7-MEMBERED RING FORMATION 168
Medium Sized Rings
7-Membered Rings
[4+2] cycloadditions
- [4+2] cycloadditions between dienes and allylcations leads to cycloheptadienes
review: ACIEE 1984, 23 , 1; ACIEE 1973, 12 , 819
+ + +
I CF3CO2Ag ACIEE 1973, 12, 819
+ ACIEE 1984, 23, 1
-78°C
Me
ZnCl2, -30°C
ACIEE 1982,
+
21, 442
+
H H
F3CCO2
SiMe3 SiMe3
O O
OTMS
+ JACS 1982,
104 , 1330
ZnCl2
Br
OMe O O
O O + O
O O O
+ O
O
O O JACS 1979, 101, 226
mCPBA
O
HO
- Noyori [4+2] cycloaddition of α,α'-dibromoketones and dienes
review: ACR 1979, 12 , 61
O Fe2(CO)9 O
-or- OM
R R ACR 1979, 61
R R Zn-Cu R R
Organic Reactions
+ 1983, 29, 163
Br Br
7-MEMBERED RING FORMATION 169
O O O
Br Br Fe2(CO)9 Br Br Zn
O O O
Br Br
CO2Me
O N
MeO2C
Br Br 1) N JACS 1978, 100 , 1786
Tetrahedron 1985, 41, 5879
Br Br Fe2(CO)9
2) Zn O
OMe O O
O O + O
O O O
+ O
O
O O
mCPBA JACS 1979, 101, 226
O
HO
O O
1) O 1) H2, Pd/C OH
Me Me O
2) CF3CO3H JACS 1972, 94, 3940
O JOC 1976, 41, 2075
Br Br Fe2(CO)9 O
O H H
O CO2H
O O Me Me Me
O 1) CF3CO3H
OH
2) LDA, MeI JCSCC 1985, 55
O
O OBn Me OBn OH OH OBn
O
O
- [4+2] cycloaddition between pentadienyl cations and olefins
+ + +
O OH
HO - O
∆ O Tetrahedron 1966, 22, 2387
+ O
JOC 1987, 52, 759
O O
7-MEMBERED RING FORMATION 170
O
MeO OMe
OMe
SnCl4 JACS 1977, 99, 8073
JACS 1979, 101, 6767
JACS 1981, 103, 2718
OMe
O O
Seven-Membered Rings from Funnctionalization of Tropone
Organic Reactions 1997, 49, 331-425
O O-
O
Cl
R R
JOC 1988, 53, 4596
JACS 1987, 109, 3147
O
- [6+4] cycloadditions of tropones with dienes
[6+4]
O
150°C JACS 1986, 108, 4655
O
JOC 1986, 51, 2400
(88%)
HO HO
HO OH
Ingenol
- [4+2] cycloaddition between tropone and olefins
O
O
[4+2]
150°C
(81%)
Radical Ring Expansion Reactions
- one carbon ring expansions
O O O
Br •
nBu3SnH,
NaH, CH2Br2 CO2Me AIBN CO2Me
CO2Me
(CH2)n (CH2)n (CH2)n
n = 1,2,3
O O
•O nBu3SnH JACS 1987,109, 3493
CO2Me JACS 1987,109 , 6548
(CH2)n •
(CH2)n (CH2)n
CO2Me CO2Me
7-MEMBERED RING FORMATION 171
O O O
Bu3SnLi
CH3 •
BrCH2SePh SePh
SnBu3 SnBu3
Tetrahedron 1989, 45, 909
O Tetrahedron 1991, 47, 6795
•O
+ Bu3Sn•
SnBu3
- more than one carbon expansion
O X O
R
(CH2)n
(CH2)n Tetrahedron 1989, 45, 909
Tetrahedron 1991, 47, 6795
SnBu3
R
X= I, SePh
n= 1,2
Br Br Bu3SnH, AIBN,
+ C6H6, reflux JOC 1992, 57, 7163
O O
O
Eight-Membered Rings review:Tetrahedron 1992, 48 , 5757.
[4+4] Cycloaddition of Dienes
Ni(COD)2, Ph3P MeO2C JACS 1986,
MeO2C
108 , 4678
MeO2C 60°C MeO2C
O O
O
O O
O
JACS 1988,
Ni(COD)2, Ph3P
H 110 , 5904
60°C H
O
Asteriscanolide
Carbonyl Coupling Reactions
- Acyloin Reaction
CO2Me O
Na JACS 1971,
93 , 1673
CO2Me OH
- McMurry Reaction
R R
CO2Et Ti (0)
O
O
7-MEMBERED RING FORMATION 172
CHO OHC
TiCl3, Zn-Cu
JACS 1986,
H H 108 , 3513
Aldol-like Condensations
O
TiCl4 O
O OH JCSCC 1983, 703
OTMS O
SiMe3 SiMe3
R Lewis Acid R
JACS 1986,
O 108 , 3516
(CH2)n O OMe (CH2)n O
n= 1,2
Me3Si Cl Cl
Me3Si Cl
SnCl4
OTs
O OTs O
tBuPh2SiO O
tBuPh2SiO JACS 1988,
OEt Laurenyne 110 , 2248
TiCl4
JOC 1988,
53 , 50
O SiMe3 O
Pinocol Rearrangement
O
Me3SiO SnCl4 Me3SiO
+ JACS 1989,
OMe 111 , 1514
OMe
OMe H
OMe
Tiffeneu-Demyanov Ring Expansion
- one carbon ring expansion for virtually any size ring
N2
O HO NH2 O H O
1) Me3SiCN JOC 1980,
2) LAH HONO 45 , 185
- also see Beckman and Schmidt rearrangements as a one atom ring expansion
for the conversion of cyclic ketones to lactams.
7-MEMBERED RING FORMATION 173
DeMayo Reaction
O
O O O
hν O O
+
OAc
AcO
O
JCSCC 1984, 1695
O O
O
CO2Me
O O H
O pTSA, MeOH
hν, pyrex O reflux JACS 1986,
O O 108 , 6425
O
H
Ring Expansion/Contraction via Sigmatropic Rearrangements
- Cope Rearrangement
O
O
SMe TL 1991,
55°C
32 , 6969
O
O
O O
- Anion Accelerated Cope
KH, 18-C-6
115°C O JACS 1989,
111, 8284
OH O
OCOCH2OH
Pleuromutilin
- Claisen Rearrangement
O
O
Tebbe
reagent O 185°C
O H TL 1990,
31 , 6799
7-MEMBERED RING FORMATION 174
- Ester Enolate Claisen- 4 carbon ring contractions
O
1) LDA, TBS-Cl
2) 110°C CO2H
O
JACS 1982, 104 , 4030
Tetrahedron 1986, 42 , 2831
MOMO MOMO
1) LDA, TBS-Cl
H 2) 110°C JOC 1988, 53 , 4141
O
H
O H CO2TBS