084, 1454, 1748, 2866; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.55 – 7.24 (m, 25H,
CHarom), 5.54 (s, 1H, CHPh), 5.06 (d, 1H, J = 10.6 Hz, CHH Bn), 4.88 – 4.71 (m, 5H, CHH Bn, CHH Bn, CHH Bn, CHHBn,
CHH Bn), 4.67 – 4.53 (m, 4H, CHH Bn, CHH Bn, H-1), 4.45 (s, 1H, H-1), 4.17 – 4.01 (m, 3H, H-4, H-4’, H-6’), 3.95 – 3.85
(m, 2H, H-3, H-5), 3.82 – 3.75 (m, 1H, H-2’), 3.65 – 3.55 (m, 4H, H-6’, CH3 CO2Me), 3.55 – 3.47 (m, 2H, H-2, H-3’), 3.44 (s,
3H, CH3 OMe), 3.19 (td, 1H, J = 9.6, 4.8 Hz, H-5’); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 170.2 (C=O CO2Me), 139.2,
138.7, 138.5, 138.1, 137.7 (Cq), 128.6, 128.5, 128.4, 128.3, 128.2, 128.2, 128.1, 127.7, 127.7, 127.6, 127.4, 126.2 (CH arom),
102.5 (H-1’), 101.5 (CHPh), 98.9 (C-1), 80.2 (C-3/C-5), 79.8 (C-3/C-5), 78.7 (C-4’), 78.5 (H-2, H-3’), 77.9 (C-2’), 77.2 (CH2
Bn), 75.6 (CH2 Bn), 75.2 (CH2 Bn), 74.0 (CH2 Bn), 72.7 (CH2 Bn), 69.7 (C-6), 68.6 (C-6’), 67.7 (C-5’), 56.0 (CH3 CO2Me) ,
52.5 (CH3 OMe); 13C-GATED NMR (101 MHz, CDCl3): δ 102.5 (JC1,H1 = 157 Hz, C-1 β); Diagnostic peaks α-anomer: 1H
NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 5.58 (s, 0.10H, CHPh), 5.27 (s, 0.10H, H-1’), 4.98 (d, 0.10H, J = 11.4 Hz,
CHH Bn), 4.31 (d, 0.10H, J = 11.9 Hz, CHH Bn); 13C-APT NMR (101 MHz, CDCl3): δ 101.54 (CHPh), 100.45 (C-1’), 98.63
(C-1); HRMS: [M+Na]+ calcd for C49H52O12Na 855.33510, found 855.33507.

S19
Methyl 4-O-(2,3-di-O-benzyl-4,6-O-benzylidene-β-D-mannopyranosyl)-2,3,6-tri-O-benzyl-β-D-galactopyranoside (23).

Donor 1 and acceptor 13 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 23 (62.7 mg, 70 μmol, 70%, α:β = < 1:20). Rf: 0.80 (7/3 pentane/EtOAc); [𝛼]26
𝐷 = -26.8° (c = 1, CHCl3); IR (neat): 737,

1072, 1454, 2866; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.46 – 7.14 (m, 30H, CHarom),
5.59 (s, 1H, CHPh), 4.96 (d, 1H, J = 12.4 Hz, CHH Bn), 4.91 (d, 1H, J = 11.0 Hz, CHH Bn), 4.86 (d, 1H, J = 12.4 Hz, CHH
Bn), 4.79 (s, 1H, H-1’), 4.78 (d, 1H, J = 11.6 Hz, CHH Bn), 4.68 (d, 1H, J = 11.0 Hz, CHH Bn), 4.62 – 4.47 (m, 5H, CHH Bn,
CHH Bn, CHH Bn, CHH Bn, CHH Bn), 4.31 (d, 1H, J = 7.7 Hz, H-1), 4.21 – 4.09 (m, 3H, H-4’, H-6’), 4.01 (d, 1H, J = 3.0
Hz, H-2’), 3.90 – 3.81 (m, 2H, H-6, H-6’), 3.72 (dd, 1H, J = 9.8, 5.7 Hz, H-6), 3.67 (dd, 1H, J = 9.6, 7.7 Hz, H-2), 3.63 – 3.55
(m, 4H, H-5, CH3 OMe), 3.52 (dd, 1H, J = 9.6, 3.0 Hz, H-3), 3.40 (dd, 1H, J = 9.9, 3.1 Hz, H-3’), 3.18 (td, 1H, J = 9.8, 4.9 Hz,
H-5); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 138.9, 138.8, 138.5, 138.4, 138.2, 137.6 (C q), 129.0, 128.7, 128.7, 128.5,
128.4, 128.4, 128.3, 128.3, 128.2, 128.0, 127.8, 127.7, 127.6, 127.6, 127.5, 126.1 (CH arom), 105.1 (C-1), 102.6 (C-1’), 101.4
(CHPh), 81.8 (H-3), 79.5 (H-2), 78.5 (C-3’), 78.5 (C-4’), 75.4 (C-2’), 75.1 (CH2 Bn), 74.7 (CH2 Bn), 73.7 (CH2 Bn), 73.6 (H-
5), 73.6 (CH2 Bn), 73.3 (C-4), 72.2(CH2 Bn), 69.5 (C-6), 68.7 (C-6’), 67.8 (C-5), 57.2 (CH3 OMe); 13C-GATED NMR (101
MHz, CDCl3): δ 102.6 (JC1,H1 = 159 Hz, C-1 β); HRMS: [M+Na]+ calcd for C55H58O11Na 917.38713, found 917.38696.

Methyl 2-O-(2,3-di-O-benzyl-4,6-O-benzylidene-β-D-mannopyranosyl)-3-O-benzyl-4,6-O-benzylidene-α-D-
mannopyranoside (24).

Donor 1 and acceptor 14 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 24 (70.2 mg, 87 μmol, 87%, α:β = < 1:20). Rf: 0.68 (7/3 pentane/EtOAc). Spectroscopic data were in accord with those

𝐷 44.4° (c = 1, CHCl3); (lit: [𝛼]𝐷 = –44.2° (c = 4.2, CHCl3), lit: [𝛼]𝐷 = –44.8° (c = 3.9,
previously reported.36–39 [𝛼]26 38 25 39 20

CHCl3)); IR (neat): 733, 1002, 1028, 1055, 1083, 1452, 2862; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY,
HSQC): δ 7.53 – 7.16 (m, 25H, CHarom), 5.60 (s, 1H, CHPh), 5.51 (s, 1H, CHPh), 5.06 (d, 1H, J = 12.3 Hz, CHH Bn), 4.97 (d,
1H, J = 12.3 Hz, CHH Bn), 4.81 – 4.56 (m, 6H, CHH Bn, CHH Bn, CHH Bn, CHH Bn, H-1, H-1’), 4.30 – 4.18 (m, 4H, H-2,
H-4´, H-6, H-6’), 4.10 (t, 1H, J = 9.2 Hz, H-4), 3.98 (d, 1H, J = 2.8 Hz, H-2’), 3.94 (dd, 1H, J = 10.0, 3.2 Hz, H-3) 3.88 (t, 1H,
J = 10.3 Hz, H-6’), 3.78 (m, 2H, H-5, H-6), 3.59 (dd, 1H, J = 9.9, 3.0 Hz, H-3’), 3.46 – 3.21 (m, 4H, H-5’, CH3 OMe); 13C-
APT NMR (101 MHz, CDCl3, HSQC): δ δ 139.0, 138.7, 138.5, 137.7, 137.7 (C q), 129.0, 128.7, 128.4, 128.3, 128.3, 128.2,
127.7, 127.6, 127.6, 127.4, 126.2, 126.2 (CHarom), 101.7 (CHPh), 101.5 (CHPh), 101.0 (C-1’), 99.6 (C-1), 78.8 (C-4), 78.6 (H-
4’), 77.8 (C-3’), 76.1 (C-2’), 75.3 (H-2), 74.7 (H-3), 74.2 (CH2 Bn), 72.4 (CH2 Bn), 71.5 (CH2 Bn), 69.1 (C-6), 68.7 (C-6’),
67.9 (C-5’), 64.2 (C-5), 55.1 (CH3 OMe); 13C-GATED NMR (101 MHz, CDCl3): δ 101.0 (JC1,H1 = 154 Hz, C-1’ β); HRMS:
[M+Na]+ calcd for C48H50O11Na 825.32453, found 825.32425.

S20
Glycosylations with donor 2.

Cyclohexyl 2,3-di-O-benzyl-4,6-O-benzylidene- α/β-D-glucopyranoside (2A)

Donor 2 and cyclohexanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations and purified
by flash column chromatography (1/0 to 0/1 pentane/toluene to 6% EtOAc in toluene) to yield glycosylation product 2A (37.8
mg, 71 µmol, 71%, α:β = 1:5). Rf: 0.22 (toluene). Spectroscopic data were in accord with those previously reported. 40 IR (neat):
696, 735, 746, 997, 1028, 1049, 1072, 1366, 1452, 1497, 2857, 2930; Data for the β-anomer:1H NMR (CDCl3, 400 MHz, HH-
COSY, HSQC): δ 7.51 – 7.46 (m, 2H, CHarom), 7.41 – 7.24 (m, 13H, CHarom), 5.56 (s, 1H, CHPh), 4.94 (d, 1H, J = 10.8 Hz,
CHH Bn), 4.90 (d, 1H, J = 11.1 Hz, CHH Bn), 4.79 (d, 1H, J = 11.5 Hz, CHH Bn), 4.76 (d, 1H, J = 10.9 Hz, CHH Bn), 4.62
(d, 1H, J = 7.7 Hz, H-1), 4.33 (dd, 1H, J = 10.5, 5.0 Hz, H-6), 3.79 (t, 1H, J = 10.3 Hz, H-6), 3.76 – 3.65 (m, 3H, CH Cy, H-3,
H-4), 3.46 (t, 1H, J = 8.1 Hz, H-2), 3.39 (td, 1H, J = 9.5, 5.0 Hz, H-5), 2.00 – 1.91 (m, 2H, CH2 Cy), 1.82 – 1.72 (m, 2H, CH2
Cy), 1.59 – 1.18 (m, 6H, CH2 Cy); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 138.7, 138.6, 137.5 (Cq), 129.0, 128.4, 128.4,
128.3, 128.3, 128.1, 127.8, 127.7, 126.1 (CHarom), 102.5 (C-1), 101.2 (CHPh), 82.3 (C-2), 81.6, 81.2 (C-3, C-4), 78.3 (CH Cy),
75.5, 75.2 (CH2 Bn), 69.0 (C-6), 66.1 (C-5), 33.9, 32.1, 25.7, 24.2, 24.1 (CH2 Cy); Diagnostic peaks α-anomer: 1H NMR
(CDCl3, 400 MHz, HH-COSY, HSQC): δ 4.69 (d, 1H, J = 12.1 Hz, CHH Bn), 4.26 (dd, 1H, J = 10.2, 4.9 Hz, H-6), 4.07 (t,
1H, J = 9.3 Hz, H-3), 3.96 (td, 1H, J = 10.0, 4.9 Hz, H-5), 3.61 (t, 1H, J = 9.4 Hz, H-4), 3.58 – 3.50 (m, 2H, CH Cy, H-2); 13C-
APT NMR (CDCl3, 101 MHz, HSQC): δ 101.3 (CHPh), 96.1 (C-1), 82.5 (C-4), 79.5 (C-2) 78.8 (C-3), 76.1 (CH Cy), 75.4,
73.4 (CH2 Bn), 69.2 (C-6), 62.6 (C-5); HRMS: [M+H]+ calcd for C33H39O6 531.27412, found 531.27400.

Ethyl 2,3-di-O-benzyl-4,6-O-benzylidene-α/β-D-glucopyranoside (2B)

Donor 2 and ethanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations and purified by
flash column chromatography (1/1 to 0/1 pentane/toluene to 6% EtOAc in toluene) to yield glycosylation product 2B (32.2 mg,
68 µmol, 68%, α:β = 1:10). Rf: 0.43 (6% EtOAc in toluene). IR (neat): 692, 743, 1006, 1028, 1183, 1364, 1453, 2872; Data for
the β-anomer: 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 7.52 – 7.46 (m, 2H, CHarom), 7.41 – 7.24 (m, 13H, CHarom),
5.56 (s, 1H, CHPh), 4.93 – 4.88 (m, 2H, 2xCHH Bn), 4.83 – 4.74 (m, 2H, 2xCHH Bn), 4.51 (d, 1H, J = 7.7 Hz, H-1), 4.34 (dd,
1H, J = 10.5, 5.0 Hz, H-6), 3.97 (dq, 1H, J = 9.6, 7.1 Hz, CHH Et), 3.79 (t, 1H, J = 9.5 Hz, H-6), 3.76 – 3.63 (m, 3H, H-3, H-
4, CHH Et), 3.46 (t, 1H, J = 8.1 Hz, H-2), 3.40 (ddd, 1H, J = 10.0, 9.0, 5.0 Hz, H-5), 1.29 (t, 3H, J = 7.0 Hz, CH3 Et); 13C-APT
NMR (CDCl3, 101 MHz, HSQC): δ 138.7, 138.6, 137.5 (Cq), 129.0, 128.5, 128.4, 128.4, 128.2, 128.1, 127.8, 127.7, 126.1
(CHarom), 104.1 (C-1), 101.3 (CHPh), 82.3 (C-2), 81.7 (C-4), 81.0 (C-3), 75.5, 75.2 (CH2 Bn), 69.0 (C-6), 66.2 (CH2 Et), 66.2
(C-5), 15.5 (CH3 Et); Diagnostic peaks α-anomer: 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 5.55 (s, 1H, CHPh), 4.92
(d, 1H, J = 11.2 Hz, CHH Bn), 4.86 – 4.83 (m, 2H, CHH Bn, CHH Bn), 4.73 (d, 1H, J = 3.8 Hz, H-1), 4.68 (d, 1H, J = 12.2
Hz, CHH Bn), 4.25 (dd, 1H, J = 10.2, 4.8 Hz, H-6), 4.06 (t, 1H, J = 9.3 Hz, H-3), 3.88 (td, 1H, J = 10.0, 4.8 Hz, H-5), 3.63 –
3.60 (m, 1H, H-4), 3.59 – 3.52 (m, 2H, H-2, CHH Et); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 101.3 (CHPh), 97.9 (C-
1), 82.4 (C-4), 79.5 (C-2), 78.8 (C-3), 73.7 (CH2 Bn), 69.2 (C-6), 63.8 (CH2 Et), 62.5 (C-5); HRMS: [M+H]+ calcd for C29H33O6
477.22717, found 477.22699.

