SELECTIVITY 1

SELECTIVITY
Science 1983, 219, 245
Chemoselectivity
preferential reactivity of one functional group (FG) over another

- Chemoselective reduction of C=C over C=O:

O H2, O
Pd/C

- Chemoselective reduction of C=O over C=C:

O OH O
NaBH4
+

O OH
NaBH4, CeCl3
only

- Epoxidation:
MCPBA
+
OH OH OH
O O
(2 : 1)

VO(acac)2,
tBuOOH
exclusively
OH OH
O

Regioselectivity
- Hydration of C=C:
1) B2H6
2) H2O2, NaOH OH
R

R OH

R
1) Hg(OAc)2, H2O
2) NaBH4

- Friedel-Crafts Reaction:
O
RCOCl,
AlCl3 R
+ R

O
O
RCOCl,
SiMe3 AlCl3 R
 SELECTIVITY 2
- Diels-Alder Reaction:
R O R O R

+ +

O
major minor
O R O
R R
+ +

O
major minor

O O

O O OAc O O OAc
H H

O OAc O OAc O OAc

Raney Ni, H2

O O SPh O O SPh O O
H H H

Change in mechanism:
SPh
PhSH, H+
R

SPh
R
PhSH, (PhCO2)2

Stereochemistry:
Relative stereochemistry: Stereochemical relationship between two or more stereogenic centers
within a molecule

H H H H
HO OH
enantiomers
cholesterol same relative stereochemistry

syn: on the same side ( cis)

anti: on the opposite side (trans)

- differences in relative stereochemistry lead to diastereomers.

Diastereomers= stereoisomers which are not mirror images; usually have different physical
properties
 SELECTIVITY 3
Absolute Stereochemistry: Absolute stereochemical assignment of each stereocenter (R vs S)
Cahn-Ingold-Prelog Convention (sequence rules)

- differences in absolute stereochemistry (of all stereocenters within the molecule) leads to
enantiomers.

- Reactions can "create" stereocenters

O MeMgBr HO CH3

Ph H Ph H

MeMgBr
H 3C OH

Ph H
O enantiomers
Ph (racemic product)
H
HO CH3

Ph H
MeMgBr

Diastereomeric transition states- not necessarily equal in energy

Me Me Me Me
N O N
Ph O H
O Zn Zn
O
CH3 CH3 CH3 CH3
H Ph
Zn Zn
H 3C H 3C

HO CH3 HO CH3

Ph H H Ph

Diastereoselectivity

CH3MgBr
CH3 + CH3
Ph Ph
Ph CHO
HO H H OH
syn anti

Diastereomers

Cram Model (Cram's Rule): empirical

O
O O
M S
M H 3C H
R S Nu
CH3MgBr CH3MgBr
L
favored
R H
L Ph
 SELECTIVITY 4
Felkin-Ahn Model
O M S O

L Nu L
Nu

S M R
R

favored disfavored

Chelation Control Mode

M
OR
O
O
HO M
OR CH3MgBr S
R CH3MgBr
S M Nu
S M R OR
favored
R
HO
TBSO MgBr TBSO
O
H O relative stereochemical control
H O

OBn OBn

Stereospecific
Stereochemictry of the product is related to the reactant in a mechanistically defined manner; no
other stereochemical outcome is mechanistically possible.
i.e.; SN2 reaction- inversion of configuration is required
Br2 H Br
H 3C
meso
H
Br CH3

Br2 CH3 Br Br CH3

H H
H
+ H
Br CH3 CH3 Br

enantiomers (racemic)

Stereoselective
When more than one stereochemical outcome is possible, but one is formed in excess (even if that
excess is 100:0).
CH3 H
H2, Pd/C H H
H + CH3
H H

α-pinene only isomer not observed

O O O O O O
LDA, CH3I
N O N O + N O Diastereoselective
Enantiospecific
S S S
(96 : 4)

Diasteromers