Page 204 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Scheme 2.20. Julia Olefination Reactions
176
1 TBDMSO TBDMSO
a
CHAPTER 2 OTBDMS
O O
Reactions of Carbon + 1) BuLi
Nucleophiles with CH O CH 3
Carbonyl Compounds OTBDMS 2) PhCOCl
3) Na(Hg) 92:8 E:Z 63%
CH 3
PhSO 2
2 b N LiHMDS CH 3 O
CH 3 O CH O + ClCH 2 SO 2
S MgBr 2
Cl 69%
94:6 E:Z
3 c N N 1) KHMDS
CH 3 O 2 C(CH 2 ) 9 CH 2 SO 2 N CH 3 (CH 2 ) 5
N (CH 2 ) 9 CO 2 CH 3
2) O CH(CH 2 ) 5 CH 3
Ph 50%
85:15 E:Z
4 d OTIPS
OTIPS H
KHMDS
TBDPSO CH O O
OPMB TBDPSO
N N H OPMB
+ N O CH 3 81%
N SO 2
Ph 5:1 E:Z
CH 3
5 e (CH 3 ) 3 Si OCH 3 KHMDS (CH 3 ) 3 Si OCH 3
N CH 3
SO 2 I
+ S
CH 3
O CH 74%
I
6 f
N
Br SO 2 +
S PMBO OCH 3
PMBO OCH 3
NaHMDS Br CH(OCH 3 ) 2
O CH CH(OCH 3 ) 2
CH 3 OTBDMS 75%
CH3 OTBDMS > 95:5 E:Z
7 g CH 3 O 2 C CH 3 O 2 C
O CO 2 C(CH 3 ) 3 O CO 2 C(CH 3 ) 3
HN HN
N LiHMDS N
N N
O H
H O O H Ph H C(CH 3 ) 2 78%
+ N
N
N
(CH 3 ) 2 CHSO 2
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