S21
2-Fluoroethyl 2,3-di-O-benzyl-4,6-O-benzylidene-α/β-D-glucopyranoside (2C)

Donor 2 and 2-fluoroethanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations and purified
by flash column chromatography (1/1 to 0/1 pentane/toluene to 6% EtOAc in toluene) to yield glycosylation product 2C (34.7
mg, 70 µmol, 70%, α:β = 1:3). Rf: 0.30 and 0.34 (4% EtOAc in toluene). IR (neat): 695, 744, 1000, 1028, 1072, 1085, 1177,
1452, 2868. Reported as a 0.33 : 1.00 mixture of anomers: 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 7.52 – 7.44 (m,
2.66H, CHarom), 7.42 – 7.24 (m, 17.29H, CHarom), 5.56 (s, 1H, CHPhβ), 5.55 (s, 0.33H, CHPhα), 4.92 (dd, 2.33H, J = 11.1, 3.4
Hz, 2xCHH Bnβ, CHH Bnα), 4.87 – 4.73 (m, 2.99H, 2xCHH Bnβ, CHH Bnα, CHH Bnα, H-1α), 4.72 – 4.60 (m, 1.66H, CHH
Bnα, CHH-CH2Fα, CHH-CH2Fβ), 4.59 – 4.49 (m, 2.33H, CHH-CH2Fα, CHH-CH2Fβ, H-1β), 4.34 (dd, 1H, J = 10.5, 5.0 Hz, H-
6β), 4.26 (dd, 0.33H, J = 10.2, 4.9 Hz, H-6α), 4.13 (ddd, 0.50H, J = 12.1, 4.7, 2.6 Hz, CHHFβ), 4.10 – 4.02 (m, 0.83H, CHHFβ,
H-3α), 3.94 – 3.66 (m, 5.32H, CHHFβ, CH2Fα, H-3β, H-4β, H-5α, H-6α, H-6β), 3.61 (t, 0.33H, J = 9.4 Hz, H-4α), 3.58 (dd, 0.33H,
J = 9.3, 3.8 Hz, H-2α), 3.50 (t, 1H, J = 8.1 Hz, H-2β), 3.41 (ddd, 1H, J = 10.0, 9.0, 5.0 Hz, H-5β); 13C-APT NMR (CDCl3, 101
MHz, HSQC): δ 138.9, 138.6, 138.4, 138.3, 137.5, 137.4 (C q), 129.1, 129.0, 128.6, 128.5, 128.4, 128.4, 128.3, 128.2, 128.1,
128.1, 128.0, 127.7, 126.1 (CHarom), 104.4 (C-1β, 101.4 (CHPhα), 101.3 (CHPhβ), 98.4 (C-1α), 82.7 (d, J = 170.2 Hz, CH2Fα),
82.6 (d, J = 170.2 Hz, CH2Fβ), 82.2 (C-4α), 82.1 (C-2β), 81.5 (C-4β), 80.9 (C-3β), 79.4 (C-2α), 78.6 (C-3α), 75.5 (CH2 Bnα,β),
75.2 (CH2 Bnβ), 73.7 (CH2 Bnα), 69.4 (d, J = 20.0 Hz, CH2-CH2Fβ), 69.1 (C-6α), 68.8 (C-6), 67.3 (d, J = 20.2 Hz, CH2-CH2Fα),
66.2 (C-5β), 62.6 (C-5α); HRMS: [M+H]+ calcd for C29H32FO6 495.21774, found 495.21745.

2,2-Difluoroethyl 2,3-di-O-benzyl-4,6-O-benzylidene-α/β-D-glucopyranoside (2D)

Donor 2 and 2,2-difluoroethanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations and
purified by flash column chromatography (1/1 to 0/1 pentane/toluene to 6% EtOAc in toluene) to yield glycosylation product
2D (36 mg, 70 µmol, 70%, α:β = 5:1). Rf: 0.32 and 0.36 (4% EtOAc in toluene). IR (neat): 696, 747, 996, 1028, 1071, 1086,
1369, 1453, 2865. Data for the α-anomer: 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 7.48 (m, 2H, CHarom), 7.41 –
7.26 (m, 13H, CHarom), 5.95 (tt, 1H, J = 55.4, 4.2 Hz, CHF2), 5.55 (s, 1H, CHPh), 4.92 (d, 1H, J = 11.3 Hz, CHH Bn), 4.84 (d,
1H, J = 12.0 Hz, CHH Bn), 4.83 (d, 1H, J = 11.4 Hz, CHH Bn), 4.75 (d, 1H, J = 3.9 Hz, H-1), 4.66 (d, 1H, J = 12.0 Hz, CHH
Bn), 4.25 (dd, 1H, J = 10.2, 4.8 Hz, H-6), 4.03 (t, 1H, J = 9.3 Hz, H-3), 3.90 – 3.65 (m, 4H, CH2-CHF2, H-5, H-6), 3.62 (t, 1H,
J = 9.4 Hz, H-4), 3.58 (dd, 1H, J = 9.3, 3.8 Hz, H-2); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 138.8, 138.2, 137.4 (Cq),
129.1, 128.6, 128.4, 128.4, 128.2, 128.1, 128.1, 127.7, 126.1 (CHarom), 114.2 (t, J = 241.5 Hz, CHF2), 101.4 (CHPh), 98.9 (C-
1), 82.0 (C-4), 79.3 (C-2), 78.4 (C-3), 75.5, 74.0 (CH2 Bn), 69.0 (C-6), 67.4 (t, J = 28.8 Hz, CH2-CHF2), 63.0 (C-5); Diagnostic
peaks β-anomer: 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 5.90 (tdd, 1H, J = 55.4, 5.0, 3.4 Hz, CHF2), 5.56 (s, 1H,
CHPh), 4.54 (d, 1H, J = 7.6 Hz, H-1), 4.34 (dd, 1H, J = 10.5, 5.0 Hz, H-6), 3.48 (t, 1H, J = 8.1 Hz, H-2), 3.41 (td, 1H, J = 9.6,
5.0 Hz, H-5); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 104.5 (C-1), 101.3 (CHPh), 81.9 (c-2), 81.4, 80.8 (C-3, C-4), 75.6,
75.3 (CH2 Bn), 68.7 (C-6), 66.3 (C-5); HRMS: [M+H]+ calcd for C29H31F2O6 513.20832, found 513.20808.

S22
2,2,2-Trifluoroethyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside (2E)

Donor 2 and 2,2,2-trifluoroethanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations and
purified by flash column chromatography (1/1 to 0/1 pentane/toluene to 6% EtOAc in toluene) to yield glycosylation product
2E (33.7 mg, 64 µmol, 64%, α:β = > 20:1). Rf: 0.45 (4% EtOAc in toluene). [𝛼]23
D = +7.0° (c = 0.67, DCM); IR (neat): 697,

747, 1001, 1029, 1077, 1161, 1279, 1373, 1454, 2864; Data for the α-anomer: 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC):
δ 7.51 – 7.46 (m, 2H, CHarom), 7.41 – 7.26 (m, 13H, CHarom), 5.55 (s, 1H, CHPh), 4.92 (d, 1H, J = 11.2 Hz, CHH Bn), 4.84 (d,
1H, J = 12.0 Hz, CHH Bn), 4.83 (d, 1H, J = 11.3 Hz, CHH Bn), 4.80 (d, 1H, J = 3.9 Hz, H-1), 4.67 (d, 1H, J = 12.0 Hz, CHH
Bn), 4.25 (dd, 1H, J = 10.2, 4.8 Hz, H-6), 4.05 (t, 1H, J = 9.3 Hz, H-3), 3.92 (q, 2H, J = 8.7 Hz, CH2-CF3), 3.85 (td, 1H, J =
9.9, 4.8 Hz, H-5), 3.70 (t, 1H, J = 10.3 Hz, H-6), 3.63 (t, 1H, J = 9.4 Hz, H-4), 3.59 (dd, 1H, J = 9.3, 3.8 Hz, H-2); 13C-APT
NMR (CDCl3, 101 MHz, HSQC): δ 138.8, 138.2, 137.4 (Cq), 129.1, 128.6, 128.4, 128.4, 128.2, 128.1, 128.1, 127.8, 126.2
(CHarom), 123.8 (q, J = 278.6 Hz, CF3), 101.4 (CHPh), 99.0 (C-1), 81.9 (C-4), 79.2 (C-2), 78.3 (C-3), 75.5, 73.9 (CH2 Bn), 68.9
(C-6), 65.2 (q, J = 35.0 Hz, CH2-CF3), 63.3 (C-5); Diagnostic peaks β-anomer: 1H NMR (CDCl3, 400 MHz, HH-COSY,
HSQC): δ 5.56 (s, 1H, CHPh), 4.73 (d, 1H, J = 10.7 Hz, CHH Bn), 4.60 (d, 1H, J = 7.7 Hz, H-1), 4.34 (dd, 1H, J = 10.5, 5.0
Hz, H-6), 3.51 (t, 1H, J = 8.0 Hz), 3.41 (td, 1H, J = 9.6, 5.2 Hz, H-5); HRMS: [M+H]+ calcd for C29H30F3O6 531.19890, found
531.19857.

1,1,1,3,3,3-Hexafluoro-2-propyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside (2F)

Donor 2 and 1,1,1,3,3,3-hexafluoroisopropanol were condensed using the general procedure for Tf2O/Ph2SO mediated
glycosylations (for an additional 144 hours at -40°C) and purified by flash column chromatography (1/1 to 0/1 pentane/toluene
to 10% EtOAc in toluene) to yield glycosylation product 2F (39 mg, 65 µmol, 65%, α:β = > 20:1). Rf: 0.31 (4/1 pentane/Et2O).
[𝛼]25 1
D = -40.9° (c = 0.68, CHCl3); IR (neat): 689, 746, 997, 1086, 1196, 1219, 1368, 1454, 2868; H NMR (CDCl3, 400 MHz,

HH-COSY, HSQC): δ 7.51 – 7.47 (m, 2H, CHarom), 7.40 – 7.27 (m, 13H, CHarom), 5.55 (s, 1H, CHPh), 5.07 (d, 1H, J = 4.0 Hz,
H-1), 4.93 (d, 1H, J = 11.1 Hz, CHH Bn), 4.83 (d, 1H, J = 11.1 Hz, CHH Bn), 4.79 (d, 1H, J = 11.7 Hz, CHH Bn), 4.73 (d, 1H,
J = 11.7 Hz, CHH Bn), 4.41 (hept, 1H, J = 5.9 Hz, CH HFIP), 4.24 (dd, 1H, J = 10.2, 5.0 Hz, H-6), 4.06 (t, 1H, J = 9.4 Hz, H-
3), 3.94 (td, 1H, J = 10.0, 4.9 Hz, H-5), 3.70 (t, 1H, J = 10.2 Hz, H-6), 3.75 – 3.60 (m, 2H, H-2, H-4); 13C-APT NMR (CDCl3,
101 MHz, HSQC): δ 138.6, 137.7, 137.2 (Cq), 129.2, 128.6, 128.5, 128.4, 128.2, 128.1, 127.8, 126.1 (CHarom), 121.7 (q, J =
285 Hz, CF3), 121.2 (q, J = 285 Hz, CF3), 101.4 (CHPh), 100.4 (C-1), 81.5 (C-4), 78.3, 78.3 (C-2, C-3), 75.6, 74.1 (CH2 Bn),
13C-HMBC
73.4 (hept, J = 32.9 Hz, CH HFIP), 68.5 (C-6), 64.0 (C-5); NMR (CDCl3, 101 MHz): 3J(HHFIP-C1) observed;
HRMS: [2M-2(CF3)2CHO+H2O+NH4]+ calcd for (C27H27O5)2O 896.40044, found 896.40115; LC-MS: Rt = 10.09, no
conclusive mass. TLC-MS: [M+Na]+ calcd for C30H28F6O6Na 621.17 found 621.2, and [M+H2O-benzaldehyde+Na]+ calcd for
C23H24F6O6Na 533.14 found 533.0.

S23
1-[2H]-1,5-anhydro-2,3-di-O-benzyl-4,6-O-benzylidene-α-D-glucitol (2G)

Donor 2 and triethylsilane-D were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 144 hours at -40°C) and purified by flash column chromatography (19/1 to 4/1 Et2O/pentane) to yield glycosylation
product 2G (34 mg, 79 µmol, 79%, α:β = > 20:1). Rf: 0.38 (4/1 pentane/Et2O). Spectroscopic data of the non-dueterated glucitol
were in accord with those previously reported.41 [𝛼]23
D = +5.4° (c = 0.78, CHCl3); IR (neat): 696, 748, 1009, 1028, 1088, 1368,

1454, 2868; 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC): δ 7.51 – 7.48 (m, 2H, CHarom), 7.41 – 7.34 (m, 5H, CHarom), 7.34
– 7.26 (m, 7H, CHarom), 5.55 (s, 1H, CHPh), 4.96 (d, 1H, J = 11.4 Hz, CHH Bn), 4.83 (d, 1H, J = 11.6 Hz, CHH Bn), 4.80 (d,
1H, J = 11.7 Hz, CHH Bn), 4.66 (d, 1H, J = 11.6 Hz, CHH Bn), 4.31 (dd, 1H, J = 10.4, 5.0 Hz, H-6), 3.98 (d, 1H, J = 5.6 Hz,
H-1), 3.75 (t, 1H, J = 8.8 Hz, H-3), 3.70 – 3.63 (m, 2H, H-2, H-6), 3.61 (t, 1H, J = 9.2 Hz, H-4), 3.36 (ddd, 1H, J = 10.1, 9.2,
5.0 Hz, H-5); 13C-APT NMR (CDCl3, 101 MHz, HSQC): δ 138.8, 138.3, 137.5 (Cq), 129.0, 128.6, 128.4, 128.4, 128.1, 128.0,
128.0, 127.7, 126.1 (CHarom), 101.3 (CHPh), 82.5 (C-3), 82.2 (C-4), 77.7 (C-2, 75.1, 74.0 (CH2 Bn), 71.4 (C-5), 69.0 (C-6),
68.7 (t, JC1,D1 = 22.3 Hz); 2H NMR (CHCl3, 61 MHz): 3.34 (s, 1D, D-1); HRMS: [M+H]+ calcd for C27H28DO5S 434.20723,
found 434.20714.

Allyl 2,3-di-O-benzyl-1-deoxy-4,6-O-benzylidene-α-D-glucopyranoside (2H)

Donor 2 and allyl trimethylsilane were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (19/1 to 9/1 pentane/EtOAc) to yield glycosylation
product X12 (20 mg, 42 µmol, 42%, α:β = > 1:20). Contaminated with a 1-OTMS glycoside by-product. α-Thio glycoside 2α
was formed as a by-product. Rf: 0.60 (9/1 pentane/EtOAc). Spectroscopic data were in accord with those previously
reported.35,42 1H NMR (CDCl3, 400 MHz, HH-COSY, HH-NOESY, HSQC): δ 7.53 – 7.47 (m, 2H, CHarom), 7.42 – 7.27 (m,
13H, CHarom), 5.77 (ddt, 1H, J = 17.1, 10.2, 6.9 Hz, CH allyl), 5.57 (s, 1H, CHPh), 5.18 – 5.05 (m, 2H, CH2 allyl), 4.93 (d, 1H,
J = 11.4 Hz, CHH Bn), 4.81 (d, 1H, J = 11.4 Hz, CHH Bn), 4.78 (d, 1H, J = 11.7 Hz, CHH Bn), 4.64 (d, 1H, J = 11.7 Hz, CHH
Bn), 4.27 – 4.21 (m, 1H, H-6), 4.08 (td, 1H, J = 7.7, 5.7 Hz, H-1), 3.92 – 3.85 (m, 1H, H-3), 3.76 (dd, 1H, J = 8.6, 5.7 Hz, H-
2), 3.69 – 3.63 (m, 3H, H-4, H-5, H-6), 2.57 – 2.51 (m, 2H, CH2 allylic); 13C-APT NMR (CDCl3, 101 MHz, HSQC, HMBC):
δ 138.7, 138.3, 137.5 (Cq-arom), 134.4 (CH allyl), 129.0, 128.6, 128.5, 128.4, 128.1, 128.0, 127.9, 127.8, 126.1 (CH arom), 117.4
(CH2 allyl), 101.3 (CHPh), 82.9 (C-4), 79.5 (C-2), 78.9 (C-3), 75.0 (C-1), 75.0, 73.7 (CH2 Bn), 69.6 (C-6), 63.5 (C-5), 30.8
(CH2 allylic); HRMS: [M+H]+ calcd for C30H33O5 473.23225, found 473.23228.

Phenyl 2,3-di-O-benzyl-4,6-O-benzylidene-1-thio-α-D-glucopyranoside (2α)

Rf: 0.38 (4/1 pentane/Et2O). Spectroscopic data were in accord with those previously reported.16 1H NMR (CDCl3, 400 MHz,
HH-COSY, HSQC): δ 7.53 – 7.44 (m, 4H, CHarom), 7.43 – 7.36 (m, 7H, CHarom), 7.36 – 7.27 (m, 9H, CHarom), 5.59 (d, 1H, J =

S24
5.5 Hz, H-1), 5.57 (s, 1H, CHPh), 4.92 (d, 1H, J = 11.3 Hz, CHH Bn), 4.86 (d, 1H, J = 11.3 Hz, CHH Bn), 4.81 (d, 1H, J =
11.8 Hz, CHH Bn), 4.76 (d, 1H, J = 11.8 Hz, CHH Bn), 4.39 (td, 1H, J = 9.9, 4.9 Hz, H-5), 4.19 (dd, 1H, J = 10.3, 5.0 Hz, H-
6), 3.98 (t, 1H, J = 9.2 Hz, H-3), 3.90 (dd, 1H, J = 9.3, 5.5 Hz, H-2), 3.71 (t, J = 10.3 Hz, H-6), 3.66 (t, J = 9.3 Hz, H-4);
HRMS: [M+NH4]+ calcd for C33H36NO5 558.23087, found 558.23075.

Methyl 6-O-(2,3-di-O-benzyl-4,6-O-benzylidene-α/β-ᴅ-glucopyranosyl)-2,3,4-tri-O-benzyl-α-ᴅ-glucopyranoside (25)

Donor 2 and acceptor 10 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (9/1 to 3/1 pentane/EtOAc) to yield glycosylation
product 25 (72.1 mg, 81 µmol, 81%, α:β = 1:2.7). Rf: 0.83 (6/4 pentane/EtOAc). Spectroscopic data were in accord with those
previously reported.36 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC, HMBC): δ 7.51 – 7.44 (m, 2H, CHarom), 7.41 – 7.12
(m, 28H, CHarom), 5.54 (s, 1H, CHPh), 4.97 (d, 1H, J = 10.8 Hz, CHH Bn), 4.93 – 4.88 (m, 2H, 2xCHH Bn), 4.84 – 4.76 (m,
4H, 3xCHH Bn, CHH Bn), 4.73 – 4.63 (m, 2H, CHH Bn, CHH Bn), 4.61 (d, 1H, J = 3.6 Hz, H-1), 4.49 (d, 1H, J = 11.2 Hz,
CHH Bn), 4.44 (d, 1H, J = 7.7 Hz, H-1’), 4.31 (dd, 1H, J = 10.5, 5.0 Hz, H-6’), 4.11 (dd, 1H, J = 10.7, 2.0 Hz, H-6), 3.99 (t, J
= 9.3 Hz, 1H, H-3), 3.82 – 3.65 (m, 5H, H-3’, H-4’, H-5, H-6, H-6’), 3.56 – 3.48 (m, 3H, H-2, H-2’, H-4), 3.40 – 3.34 (m, 1H,
H-5’), 3.33 (s, 3H, CH3 OMe); 13C-APT NMR (CDCl3, 101 MHz, HSQC, HMBC): δ 138.9, 138.5, 138.4, 138.3, 138.2, 137.4
(Cq), 128.6, 128.5, 128.5, 128.4, 128.4, 128.4, 128.4, 128.3, 128.3, 128.3, 128.2, 128.1, 128.1, 128.1, 128.1, 128.0, 128.0, 128.0,
127.7, 127.7, 127.7, 127.7, 126.1 (CHarom), 104.2 (C-1’), 101.2 (CHPh), 98.2 (C-1), 82.1 (C-3), 81.9 (C-2’), 81.5, 81.2 (C-3’,
C-4’), 79.8 (C-2), 77.9 (C-4), 75.8, 75.5, 75.2, 75.0, 73.5 (CH2 Bn), 69.8 (C-5), 68.8 (C-6, C-6’), 66.2 (C-5’), 55.3 (OMe);
Diagnostic peaks α-anomer: 1H NMR (CDCl3, 400 MHz): δ 5.53 (s, 0.33H), 4.57 (d, 0.33H, J = 3.6 Hz), 4.20 (dd, 0.33H, J =
10.1, 4.8 Hz), 3.89 (td, 0.33H, J = 10.0, 4.8 Hz), 3.43 (dd, 0.33H, J = 9.6, 3.6 Hz), 3.34 (s, 1H); 13C-APT NMR (CDCl3, 101
MHz): δ 138.9, 138.8, 138.5, 138.3, 137.6, 129.0-126.2, 101.4, 98.3, 98.1, 82.3, 82.2, 80.2, 79.4, 78.0, 77.8, 75.8, 75.1, 75.1,
73.5, 73.0, 70.5, 69.2, 66.4, 62.6, 55.3; HRMS: [M+Na]+ calcd for C55H58O11Na 917.38713, found 917.38678.

Methyl 4-O-(2,3-di-O-benzyl-4,6-O-benzylidene-α/β-ᴅ-glucopyranosyl)-2,3,6-tri-O-benzyl-α-ᴅ-glucopyranoside (26)

Donor 2 and acceptor 11 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (19/1 to 4/1 pentane/EtOAc) to yield glycosylation
product 26 (71 mg, 79 µmol, 79%, α:β = 1:1). Rf: 0.54 (4/1 pentane/EtOAc). Spectroscopic data were in accord with those
previously reported for the α-anomer.36 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC, HMBC): δ 7.52 – 7.45 (m, 4H,
CHarom), 7.44 – 7.18 (m, 56H, CHarom), 5.75 (d, 1H, J = 3.8 Hz, H-1’α), 5.52 (s, 1H, CHPhα), 5.49 (s, 1H, CHPhβ), 5.04 (d, 1H,
J = 11.7 Hz, CHH Bnα), 4.95 – 4.87 (m, 3H, 3xCHH Bn), 4.84 – 4.51 (m, 17H, 6xCHH Bn, 9xCHH Bn, H-1, H-1β), 4.36 (d,
1H, J = 7.8 Hz, H-1’β), 4.30 (d, 1H, J = 12.0 Hz, CHH Bnβ), 4.19 (dd, 1H, J = 10.5, 5.0 Hz, H-6’β), 4.15 – 4.09 (m, 3H, H-3α,
H-4α, H-6’α), 3.99 (t, 1H, J = 9.3 Hz, H-3’α), 3.94 (t, 1H, J = 9.4 Hz, H-4β), 3.90 – 3.78 (m, 5H, H-2β, H-5α, H-5α’, H-6α, H-6β),
3.69 – 3.41 (m, 11H, H-2α, H-2’α, H-3β, H-3’β, H-4’α, H-4’β, H-5β, H-6α, H-6β, H-6’α, H-6’β), 3.40 – 3.31 (m, 7H, CH3 OMe,

S25
CH3 OMeβ, H-2’β), 3.10 (td, 1H, J = 9.5, 4.9 Hz, H-5’β); 13C-APT NMR (CDCl3, 101 MHz, HSQC, HMBC): δ 139.4, 139.0,
138.7, 138.6, 138.5, 138.4, 138.2, 138.0, 137.9, 137.9, 137.6, 137.5 (C q), 129.0, 128.9, 128.6, 128.5, 128.5, 128.4, 128.3, 128.3,
128.3, 128.2, 128.2, 128.2, 128.1, 128.1, 128.0, 128.0, 127.9, 127.8, 127.7, 127.7, 127.5, 127.5, 127.4, 127.3, 126.8, 126.1,
126.1 (CHarom), 102.9 (C-1’β), 101.2 (CHPh), 98.5, 97.8 (C-1α, C-1β), 97.2 (C-1’α), 82.7 (C-2’β), 82.4 (C-4’α), 82.2 (C-3α), 81.8
(C-4’β), 81.0 (C-3’β), 80.3 (C-2β), 80.3, 78.9 (C-2α, C-3’α), 78.8 (C-2’α, C-3β), 76.9 (C-4β), 75.6, 75.5, 75.4, 75.0, 74.4, 73.9,
73.7, 73.4, 73.4 (CH2 Bn), 71.6 (C-4α), 70.0 (C-5β), 69.4 (C-5α), 69.0, 68.9, 68.8 (C-6α, C-6’α, C-6’β), 67.7 (C-6β), 65.8 (C-5’β),
63.4 (C-5’α), 55.5 (OMeβ), 55.3 (OMeα); HRMS: [M+NH4]+ calcd for C55H62O11N 912.43174, found 912.43282.

Methyl (methyl 4-O-[2,3-di-O-benzyl-4,6-O-benzylidene-α/β-ᴅ-glucopyranosyl]-2,3,6-tri-O-benzyl-α-ᴅ-glucopyranosyl

uronate) (27)

Donor 2 and acceptor 12 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 24 hours at -40°C) and purified by flash column chromatography (19/1 to 4/1 pentane/EtOAc) to yield glycosylation
product 27 (75.2 mg, 90 µmol, 90%, α:β = 5:1). Rf: 0.77 (7/3 pentane/EtOAc). IR (neat): 694, 732, 912, 988, 1026, 1043, 1074,
1086, 1358, 1454, 1749, 28866, 2932; Data for the α-anomer: 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC, HMBC): δ 7.48
– 7.43 (m, 2H, CHarom), 7.40 – 7.16 (m, 23H, CHarom), 5.51 (s, 1H, CHPh), 5.44 (d, 1H, J = 3.8 Hz, H-1’), 4.95 – 4.86 (m, 3H,
CH2 Bn, CHH Bn), 4.78 (d, 1H, J = 11.2 Hz, CHH Bn), 4.71 (d, 1H, J = 12.1 Hz, CHH Bn), 4.67 (d, 1H, J = 12.0 Hz, CHH
Bn), 4.59 – 4.53 (m, 3H, 2xCHH Bn, H-1), 4.28 (dd, 1H, J = 6.5, 3.8 Hz, H-6’), 4.25 (d, 1H, J = 9.5 Hz, H-5), 4.11 (t, 1H, J =
9.1 Hz, H-4), 4.05 (t, 1H, J = 8.9 Hz, H-3), 3.98 (t, 1H, J = 9.1 Hz, H-3’), 3.76 (s, 3H, CH3 CO2Me), 3.64 (t, 1H, J = 10.0 Hz,
H-6’), 3.61 – 3.54 (m, 3H, H-2, H-4’, H-5’), 3.48 (dd, 1H, J = 5.6, 3.9 Hz, H-2’), 3.40 (s, 3H, CH3 OMe); 13C-APT NMR
(CDCl3, 101 MHz, HSQC, HMBC): δ 170.1 (C=O CO2Me), 139.0, 138.6, 138.0, 137.8, 137.6 (Cq), 129.0, 128.6, 128.4, 128.4,
128.3, 128.3, 128.3, 128.2, 128.1, 128.1, 127.8, 127.7, 127.7, 127.3, 127.0, 126.1 (CH arom), 101.3 (CHPh), 98.6 (C-1), 98.4 (C-
1’), 82.0 (C-4’), 80.8 (C-3), 79.2 (C-2), 78.7 (C-2’), 78.4 (C-3’), 76.1 (C-4), 75.3, 75.0, 73.7, 73.7 (CH2 Bn), 70.3 (C-5), 68.6
(C-6’), 63.1 (C-5’), 55.8 (CH3 OMe), 52.9 (CH3 CO2Me); 13C-HMBC NMR (CDCl3, 101 MHz): δ 98.4 (JC1’,H1’ = 174 Hz, C-
1’ α); Diagnostic peaks β-anomer: 1H NMR (CDCl3, 400 MHz): δ 5.47 (s, 0.18H, CHPh), 4.62 (d, 0.18H, J = 12.1 Hz), 3.87
(dd, 0.18H, J = 9.6, 8.4 Hz), 3.50 (s, 0.54H, CH3 CO2Me), 3.44 (s, 0.54H, CH3 OMe), 3.38 – 3.28 (m, 0.36H, H-2’, H-5’); 13C-
APT NMR (CDCl3, 101 MHz): δ 170.1, 139.2, 138.6, 138.2, 137.4, 129.0, 128.5, 128.3, 128.1, 127.7, 127.5, 126.1, 102.9 (C-
1’), 101.2 (CHPh), 99.0 (C-1), 82.3, 81.8, 81.3, 79.6, 78.5, 78.2, 75.6, 75.5, 75.2, 73.9, 70.0, 68.8, 65.9, 55.9, 52.7; 13C-HMBC
NMR (CDCl3, 101 MHz): δ 102.9 (JC1’,H1’ = 164 Hz, C-1’ β); HRMS: [M+Na]+ calcd for C49H52O12Na 855.33510, found
855.33496.

Methyl 4-O-(2,3-di-O-benzyl-4,6-O-benzylidene-α-ᴅ-glucopyranosyl)-2,3,6-tri-O-benzyl-β-ᴅ-galactopyranoside (28)

S26
Donor 2 and acceptor 13 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (19/1 to 4/1 pentane/EtOAc) to yield glycosylation
product 28 (74 mg, 83 µmol, 83%, α:β = > 20:1). Rf: 0.50 (4/1 pentane/EtOAc). [𝛼]23
D = +38.4° (c = 1.0, CHCl3); IR (neat):

696, 735, 997, 1028, 1072, 1366, 1452, 1497, 2859, 2922; 1H NMR (CDCl3, 400 MHz, HH-COSY, HSQC, HMBC): δ 7.49
(dd, 2H, J = 7.9, 1.8 Hz, CHarom), 7.42 – 7.16 (m, 28H, CHarom), 5.50 (s, 1H, CHPh), 4.98 (d, J = 3.7 Hz, H-1’), 4.97 (d, J =
11.0 Hz, CHH Bn), 4.93 – 4.87 (m, 2H, 2xCHH Bn), 4.85 – 4.74 (m, 3H, 2xCHH Bn, CHH Bn), 4.72 – 4.63 (m, 2H, 2xCHH
Bn), 4.31 – 4.22 (m, 4H, CH2 Bn, H-1, H-5’), 4.18 (t, 1H, J = 9.4 Hz, H-3’), 4.06 – 3.97 (m, 2H, H-4, H-6), 3.84 (dd, 1H, J =
10.1, 4.9 Hz, H-6’), 3.72 (dd, 1H, J = 10.0, 7.6 Hz, H-2), 3.63 – 3.45 (m, 8H, CH3 OMe, H-2’, H-4’, H-5, H-6, H-6’), 3.42 (dd,
1H, J = 10.0, 2.9 Hz, H-3); 13C-APT NMR (CDCl3, 101 MHz, HSQC, HMBC): δ 138.9, 138.7, 138.6, 138.4, 138.2, 137.8 (Cq),
128.9, 128.5, 128.4, 128.4, 128.3, 128.3, 128.1, 128.0, 127.8, 127.7, 127.6, 126.2 (CHarom), 105.1 (C-1), 101.2 (CHPh), 100.7
(C-1’), 83.0 (C-4’), 80.6 (C-3), 79.7 (C-2’), 78.9 (C-2, C-3’), 75.9 (C-4), 75.3, 75.2, 74.0 (CH2 Bn), 73.5 (C-5), 73.2, 72.8 (CH2
Bn), 69.1 (C-6’), 68.0 (C-6), 63.0 (C-5’), 57.2 (OMe); 13C-HMBC NMR (CDCl3, 101 MHz): δ 105.1 (JC1’,H1’ = 159 Hz, C-1
β), 100.7 (JC1’,H1’ = 170 Hz, C-1’ α); HRMS: [M+NH4]+ calcd for C55H62O11N 912.43174, found 912.43266.

Methyl 2-O-(2,3-di-O-benzyl-4,6-O-benzylidene-α/β-ᴅ-glucopyranosyl)-3-O-benzyl-4,6-O-benzylidene-α-ᴅ-
mannopyranoside (29)

Donor 2 and acceptor 14 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (19/1 to 4/1 pentane/EtOAc) to yield glycosylation
product 29 (64.3 mg, 80 µmol, 80%, α:β = > 20:1). Rf: 0.27 (8/1 pentane/EtOAc). Spectroscopic data were in accord with those
previously reported.36 IR (neat): 696, 748, 999, 1028, 1074, 1088, 1369, 1454, 1498, 2864, 2911; 1H NMR (CDCl3, 400 MHz,
HH-COSY, HSQC, HMBC): δ 7.49 (ddd, 4H, J = 8.9, 5.8, 1.9 Hz, CHarom), 7.44 – 7.35 (m, 8H, CHarom), 7.35 – 7.24 (m, 10H,
CHarom), 7.17 (dp, 3H, J = 4.4, 1.6 Hz, CHarom), 5.60 (d, 1H, J = 3.9 Hz, H-1’), 5.57 (s, 1H, CHPh’), 5.43 (s, 1H, CHPh), 4.95
– 4.85 (m, 3H, CHH Bn, CH2 Bn), 4.78 (d, 1H, J = 11.2 Hz, CHH Bn), 4.72 (d, 1H, J = 11.7 Hz, CHH Bn), 4.71 (d, 1H, J =
1.7 Hz, H-1), 4.47 (d, 1H, J = 11.1 Hz, CHH Bn), 4.33 – 4.26 (m, 2H, H-4, H-6’), 4.24 – 4.18 (m, 2H, H-2, H-6), 4.08 (t, 1H,
J = 9.3 Hz, H-3’), 4.02 (dd, 1H, J = 9.9, 2.9 Hz, H-3), 3.93 – 3.70 (m, 4H, H-5, H-5’, H-6, H-6’), 3.63 (t, 1H, J = 9.4 Hz, H-
4’), 3.56 (dd, 1H, J = 9.3, 3.9 Hz, H-2’), 3.36 (s, 3H, CH3 OMe); 13C-APT NMR (CDCl3, 101 MHz, HSQC, HMBC): δ 139.1,
138.6, 138.5, 137.9, 137.5 (Cq), 129.1, 129.0, 128.5, 128.4, 128.3, 128.3, 128.3, 128.0, 127.9, 127.9, 127.8, 127.6, 127.6, 126.1,
126.1 (CHarom), 101.3, 101.3, 101.2 (CHPh, C-1’), 98.0 (C-1), 82.1 (C-4’), 79.4 (C-2’), 79.3 (C-4), 77.9 (C-3’), 76.9 (C-3),
75.3 (CH2 Bn), 74.4 (C-2), 74.0, 71.9 (CH2 Bn), 69.1 (C-6’), 68.8 (C-6), 64.4 (C-5), 63.0 (C-5’), 54.9 (OMe); 13C-HMBC NMR
(CDCl3, 101 MHz): δ 101.3 (JC1’,H1’ = 168 Hz, C-1’ α), 98.0 (JC1’,H1’ = 170 Hz, C-1’ α); HRMS: [M+NH4]+ calcd for C48H54NO11
820.36914, found 820.36958.

S27
Glycoslyations with donor 3

Methyl (cyclohexyl 4-O-acetyl-2,3-di-O-benzyl-α/β-D-mannopyranosyl uronate) (3A).

Donor 3 and cyclohexanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (9/1 to 4/1 pentane/EtOAc) to yield glycosylation
product 3A (42.5 mg, 83 μmol, 83%, α:β = 1:8.3). Rf: 0.46 (7/3 pentane/EtOAc). IR (neat): 1026, 1047, 1105, 1238, 1368,
1452, 1740, 1751, 2855, 2930; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.48 – 7.18 (m, 10H,
CHarom), 5.50 (t, 1H, J = 9.7 Hz, H-4), 5.00 (d, 1H, J = 12.8 Hz, CHH Bn), 4.88 (d, 1H, J = 12.8 Hz, CHH Bn), 4.54 (s, 1H, H-
1), 4.46 (d, 1H, J = 12.4 Hz, CHH Bn), 4.31 (d, 1H, J = 12.4 Hz, CHH Bn), 3.84 (d, 1H, J = 2.8 Hz, H-2), 3.82 (d, 1H, J = 9.7
Hz, H-5), 3.73 (s, 3H, CH3 CO2Me), 3.73 – 3.65 (m, 1H, CH Cy), 3.46 (dd, 1H, J = 9.8, 2.9 Hz, H-2), 2.02 (s, 3H, CH3 OAc),
1.99 – 1.21 (m, 15H, CH2 Cy); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 169.7, 168.3 (C=O CO2Me, Ac), 138.6, 138.0
(Cq), 128.7, 128.5, 128.2, 127.8, 127.5, 127.5 (CHarom), 99.5 (C-1), 78.7 (C-3), 77.0 (CH Cy), 74.0 (C-5), 73.9 (CH2 Bn), 73.4
(C-2), 71.4 (CH2 Bn), 69.1 (C-4), 52.7 (CH3 CO2Me), 33.4, 31.4, 25.8, 23.9 (CH2 Cy), 21.0 (CH3 Ac); Diagnostic peaks α-
anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 5.50 (t, 0.12H, J = 9.7 Hz, H-4), 5.24 (d, 0.12H, J = 3.3 Hz, H-1),
4.78 (d, 0.12H, J = 12.0 Hz, CHH Bn), 4.68 (d, 0.12H, J = 12.4 Hz, CHH Bn); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ
69.7 (C-1); HRMS: [M+NH4]+ calcd for C29H40NO8 530.27484, found 530.27495.

Methyl (ethyl 4-O-acetyl-2,3-di-O-benzyl-α/β-D-mannopyranosyl uronate) (3B).

Donor 3 and ethanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an additional
16 hours at -40°C) and purified by flash column chromatography (9/1 to 4/1 pentane/EtOAc) to yield glycosylation product 3B
(43.4 mg, 95 μmol, 95%, α:β = 1:8.3). Rf: 0.36 (7/3 pentane/EtOAc). IR (neat): 735, 1026, 1047, 1103, 1229, 1369, 1454, 1744,
2924; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.68 – 7.15 (m, 10H, CHarom), 5.51 (t, 1H, J
= 9.5 Hz, H-4), 4.96 (d, 1H, J = 12.6 Hz, CHHBn), 4.84 (d, 1H, J = 12.6 Hz, CHH Bn), 4.48 (d, 1H, J = 12.4 Hz, CHH Bn),
4.43 (s, 1H, H-1), 4.33 (d, 1H, J = 12.4 Hz, CHH Bn), 4.02 (dq, 1H, J = 9.2, 7.1 Hz, CHHCH3 Et), 3.88 (d, 1H, J = 2.8 Hz, H-
2), 3.84 (d, 1H, J = 9.5 Hz, H-5), 3.73 (s, 3H, CH3 CO2Me), 3.54 – 3.44 (m, 2H, H-3, CHHCH3 Et, H-3), 2.02 (s, 3H, CH3
OAc), 1.27 (t, 3H, J = 7.0 Hz, CH3 Et); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 169.7, 168.2 (C=O CO2Me, Ac), 138.5,
137.9 (Cq), 129.4, 128.6, 1285, 128.2, 124.9 (CHarom), 101.5 (C-1), 78.2 (C-3), 73.9 (CH2 Bn), 73.9 (C-5), 73.1 (C-2), 71.4
(CH2 Bn), 69.1 (C-4), 65.9 (CH2 Et), 52.7 (CH3 CO2Me), 21.0 (CH3 Ac), 15.2 (CH3 Et); 13C-GATED NMR (101 MHz, CDCl3):
δ 101.5 (JC1,H1 = 160 Hz, C-1 β); Diagnostic peaks α-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 5.51 (t, 0.12H,
H-4), 5.13 (d, 0.12H, J = 4.3 Hz, H-1), 4.78 (d, 0.12H, J = 12.4 Hz, CHH Bn), 4.68 (d, 0.12H, J = 12.3 Hz, CHH Bn), 3.67 (s,
0.36H, CH3 CO2Me). 13C-APT NMR (101 MHz, CDCl3) δ 98.4 (C-1), 77.4 (C-3), 74.6 (C-5), 73.2 (CH2 Bn), 72.5 (CH2 Bn),
69.5 (CH2 Et), 52.6 (CH3 CO2Me); HRMS: [M+Na]+ calcd for C25H30O8Na 481.18329, found 481.18250.

S28
Methyl (2-fluoroethyl 4-O-acetyl-2,3-di-O-benzyl-α/β-D-mannopyranosyl uronate) (3C).

Donor 3 and 2-fluoroethanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 3C (33.2 mg, 70 μmol, 70%, α:β = 1:5). Rf: 0.18 (7/3 pentane/EtOAc). IR (neat): 1045, 1103, 1231, 1369, 1454, 1746,
2895, 2924; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.69 – 7.18 (m, 10H, CHarom), 5.52 (t,
1H, J = 9.3 Hz, H-4), 4.95 (d, 1H, J = 12.5 Hz, CHH Bn), 4.83 (d, 1H, J = 12.5 Hz, CHH Bn), 4.76 – 4.94 (m, 2H, CH2F), 4.54
(s, 1H, H-1), 4.49 (d, 1H, J = 12.4 Hz, CHH Bn), 4.34 (d, 1H, J = 12.4 Hz, CHH Bn) 4.13 (dddd, 1H, J = 37.0, 12.2, 3.3, 2.2
Hz, CHHCH2F), 3.95 (d, 1H, J = 2.6 Hz, H-2), 3.86 (d, 1H, J = 9.2 Hz, H-5), 3.84 – 3.74 (m, 1H, CHHCH2F), 3.72 (s, 3H,
CH3 CO2Me), 3.49 (dd, 1H, J = 9.4, 2.9 Hz, H-3), 2.10 – 1.94 (s, 3H, CH3 OAc); 13C-APT NMR (101 MHz, CDCl3, HSQC):
δ 169.7, 168.1 (C=O CO2Me, Ac), 138.3, 137.81 (Cq), 131.2, 129.46, 128.6, 128.5, 128.4, 128.3, 128.0, 127.9, 127.7, 127.7,
127.6, 124.9 (CHarom), 101.6 (C-1), 82.96 (d, J = 169.5 Hz, CH2F), 77.9 (C-3), 74.5 (CH2 Bn), 74.1 (C-5), 73.8 (C-2), 72.9
(CH2 Bn), 69.01 (d, J = 19.5 Hz, CH2CH2F), 68.9 (C-4), 52.8 (CH3 CO2Me), 21.0 (CH3 Ac). 13C-GATED NMR (101 MHz,
CDCl3) δ 101.6 (JC1,H1 = 156 Hz, C-1); Diagnostic peaks α-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 5.52 (t,
0.20H, J = 9.3 Hz, H-4), 5.19 (d, 0.20H, J = 4.7 Hz, H-1), 3.66 (s, 0.60H, CH3 CO2Me), 2.04 (s, 0.6H, CH3 OAc); 13C-APT
NMR (101 MHz, CDCl3): δ 98.9 (C-1); HRMS: [M+Na]+ calcd for C25H29FO8Na 499.17387, found 499.17297.

Methyl (2,2-difluoroethyl 4-O-acetyl-2,3-di-O-benzyl-α/β-D-mannopyranosyl uronate) (3D).

Donor 3 and 2,2-difluoroethanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 3D (43.1 mg, 87 μmol, 87%, α:β = 1:4.2). Rf: 0.51 (7/3 pentane/EtOAc). IR (neat): 737, 1026, 1051, 1078, 1232, 1439,
1454, 1741, 2870, 2924; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.57 – 7.12 (m, 10H,
CHarom), 5.94 (dddd, 1H, J = 56.7, 54.4, 5.7, 2.5 Hz, CH2CHF2), 5.54 (t, 1H, J = 8.9 Hz, H-4), 4.89 (d, 1H, J = 12.4 Hz, CHH
Bn), 4.78 (d, 1H, J = 12.4 Hz, CHH Bn), 4.56 (s, 1H, H-1), 4.53 (d, 1H, J = 12.3 Hz, CHH Bn), 4.38 (d, 1H, J = 12.4 Hz, CHH
Bn), 4.19 – 4.04 (m, 1H, CHHCHF2), 3.92 (d, 1H, J = 2.1 Hz, H-2), 3.89 (d, 1H, J = 8.7 Hz, H-5), 3.80 – 3.67 (m, 1H,
CHHCHF2), 3.70 (s, 3H, CH3 CO2Me), 3.52 (dd, 1H, J = 9.0, 2.9 Hz, H-3), 2.03 (s, 3H, CH3 OAc); 13C-APT NMR (101 MHz,
CDCl3, HSQC):δ 169.7, 167.9 (C=O CO2Me, Ac), 138.1, 137.8 (Cq), 131.2, 129.5, 128.5, 128.3, 127.9, 127.8, 127.6, 124.9
(CHarom), 114.3 (dd, J = 242.2, 239.7 Hz, CHF2), 101.3 (C-1), 77.4 (C-3), 74.0 (CH2 Bn), 73.6 (C-5), 72.8 (C-2), 71.7 (CH2
Bn), 69.0 (C-4) 68.5 (dd, J = 31.2, 25.6 Hz, CH2CHF2), 52.8 (CH3 CO2Me), 21.0 (CH3 Ac); 13C-GATED NMR (101 MHz,
CDCl3): δ 101.3 (JC1,H1 = 160 Hz, C-1 β); Diagnostic peaks α-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 5.52
(t, 0.24H, J = 11.2 Hz, H-4), 5.23 (d, 0.24H, J = 5.6 Hz, H-1), 3.64 (s, 0.72H, CH3 CO2Me); 13C-APT NMR (101 MHz, CDCl3,
HSQC):δ 99.31 (C-1), 75.45 (C-3), 74.47 (C-2), 73.41 (CH2 Bn), 69.46 (C-4), 52.61 (CH3 CO2Me); HRMS: [M+NH4]+ calcd
for C25H32F2NO8 512.20905, found 512.20889.

S29
Methyl (2,2,2-trifluoroethyl 4-O-acetyl-2,3-di-O-benzyl-α/β-D-mannopyranosyl uronate) (3E).

Donor 3 and 2,2,2-trifluoroethanol were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for
an additional 24 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield
glycosylation product 3E (43.7 mg, 85 μmol, 85%, α:β = 1:2.6). Rf: 0.60 (9/1 pentane/EtOAc). IR (neat): 741, 1058, 1161,
1234, 1280, 1371, 1443, 1748, 2854, 2924; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.83 –
6.86 (m, 10H, CHarom), 5.55 (t, 1H, J = 8.6 Hz, H-4), 4.90 (d, 1H, J = 12.3 Hz, CHH Bn), 4.78 (d, 1H, J = 12.4 Hz, CHH Bn),
4.65 (s, 1H, H-1), 4.54 (d, 1H, J = 12.3 Hz, CHH Bn), 4.37 (d, 1H, J = 12.3 Hz, CHH Bn), 4.35 – 4.23 (m, 1H, CHHCF3), 3.98
– 3.94 (m, 2H, CHHCF3, H-2), 3.92 (d, 1H, J = 8.3 Hz, H-5), 3.69 (s, 3H, CH3 CO2Me), 3.54 (dd, 1H, J = 8.8, 2.8 Hz, H-3),
2.03 (s, 3H, CH3 OAc); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 169.7, 167.8 (C=O CO2Me, Ac), 137.9, 137.8 (Cq), 131.2,
129.5, 129.5, 128.5, 128.5, 128.3, 128.0, 127.9, 127.8, 127.5 (CHarom), 123.8 (q, J = 278.7 Hz, CF3), 100.8 (C-1), 77.1 (C-3),
73.8 (CH2 Bn), 73.6 (C-5), 72.4 (C-2), 71.7 (CH2 Bn), 69.0 (C-4), 66.1 (q, J = 34.8 Hz, CH2CF3), 52.8 (CH3 CO2Me), 21.0
(CH3 Ac); 13C-GATED NMR (101 MHz, CDCl3): δ 100.8 (JC1,H1 = 160 Hz, C-1 β); Diagnostic peaks α-anomer: 1H NMR (400
MHz, CDCl3, HH-COSY, HSQC): δ 5.51 (t, 0.38H, J = 5.5 Hz, H-4), 5.27 (d, 0.38H, J = 5.6 Hz, H-1), 4.23 – 4.12 (m, 0.38H,
CHHCHF2), 3.86 (dd, 0.38H, J = 6.2, 3.0 Hz, H-3); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 99.1 (C-1), 75.4 (C-3), 74.3
(C-2), 73.5 (CH2 Bn), 72.9 (CH2 Bn), 69.4 (C-4), 52.6 (CH3 CO2Me), 21.0 (CH3 Ac); 13C-GATED NMR (101 MHz, CDCl3)
δ 99.1 (JC1,H1 = 172 Hz, C-1 α); HRMS: [M+Na]+ calcd for C25H27F3O8Na 535.15502, found 535.15415.

Methyl (1,1,1,3,3,3-hexafluoro-2-propyl 4-O-acetyl-2,3-di-O-benzyl-α/β-D-mannopyranosyl uronate) (3F).

Donor 3 and 1,1,1,3,3,3-hexafluoro-2-propanol were condensed using the general procedure for Tf2O/Ph2SO mediated
glycosylations (for an additional 240 hours at -40°C) and purified by flash column chromatography (9/1 to 4/1 pentane/EtOAc)
to yield glycosylation product 3F (30.1 mg, 52 μmol, 52%, α:β = 1:1). Rf: 0.85 (α), 0.75 (β) (7/3 pentane/EtOAc). IR (neat):
1105, 1371, 1454, 1751, 2872, 2924; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC): δ 7.72 – 7.13
(m, 10H, CHarom), 5.55 (t, 1H, J = 9.5 Hz, H-4), 4.92 (d, 1H, J = 12.3 Hz, CHH Bn), 4.78 (d, 1H, J = 12.1 Hz, CHH Bn), 4.74
(s, 1H, H-1), 4.51 (d, 1H, J = 12.3 Hz, CHH Bn), 4.72 – 4.56 (m, 1H, CH(CF3)2) 4.36 (d, 1H, J = 12.7 Hz, CHH Bn), 3.99 (d,
1H, J = 2.5 Hz, H-2), 3.87 (d, 1H, J = 9.4 Hz, H-5), 3.73 (s, 3H, CH3 CO2Me), 3.50 (dd, 1H, J = 9.6, 2.8 Hz, H-3), 2.02 (s, 3H,
CH3 OAc); 13C-APT NMR (101 MHz, CDCl3, HSQC): δ 169.6, 167.3 (C=O CO2Me, Ac), 137.8, 137.5 (Cq), 128.6, 128.5,
128.4, 128.0, 128.0, 127.8, 127.6, (CHarom), 120.8 (q, J = 281.0 Hz, CF3), 100.3 (C-1), 78.0 (C-3), 74.3 (CH2 Bn), 73.9 (C-5),
72.8 (C-2), 72.4 (CH2 Bn), 71.8 (hept, J = 33.0 Hz, CH(CF3)2), 68.5 (C-4), 53.0 (CH3 CO2Me), 20.9 (CH3 Ac); 13C-GATED
NMR (101 MHz, CDCl3): δ 100.3 (JC1,H1 = 165 Hz, C-1 β); Diagnostic peaks α-anomer: 1H NMR (400 MHz, CDCl3, HH-
COSY, HSQC): δ 5.49 (t, 0.90H, J = 5.6 Hz, H-4), 5.39 (d, 0.90H, J = 5.5 Hz, H-1), 4.72 – 4.56 (m, 4.5H, CHH Bn, CHH Bn,
CHH Bn, CHH Bn, CH(CF3)2), 4.37 – 4.35 (m, 0.90H, H-5), 3.84 (dd, 0.90H, J = 6.0, 2.9 Hz, H-3), 3.68 (dd, 0.90H, J = 5.5,
2.8 Hz, H-2). 13C-APT NMR (101 MHz, CDCl3, HSQC):δ 169.9, 168.3 (C=O CO2Me, Ac), 137.8, 137.65 (Cq), 128.6, 128.5,
128.4, 128.0, 128.0, 127.9, 127.8, 127.6 (CHarom), 100.0 (C-1), 75.4 (C-3), 74.3 (CH2 Bn), 74.3 (C-2), 73.7 (C-2), 73.17 (d, J
= 32.8 Hz, CH(CF3)2), 72.7 (C-5), 69.3 (C-4), 52.7 (CH3 CO2Me), 21.0 (CH3 Ac); 13C-GATED NMR (101 MHz, CDCl3): δ
100.0 (JC1,H1 = 175 Hz, C-1 α); HRMS: [M+NH4]+ calcd for C26H30F6NO8 598.18707, found 598.18711.

S30
Methyl (4-O-acetyl-2,3-di-O-benzyl-1-deoxy-β-deuterio-D-mannopyranosyl uronate) (3G).

Donor 3 and triethylsilane-D were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 240 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 3G (39.6 mg, 95 μmol, 95%, α:β = < 1:20). Rf: 0.45 (7/3 pentane/EtOAc). [𝛼]26
𝐷 = -34.4° (c = 0.5, CHCl3); IR (neat):

698, 736, 1051, 1136, 1228, 1371, 1454, 1745, 2872, 2924; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY,
HSQC, NOESY) δ 7.39 – 7.17 (m, 10H, CHarom), 5.60 (dd, 1H, J = 4.9, 3.5 Hz, H-4), 4.63 (s, 2H, CH2 Bn), 4.53 (s, 2H, CH2
Bn), 4.19 (d, 1H, J = 3.2 Hz, H-5), 3.81 (m, 2H, H-2, H-3), 3.68 (d, 1H, J = 3.9 Hz, H-1), 3.61 (s, 3H, CH3 CO2Me), 2.06 (s,
3H, CH3 OAc); 2H NMR (61 MHz, CHCl3) δ 4.73 (D-1); 13C-APT NMR (101 MHz, CDCl3, HSQC, HMBC): δ 169.9, 168.9
(C=O CO2Me, Ac), 138.1, 137.8 (Cq), 131.2, 129.4, 128.6, 128.5, 128.4, 127.9, 127.8, 127.8, 127.8, 124.9 (CH arom), 73.8 (C-
5), 73.4 (C-3), 72.3 (CH2 Bn), 71.4 (C-2), 71.3 (CH2 Bn), 70.0 (C-4), 62.4 (C-1), 52.4 (CH3 CO2Me), 21.1 (CH3 Ac). HRMS:
[M+Na]+ calcd for C23H25DO7Na 438.16335, found 438.16264.

Methyl (allyl 4-O-acetyl-2,3-di-O-benzyl-1-deoxy-β-D-mannopyranosyl uronate) (3H).

Donor 3 and allyl trimethylsilane were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 96 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 3H (18.3 mg, 40 μmol, 40%, α:β = < 1:20). Rf: 0.25 (8/2 pentane/EtOAc). [𝛼]20
𝐷 = -38.8° (c = 1, CHCl3); IR (neat):

696, 735, 1026, 1055, 1114, 1228, 1368, 1746, 2855, 2924; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY,
HSQC, NOESY): δ 7.36 – 7.20 (m, 10H, CHarom), 5.71 – 5.58 (m, 1H, CHCH2 allyl), 5.53 (t, 1H, J = 9.8 Hz, H-4), 5.07 – 4.95
(m, 1H, CHCH2 allyl), 5.01 (d, 1H, J = 11.5 Hz, CHH Bn), 4.72 (d, 1H, J = 12.2 Hz, CHH Bn), 4.66 (d, 1H, J = 11.6 Hz, CHH
Bn), 4.61 (d, 1H, J = 12.2 Hz, CHH Bn), 3.83 (d, 1H, J = 9.9 Hz, H-5), 3.79 (d, 1H, J = 2.3 Hz, H-2), 3.71 (s, 3H, CH3 CO2Me),
3.60 (dd, 1H, J = 9.9, 2.7 Hz, H-3), 3.36 (t, 1H, J = 7.1 Hz, H-1), 2.56 – 2.48 (m, 1H, CHHCH allylic), 2.40 – 2.26 (m, 1H,
CHHCH), 2.01 (s, 3H, CH3 OAc); 13C-APT NMR (101 MHz, CDCl3, HSQC, HMBC): δ 169.9, 168.5 (C=O CO2Me, Ac),
138.3, 138.0 (Cq), 134.0 (CHCH2 allyl), 131.3, 131.2, 129.4, 129.1, 128.6, 128.6, 128.6, 128.5, 128.4, 128.3, 128.1, 128.1,
128.0, 127.9, 127.8, 127.7, 127.6, 127.6, 124.9 (CHarom), 117.9 (CHCH2 allyl), 88.6 (H-3), 79.1 (H-1), 77.6 (C-5), 74.5 (CH2
Bn), 73.7 (C-2), 72.6 (CH2 Bn), 69.5 (C-4), 52.7 (CH3 CO2Me), 35.4 (CH2CH allyl), 21.0 (CH3 Ac); HRMS: [M+NH4]+ calcd
for C26H34NO7 472.23298, found 472.23294.

Methyl 6-O-(methyl [4-O-acetyl-2,3-di-O-benzyl-β-D-mannopyranosyl uronate])-2,3,4-tri-O-benzyl-α-D-

glucopyranoside (30).

S31
Donor 3 and acceptor 10 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 30 (57.5 mg, 66 μmol, 66%, α:β = < 1:20). Rf: 0.54 (7/3 pentane/EtOAc). Spectroscopic data were in accord with those
previously reported.43 [𝛼]26 43 22
𝐷 = -11,6° (c = 1, CHCl3), (lit: [𝛼]𝐷 = -11.0° (c = 0.6, CHCl3)). IR (neat): 733, 906, 1028, 1055,

1101, 1242, 1361, 1452, 1748, 2908; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC, HMBC): δ 7.40
– 7.19 (m, 25H, CHarom), 5.48 (t, 1H, J = 9.6 Hz, H-4’), 5.02 (d, 1H, J = 10.9 Hz, CHH Bn), 4.91 (d, 1H, J = 12.6 Hz, CHH
Bn), 4.83 (d, 1H, J = 10.9 Hz, CHH Bn), 4.82 (d, 1H, J = 11.7 Hz, CHH Bn), 4.80 – 4.71 (m, 3H, CHH Bn, CHH Bn, CHH
Bn), 4.67 (d, 1H, J = 12.2 Hz, CHH Bn), 4.57 (d, 1H, J = 3.5 Hz, H-1), 4.50 (d, 1H, J = 4.4 Hz, CHH Bn), 4.47 (d, 1H, J = 5.3
Hz, CHH Bn), 4.36 (d, 1H, J = 12.4 Hz, CHH Bn), 4.16 – 4.09 (m, 2H, H-6, H-1’), 4.01 (t, 1H, J = 9.2 Hz, H-3), 3.79 (dq, 1H,
J = 7.3, 2.8, 1.7 Hz, H-5), 3.74 (d, 1H, J = 9.5 Hz, H-5’), 3.72 – 3.66 (m, 4H, CH3 CO2Me, H-2’), 3.50 (dd, 1H, J = 9.7, 3.5
Hz, H-2), 3.45 – 3.34 (m, 3H, H-4, H-6, H-3’), 3.31 (s, 3H, CH3 OMe), 2.02 (s, 3H, CH3 OAc); 13C-APT NMR (101 MHz,
CDCl3, HSQC, HMBC): δ 169.7, 168.1 (C=O CO2Me, Ac), 138.9, 138.4, 138.1, 137.8 (Cq), 128.6, 128.5, 128.5, 128.5, 128.3,
128.3, 128.2, 128.1, 128.1, 127.9, 127.8, 127.8, 127.6, 127.6 (CH arom), 101.7 (C-1’), 97.9 (C-1), 82.2 (H-3), 79.9 (H-2), 78.3
(H-3’), 77.7 (H-4), 75.9 (CH2 Bn), 74.9 (CH2 Bn), 73.8 (C-5’), 73.7 (CH2 Bn), 73.5 (CH2 Bn), 72.9 (C-2’), 71.6 (CH2 Bn), 69.8
(C-5), 69.0 (C-4’), 68.8 (C-6), 55.2 (CH3 OMe), 52.7 (CH3 CO2Me), 21.0 (CH3 Ac); 13C-GATED NMR (101 MHz, CDCl3) δ
101.7 (JC1,H1 = 155 Hz, C-1’ β); HRMS: [M+Na]+ calcd for C51H56O13Na 899.36131, found 899.36111.

Methyl 4-O-(methyl [4-O-acetyl-2,3-di-O-benzyl-β-D-mannopyranosyl uronate])-2,3,6-tri-O-benzyl-α-D-

glucopyranoside (31).

Donor 3 and acceptor 11 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 31 (53.1 mg, 61 μmol, 61%, α:β = < 1:20). Rf: 0.65 (7/3 pentane/EtOAc); [𝛼]26
𝐷 = -30.2° (c = 1, CHCl3). IR (neat): 733,

1026, 1096, 1366, 1454, 1746, 2920; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC, HMBC): δ 7.39
– 7.19 (m, 25H, CHarom), 5.41 (t, 1H, J = 9.7 Hz, H-4’), 5.17 (d, 1H, J = 11.3 Hz, CHH Bn), 4.78 – 4.72 (m, 4H, CHH Bn,
CHH Bn, CHH Bn, CHH Bn), 4.64 – 4.56 (m, 3H, CHH Bn, CHH Bn, H-1), 4.44 (d, 1H, J = 12.3 Hz, CHH Bn), 4.40 (s, 1H,
H-1’), 4.36 (d, 1H, J = 12.3 Hz, CHH Bn), 4.28 (d, 1H, J = 12.1 Hz, CHH Bn), 3.89 (m, 2H, H-3, H-5), 3.68 – 3.63 (m, 1H, ),
3.62 (d, 1H, J = 2.7 Hz, H-2’), 3.57 (d, 1H, J = 9.7 Hz, H-5’), 3.55 – 3.45 (m, 5H, H-2, CH3 CO2Me, C-6), 3.38 (s, 3H, CH3
OMe), 3.18 (dd, 1H, J = 9.7, 2.8 Hz, H-3’), 2.01 (s, 3H, CH3 OAc); 13C-APT NMR (101 MHz, CDCl3, HSQC, HMBC): δ
169.7, 167.9 (C=O CO2Me, Ac), 139.6, 138.5, 138.3, 138.1, 137.9 (Cq), 128.7, 128.5, 128.5, 128.2, 128.2, 128.2, 128.2, 128.1,
128.0, 127.9, 127.9, 127.8, 127.5, 127.4, 127.1 (CHarom), 101.1 (C-1’), 98.4 (C-1), 80.4 (C-3), 79.3 (H-2), 78.8 (C-3’), 78.2 (C-
5), 75.4 (CH2 Bn), 74.6 (C-2’), 74.2 (C-5’), 73.7 (CH2 Bn), 73.7 (CH2 Bn), 73.6 (CH2 Bn), 71.8 (CH2 Bn), 69.5 (H-4), 69.0 (C-
4’), 68.7 (C-6), 55.4 (CH3 OMe), 52.5 (CH3 CO2Me), 20.9 (CH3 Ac); 13C-GATED NMR (101 MHz, CDCl3): δ 101.1 (JC1,H1 =
158 Hz, C-1’ β); HRMS: [M+Na]+ calcd for C51H56O13Na 899.36131, found 899.36094.

S32
Methyl (methyl 4-O-[methyl (4-O-acetyl-2,3-di-O-benzyl-α/β-D-mannopyranosyl uronate)]-2,3-di-O-benzyl-α-D-
glucopyranosyl uronate) (32).

Donor 3 and acceptor 12 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 48 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 32 (58.0 mg, 71 μmol, 71%, α:β = 1:10). Rf: 0.38 (7/3 pentane/EtOAc); [𝛼]26
𝐷 = -31.2° (c = 1, CHCl3). IR (neat): 733,

1026, 1043, 1229, 1454, 1744, 2855, 2926; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC, HMBC):
δ 7.42 – 7.23 (m, 20H, CHarom), 5.44 (t, 1H, J = 9.8 Hz, H-4’), 5.19 (d, 1H, J = 11.3 Hz, CHH Bn), 4.88 – 4.69 (m, 4H, CHH
Bn, CHH Bn, CHH Bn, CHH Bn), 4.62 – 4.38 (m, 5H, CHH Bn, CHH Bn, CHH Bn, H-1’, H-1), 4.08 (d, 1H, J = 9.3 Hz, H-
5), 3.96 – 3.85 (m, 2H, H-3, H-4), 3.76 (d, 1H, J = 2.7 Hz, H-2’), 3.70 (d, 1H, J = 9.7 Hz, H-5’), 3.59 (s, 3H, CH3 CO2Me),
3.53 – 3.46 (m, 4H, CH3 CO2Me, H-2), 3.46 – 3.37 (m, 4H, CH3 OMe, H-3’), 2.00 (s, 3H, CH3 OAc); 13C-APT NMR (101
MHz, CDCl3, HSQC, HMBC): δ 170.2, 169.8, 167.8 (C=O CO2Me, Ac), 139.4, 138.6, 138.1, 137.9 (Cq), 128.6, 128.5, 128.5,
128.5, 128.4, 128.3, 128.3, 128.2, 128.2, 128.1, 127.9, 127.8, 127.7, 127.6, 127.5, 127.2 (CH arom), 102.3 (C-1’), 98.9 (C-1),
80.7 (C-4), 80.0 (C-3), 78.6 (C-2), 78.4 (C-3’), 75.7 (CH2 Bn), 74.7 (C-2’), 74.5 (CH2 Bn), 73.9 (CH2 Bn, C-5’), 71.8 (CH2
Bn), 69.6 (C-5), 69.0 (C-4’), 56.0 (CH3 OMe), 52.6 (CH3 CO2Me), 52.5 (CH3 CO2Me), 20.9 (CH3 Ac); 13C-GATED NMR
(101 MHz, CDCl3): δ 102.3 (JC1,H1 = 154 Hz, C-1’ β); Diagnostic peaks α-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY,
HSQC): 5.44 (m, 0.20H, H-1’, H-4’), 2.00 (s, 0.30H, CH3 OAc); HRMS: [M+Na]+ calcd for C45H50O14Na 837.30928, found
837.30903.

Methyl 4-O-(methyl [4-O-acetyl-2,3-di-O-benzyl-β-D-mannopyranosyl uronate])-2,3,6-tri-O-benzyl-β-D-

galactopyranoside (33).

Donor 3 and acceptor 13 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 33 (66.8 mg, 76 μmol, 76%, α:β = < 1:20). Rf: 0.39 (7/3 pentane/EtOAc); [𝛼]26
𝐷 = -31.6° (c = 1, CHCl3). IR (neat): 735,

1026, 1051 1231, 1748, 2870; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC, HMBC): δ 7.35 – 7.22
(m, 25H, CHarom), 5.45 (t, 1H, J = 9.8 Hz, H-4’), 4.95 (d, 1H, J = 12.7 Hz, CHH Bn), , 4.93 (d, 1H, J = 10.9 Hz, CHH Bn), 4.85
(d, 1H, J = 12.7 Hz, CHH Bn), 4.78 (d, 1H, J = 11.7 Hz, CHH Bn), 4.75 (s, 1H, H-1’), 4.67 (d, 1H, J = 11.0 Hz, CHH Bn),
4.60 (d, 1H, J = 11.7 Hz, CHH Bn), 4.58 (d, 1H, J = 11.7 Hz, CHH Bn), 4.51 (d, 1H, J = 11.7 Hz, CHH Bn), 4.43 (d, 1H, J =
12.3 Hz, CHH Bn), 4.30 (d, 1H, J = 7.6 Hz, H-1), 4.22 (d, 1H, J = 12.3 Hz, CHH Bn), 4.15 (d, 1H, J = 2.5 Hz, H-2), 3.95 (d,
1H, J = 2.8 Hz, H-2’), 3.90 (dd, 1H, J = 9.7, 6.3 Hz, H-6), 3.74 (dd, 1H, J = 9.6, 5.7 Hz, H-6), 3.70 – 3.63 (m, 2H, H-5, H-5’),
3.63 – 3.56 (m, 7H, H-4, CH3 OMe, CH3 CO2Me), 3.56 – 3.50 (m, 1H, H-3), 3.24 (dd, 1H, J = 9.8, 2.9 Hz, H-3’), 1.99 (s, 3H,
CH3 OAc); 13C-APT NMR (101 MHz, CDCl3, HSQC, HMBC): δ 169.8, 168.1 (C=O CO2Me, Ac), 138.8, 138.7, 138.3, 138.0
(Cq), 128.7, 128.6, 128.5, 128.3, 128.2, 128.0, 127.9, 127.8, 127.8, 127.7, 127.5, 127.5 (CH arom), 105.1 (C-1), 101.9 (C-1’),
81.8 (C-3), 79.6 (C-5), 79.0 (C-3’), 75.1 (CH2 Bn), 73.9 (C-5), 73.8 (CH2 Bn), 73.6 (CH2 Bn), 73.6 (C-4), 73.2 (C-2), 72.5 (C-

S33
2’), 71.3 (CH2 Bn), 69.4 (C-6), 68.9 (C-4’ ),57.2 (CH3 CO2Me), 52.6 (CH3 OMe), 20.9 (CH3 Ac); HRMS: [M+Na]+ calcd for
C51H56O13Na 899.36131, found 899.36109.

Methyl 2-O-(methyl [4-O-acetyl-2,3-di-O-benzyl-α/β-D-mannopyranosyl uronate])-3-O-benzyl-4,6-bezylidene-α-D-

mannopyranoside (34).

Donor 3 and acceptor 14 were condensed using the general procedure for Tf2O/Ph2SO mediated glycosylations (for an
additional 16 hours at -40°C) and purified by flash column chromatography (9/1 to 7/3 pentane/EtOAc) to yield glycosylation
product 34 (60.4 mg, 77 μmol, 77%, α:β = 1:7.1). Rf: .34 (7/3 pentane/EtOAc); [𝛼]26
𝐷 = -48.6° (c = 1, CHCl3). IR (neat): 735,

1026, 1053, 1230, 1369, 1454, 1748, 2868, 2924; Data for the β-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC,
HMBC): δ 7.51 – 7.22 (m, 15H, CHarom), 5.60 – 5.53 (m, 2H, H-4’, CHPh), 5.02 (d, 1H, J = 12.5 Hz, CHH Bn), 4.93 (d, 1H, J
= 12.5 Hz, CHH Bn), 4.83 (d, 1H, J = 12.1 Hz, CHH Bn), 4.72 (d, 1H, J = 1.1 Hz, H-1), 4.64 (d, 1H, J = 12.1 Hz, CHH Bn),
4.62 (s, 1H, H-1’), 4.50 (d, 1H, J = 12.4 Hz, CHH Bn), 4.36 – 4.31 (m, 2H, CHH Bn, H-2), 4.29 – 4.24 (m, 1H, H-6), 4.15 –
4.07 (m, 1H, H-4), 4.01 – 3.91 (m, 2H, H-2’, H-3), 3.85 (d, 1H, J = 9.7 Hz, H-5’), 3.82 – 3.75 (m, 2H, H-5, H-6), 3.63 (s, 3H,
CH3 CO2Me), 3.48 (dd, 1H, J = 9.7, 2.9 Hz, H-3’), 3.35 (s, 3H, CH3 OMe), 2.03 (s, 3H, CH3 OAc); 13C-APT NMR (101 MHz,
CDCl3, HSQC, HMBC): δ 169.7, 167.9 (C=O CO2Me, Ac), 138.8, 138.5, 137.8, 137.7 (Cq), 129.0, 128.7, 128.5, 128.4, 128.4,
128.4, 128.3, 128.3, 127.9, 127.9, 127.8, 127.8, 127.7, 127.6, 127.5, 127.4, 126.3, 126.2 (Carom), 101.8 (CHPh), 99.8 (C-1’),
99.2 (C-1), 78.5 (C-4), 78.2 (C-3), 74.0 (C-5’), 73.9 (H-2), 73.9 (H-3), 73.9 (CH2 Bn), 73.0 (H-2’), 71.3 (CH2 Bn), 71.0 (CH2
Bn), 69.0 (C-6), 68.8 (C-4’), 64.1 (H-5), 55.1 (CH3 OMe), 52.7 (CH3 CO2Me), 21.0 (CH3 Ac); 13C-GATED NMR (101 MHz,
CDCl3): δ 99.8 (JC1,H1 = 154 Hz, C-1’ β); Diagnostic peaks α-anomer: 1H NMR (400 MHz, CDCl3, HH-COSY, HSQC, HMBC):
5.59 (s, 0.14H, CHPh), 5.50 (t, 0.14H, J = 7.5 Hz, H-4’), 5.45 (d, 0.14H, J = 4.0 Hz, H-1’), 3.66 (s, 0.42H, CH3 CO2Me), 3.35
(s, 0.42H, CH3 OMe), 2.03 (s, 0.42H, CH3 OAc); 13C-APT NMR (101 MHz, CDCl3, HSQC, HMBC): δ 100.3 (C-1’), 69.5 (C-
4’); HRMS: [M+NH4]+ calcd for C44H52NO13 802.34332, found 802.34387.

Literature references in Supporting Information

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2 Spartan ’04 and J. Kong, et al., 2004, Wavefunction Inc.
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1716.
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4319–4328.
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12 P. Blom, B. Ruttens, S. Van Hoof, I. Hubrecht, J. Van der Eycken, B. Sas, J. Van hemel and J. Vandenkerckhove, J. Org.
Chem., 2005, 70, 10109–10112.
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Lett., 2009, 19, 4122–4125.

S34
14 A. J. Janczuk, W. Zhang, P. R. Andreana, J. Warrick and P. G. Wang, Carbohydr. Res., 2002, 337, 1247–1259.
15 R. W. Gantt, R. D. Goff, G. J. Williams and J. S. Thorson, Angew. Chem. Int. Ed., 2008, 47, 8889–8892.
16 D. Crich and W. Cai, J. Org. Chem., 1999, 64, 4926–4930.
17 J. D. C. Codée, L. J. van den Bos, A.-R. de Jong, J. Dinkelaar, G. Lodder, H. S. Overkleeft and G. A. van der Marel, J.
Org. Chem., 2009, 74, 38–47.
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16799.
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9411.
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36 K. S. Kim, D. B. Fulse, J. Y. Baek, B.-Y. Lee and H. B. Jeon, J. Am. Chem. Soc., 2008, 130, 8537–8547.
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41 X. Nie and G. Wang, J. Org. Chem., 2005, 70, 8687–8692.
42 M. Moumé-Pymbock and D. Crich, J. Org. Chem., 2012, 77, 8905–8912.
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S35
NMR spectra of new compounds
1H NMR, 400 MHz, CDCl3 of compound 1B

13C-APT NMR, 101 MHz, CDCl3 of compound 1B

S36
COSY NMR of compound 1B

S37
HSQC NMR of compound 1B

13C GATED NMR, 101 MHz, CDCl3 of compound 1B

S38
1H NMR, 400 MHz, CDCl3 of compound 1C

13C-APT NMR, 101 MHz, CDCl3 of compound 1C

S39
COSY NMR of compound 1C

HSQC NMR of compound 1C

S40
13C GATED NMR, 101 MHz, CDCl3 of compound 1C

1H NMR, 400 MHz, CDCl3 of compound 1D

S41
13C-APT NMR, 101 MHz, CDCl3 of compound 1D

COSY NMR of compound 1D

S42
HSQC NMR of compound 1D

13C GATED NMR, 101 MHz, CDCl3 of compound 1D

S43
1H NMR, 400 MHz, CDCl3 of compound 1E

13C-APT NMR, 101 MHz, CDCl3 of compound 1D

S44
COSY NMR of compound 1E

HSQC NMR of compound 1E

S45
HMBC NMR of compound 1E

13C GATED NMR, 101 MHz, CDCl3 of compound 1E

S46
1H NMR, 400 MHz, CDCl3 of compound 1F

13C-APT NMR, 101 MHz, CDCl3 of compound 1F

S47
COSY NMR of compound 1F

HSQC NMR of compound 1F

S48
HMBC NMR of compound 1F

HMBC-GATED NMR of compound 1F

S49
1H NMR, 400 MHz, CDCl3 of compound 1G

13C-APT NMR, 101 MHz, CDCl3 of compound 1G

S50
COSY NMR of compound 1G

HSQC NMR of compound 1G

S51
HMBC-GATED NMR of compound 1G

NOESY NMR of compound 1G

S52
2D NMR, 77 MHz, CHCl3 of compound 1G

1H NMR, 400 MHz, CDCl3 of compound 22

S53
13C-APT NMR, 101 MHz, CDCl3 of compound 22

COSY NMR of compound 22

S54
HSQC NMR of compound 22

13C GATED NMR, 101 MHz, CDCl3 of compound 22

S55
1H NMR, 400 MHz, CDCl3 of compound 23

13C-APT NMR, 101 MHz, CDCl3 of compound 23

S56
COSY NMR of compound 23

HSQC NMR of compound 23

S57
13C GATED NMR of compound 23

1H NMR, 400 MHz, CDCl3 of compound 2B

S58
13C-APT NMR, 101 MHz, CDCl3 of compound 2B

COSY NMR of compound 2B

S59
HSQC NMR of compound 2B

1H NMR, 400 MHz, CDCl3 of compound 2C

S60
13C-APT NMR, 101 MHz, CDCl3 of compound 2C

COSY NMR of compound 2C

S61
HSQC NMR of compound 2C

1H NMR, 400 MHz, CDCl3 of compound 2D

S62
13C-APT NMR, 101 MHz, CDCl3 of compound 2D

COSY NMR of compound 2D

S63
HSQC NMR of compound 2D

1H NMR, 400 MHz, CDCl3 of compound 2E

S64
13C-APT NMR, 101 MHz, CDCl3 of compound 2E

COSY NMR of compound 2E

S65
HSQC NMR of compound 2E

1H NMR, 400 MHz, CDCl3 of compound 2F

S66
13C-APT NMR, 101 MHz, CDCl3 of compound 2F

COSY NMR of compound 2F

S67
HSQC NMR of compound 2F

HMBC NMR of compound 2F

S68
1H NMR, 400 MHz, CDCl3 of compound 2G

13C-APT NMR, 101 MHz, CDCl3 of compound 2G

S69
COSY NMR, CDCl3 of compound 2G

HSQC NMR, CDCl3 of compound 2G

S70
2H NMR, 61 MHz, CHCl3 of compound 2G

1H NMR, 400 MHz, CDCl3 of compound 27

S71
13C-APT NMR, 101 MHz, CDCl3 of compound 27

COSY NMR of compound 27

S72
HSQC NMR of compound 27

HMBC NMR of compound 27

S73
1H NMR, 400 MHz, CDCl3 of compound 28

13C-APT NMR, 101 MHz, CDCl3 of compound 28

S74
COSY NMR of compound 28

HSQC NMR of compound 28

S75
HMBC NMR of compound 28

1H NMR, 400 MHz, CDCl3 of compound 3

S76
13C-APT NMR, 101 MHz, CDCl3 of compound 3

COSY NMR of compound 3

S77
HSQC NMR of compound 3

1H NMR, 400 MHz, CDCl3 of compound 3A

S78
13C-APT NMR, 101 MHz, CDCl3 of compound 3A

COSY NMR of compound 3A

S79
HSQC NMR of compound 3A

1H NMR, 400 MHz, CDCl3 of compound 3B

S80
13C-APT NMR, 101 MHz, CDCl3 of compound 3B

COSY NMR of compound 3B

S81
HSQC NMR of compound 3B

13C GATED NMR, 101 MHz, CDCl3 of compound 3B

S82
1H NMR, 400 MHz, CDCl3 of compound 3C

13C-APT NMR, 101 MHz, CDCl3 of compound 3C

S83
COSY NMR of compound 3C

HSQC NMR of compound 3C

S84
13C GATED NMR, 101 MHz, CDCl3 of compound 3C

1H NMR, 400 MHz, CDCl3 of compound 3D

S85
13C-APT NMR, 101 MHz, CDCl3 of compound 3D

COSY NMR of compound 3D

S86
HSQC NMR of compound 3D

13C GATED NMR, 101 MHz, CDCl3 of compound 3D

S87
1H NMR, 400 MHz, CDCl3 of compound 3E

13C-APT NMR, 101 MHz, CDCl3 of compound 3E

S88
COSY NMR of compound 3E

HSQC NMR of compound 3E

S89
13C GATED NMR, 101 MHz, CDCl3 of compound 3E

1H NMR, 400 MHz, CDCl3 of compound 3F

S90
13C-APT NMR, 101 MHz, CDCl3 of compound 3F

COSY NMR of compound 3F

S91
HSQC NMR of compound 3F

HMBC-GATED of compound 3F

S92
NOESY of compound 3F

1H NMR, 400 MHz, CDCl3 of compound 3G

S93
13C-APT NMR, 101 MHz, CDCl3 of compound 3G

COSY NMR of compound 3G

S94
HSQC NMR of compound 3G

HMBC NMR of compound 3G

S95
NOESY NMR of compound 3G

2D NMR, 77 MHz, CHCl3 of compound 3G

S96
1H NMR, 400 MHz, CDCl3 of compound 3H

13C NMR, 101 MHz, CDCl3 of compound 3H

S97
COSY NMR of compound 3H

HSQC NMR of compound 3H

S98
NOESY NMR of compound 3H

1H NMR, 400 MHz, CDCl3 of compound 31

S99
13C-APT NMR, 101 MHz, CDCl3 of compound 31

COSY NMR of compound 31

S100
HSQC NMR of compound 31

13C-GATED NMR, 101 MHz, CDCl3 of compound 31

S101
1H NMR, 400 MHz, CDCl3 of compound 32

13C-APT NMR, 101 MHz, CDCl3 of compound 32

S102
COSY NMR of compound 32

HSQC NMR of compound 32

S103
HMBC NMR of compound 32

1H NMR, 400 MHz, CDCl3 of compound 33

S104
13C-APT NMR, 101 MHz, CDCl3 of compound 33

COSY NMR of compound 33

S105
HSQC NMR of compound 33

HMBC NMR of compound 33

S106
1H NMR, 400 MHz, CDCl3 of compound 34

13C-APT NMR, 101 MHz, CDCl3 of compound 34

S107
COSY NMR of compound 34

HSQC NMR of compound 34

S108
HMBC NMR of compound 34

S109
Methyl 2,3,4-tri-O-methyl mannopyranosyl uronate oxocarbenium ion atom coordinates and
energies of the 3H4, 4H3, B2,5 conformations

Gas phase energy = -842.538825958 Hartree

Zero-point correction= 0.272524 (Hartree/Particle)

Thermal correction to Energy= 0.290829

Thermal correction to Enthalpy= 0.291773

Thermal correction to Gibbs Free Energy= 0.224624

Sum of electronic and zero-point Energies= -842.266302

Sum of electronic and thermal Energies= -842.247997

Sum of electronic and thermal Enthalpies= -842.247053

Sum of electronic and thermal Free Energies= -842.314202

Solvated (methylene chloride) energy = -842.605384995 Hartree

Total energy: (-842.605384995 + 0.272524) Hartree

* 627.509469 kcal mol-1 Hartree-1 = -528571.845 kcal mol-1

S110
---------------------------------------------------------------------

Center Atomic Atomic Coordinates (Angstroms)

Number Number Type X Y Z

---------------------------------------------------------------------

1 6 0 0.998510 0.913869 -0.571364

2 6 0 -0.021284 1.268433 0.521163

3 6 0 -0.943782 0.066979 0.782220

4 6 0 -1.719208 -0.205693 -0.525454

5 6 0 -0.774646 -0.331514 -1.663688

6 8 0 0.366935 0.182969 -1.716623

7 6 0 2.200015 0.106263 -0.069813

8 8 0 -2.513413 -1.358974 -0.502794

9 8 0 -0.113465 -1.021864 1.105770

10 8 0 -0.838877 2.342997 0.115048

11 8 0 2.410221 -1.005123 -0.751611

12 8 0 2.865832 0.537257 0.835501

13 6 0 3.546837 -1.807672 -0.333305

14 6 0 -0.349455 3.640498 0.475033

15 6 0 -0.664580 -1.988750 2.010564

16 6 0 -3.919252 -1.127016 -0.318667

17 1 0 1.389432 1.811168 -1.060195

18 1 0 0.540859 1.493889 1.435258

19 1 0 -1.644265 0.317446 1.587998

20 1 0 -2.293334 0.710222 -0.776227

21 1 0 -1.058999 -0.904758 -2.555971

22 1 0 3.558044 -2.656429 -1.011290

23 1 0 4.463550 -1.225027 -0.421186

24 1 0 3.407502 -2.133257 0.697333

25 1 0 -0.242499 3.722357 1.561576

26 1 0 0.612395 3.855660 -0.004060

27 1 0 -1.090826 4.355942 0.123457

28 1 0 -1.500604 -2.520232 1.552232

29 1 0 0.139307 -2.688960 2.232685

30 1 0 -0.989456 -1.503551 2.937141

31 1 0 -4.386652 -2.109729 -0.301400

32 1 0 -4.113785 -0.613880 0.628670

33 1 0 -4.327461 -0.541342 -1.148481

---------------------------------------------------------------------

S111
Gas phase energy = -842.528599137 Hartree

Zero-point correction= 0.272955 (Hartree/Particle)

Thermal correction to Energy= 0.291338

Thermal correction to Enthalpy= 0.292282

Thermal correction to Gibbs Free Energy= 0.225197

Sum of electronic and zero-point Energies= -842.255644

Sum of electronic and thermal Energies= -842.237261

Sum of electronic and thermal Enthalpies= -842.236317

Sum of electronic and thermal Free Energies= -842.303402

Solvated (methylene chloride) energy = -842.597802066 Hartree

Total energy: (-842.597802066 + 0.272955) Hartree

* 627.509469 kcal mol-1 Hartree-1 = -528566.818 kcal mol-1

Relative energy to 3H4: +5.03 kcal mol-1

S112
---------------------------------------------------------------------

Center Atomic Atomic Coordinates (Angstroms)

Number Number Type X Y Z

---------------------------------------------------------------------

1 6 0 1.005063 -0.073754 -0.638312

2 6 0 -0.150594 0.692640 0.006931

3 6 0 -1.477849 0.281978 -0.636583

4 6 0 -1.661319 -1.227993 -0.492138

5 6 0 -0.430310 -2.020045 -0.779304

6 8 0 0.735326 -1.548995 -0.762598

7 6 0 2.321347 0.010106 0.148169

8 8 0 -1.731255 -1.612307 0.883241

9 8 0 -2.561987 0.918447 -0.001455

10 8 0 0.130612 2.053157 -0.246676

11 8 0 3.318499 -0.470356 -0.580168

12 8 0 2.401671 0.453461 1.264244

13 6 0 4.629328 -0.490867 0.046913

14 6 0 0.154644 2.896603 0.915304

15 6 0 -3.204678 1.935251 -0.779107

16 6 0 -2.925329 -2.318394 1.276371

17 1 0 1.164778 0.251724 -1.672067

18 1 0 -0.185976 0.481224 1.079375

19 1 0 -1.438093 0.517906 -1.711253

20 1 0 -2.512417 -1.592127 -1.079055

21 1 0 -0.473437 -3.109578 -0.889628

22 1 0 5.292920 -0.921729 -0.697513

23 1 0 4.932334 0.525272 0.299086

24 1 0 4.599049 -1.106180 0.946177

25 1 0 0.371522 3.900645 0.552820

26 1 0 -0.816045 2.890061 1.419092

27 1 0 0.937660 2.577181 1.607738

28 1 0 -3.641541 1.515979 -1.692561

29 1 0 -4.000257 2.338710 -0.153962

30 1 0 -2.503890 2.732814 -1.040841

31 1 0 -3.022988 -3.262496 0.733322

32 1 0 -2.812493 -2.516244 2.340574

33 1 0 -3.795874 -1.683572 1.096524

---------------------------------------------------------------------

S113
Gas Phase Energy = -842.526083446 Hartree

Zero-point correction= 0.272637 (Hartree/Particle)

Thermal correction to Energy= 0.290545

Thermal correction to Enthalpy= 0.291489

Thermal correction to Gibbs Free Energy= 0.225398

Sum of electronic and zero-point Energies= -842.253447

Sum of electronic and thermal Energies= -842.235539

Sum of electronic and thermal Enthalpies= -842.234594

Sum of electronic and thermal Free Energies= -842.300686

Solvated (methylene chloride) energy = -842.595751241 Hartree

Total energy: (-842.595751241 + 0.272637) Hartree

* 627.509469 kcal mol-1 Hartree-1 = -528565.730 kcal mol-1

Relative energy to 3H4: +6.12 kcal mol-1

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Center Atomic Atomic Coordinates (Angstroms)

Number Number Type X Y Z

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1 6 0 0.951799 -0.354386 -0.392622

2 6 0 0.104904 0.881365 -0.093108

3 6 0 -1.423336 0.631498 -0.199092

4 6 0 -1.730559 -0.912199 -0.500957

5 6 0 -0.826734 -1.765417 0.267468

6 8 0 0.415807 -1.542707 0.328512

7 6 0 2.399514 -0.216937 0.097813

8 8 0 -3.031730 -1.318598 -0.245004

9 8 0 -2.180098 1.083858 0.884791

10 8 0 0.550778 1.820439 -1.048358

11 8 0 3.159170 -1.141783 -0.468968

12 8 0 2.754624 0.614603 0.891892

13 6 0 4.557097 -1.166944 -0.071314

14 6 0 0.604267 3.170305 -0.565311

15 6 0 -1.956782 0.451837 2.138999

16 6 0 -4.032709 -0.756005 -1.106015

17 1 0 0.929132 -0.607587 -1.459804

18 1 0 0.350224 1.217566 0.919361

19 1 0 -1.780396 1.192649 -1.064659

20 1 0 -1.427375 -1.046353 -1.567504

21 1 0 -1.174106 -2.644581 0.825399

22 1 0 4.998395 -1.981390 -0.638788

23 1 0 5.026710 -0.215931 -0.322107

24 1 0 4.632446 -1.351163 1.000327

25 1 0 -0.387560 3.524236 -0.265372

26 1 0 1.297166 3.247730 0.278534

27 1 0 0.968064 3.774865 -1.394533

28 1 0 -0.943191 0.618409 2.519212

29 1 0 -2.672755 0.885721 2.834996

30 1 0 -2.157529 -0.628744 2.074918

31 1 0 -4.958654 -1.272238 -0.860805

32 1 0 -4.151573 0.314193 -0.919609

33 1 0 -3.782161 -0.932585 -2.157653

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