Page 671 - Advanced Organic Chemistry Part B - Reactions & Synthesis

646 Scheme 7.4. Synthetic Procedures Involving Organolithium Reagents

CHAPTER 7 A. Alkylation
Organometallic 1 a CH O CH O
Compounds of Group I 3 1) n –BuLi 3
and II Metals OSiR (CH ) C CHCH OSiR
3 3 2 2 3
2) BrCH CH C(CH )
2 3 2
CH O CH O
3
3
60%
2 b H H
C C
(CH ) COCHCH CH + CH (CH ) I
3 3
3
2
2 5
(CH ) CO (CH ) CH
Li 3 3 2 6 3 83%
3 c
CH Br
H C 2 CH O CH O CH OSiR 3
2
3
3
3
CH 3
+ Li CH OSiR CH OSiR
2 3 CH 2 2 3
H C OTHP
3
CH 3 CH 3 THPO CH OSiR 3 CH 3
2
65%
4 d CH CH
OH 3 3
O + C H Li/BF
4 9 3
(3 equiv) (CH ) CH
3
2 3
97%
B. Reactions with aldehydes and ketones to give alcohols
5 e O OH
CH 2 CHCH Li + CH CCH CH(CH ) CH 2 CHCH CCH CH(CH )
3 2
3
2
2
3 2
2
2
6 f O OH CH 3 70 –72%
CH CH CH CH
H Li + 2 2 2 3
C 4 9
89%
7 g
PhLi
CH CH O
3
N CH 3 N CH Li N CH CHCH 3 44–50%
2
2
OH
8 h 2-t -BuLi
CH CH CHBr CH CH CHLi PhCH O CH CH CHCHPh
3
–120°C 3 3
OH
9 i CH O O CH O O CH O 72% (C H ) N
3
3 3 2 5 2 OCH 3
s-BuLi O CH CH 3 CH O C O
CN(C H ) CN(C H ) OCH 3 3 CH 3
5 2
2
2
5 2
CH O CH O Li
3 3
CH O OH OCH
j 3 3
10 HO 63%
Li
CH OCH Cl + O
3
2
5 mol % DTBB CH OCH
3
2
90%
C. Reactions with carboxylic acids, acyl chlorides, acid anhydrides, and N-methoxyamides to give
ketones
k O
11
H 2 O
CO 2 Li + CH 3 Li CCH 3
91%
12 l O
H 2 O
(CH 3 ) 3 CCO 2 H + 2 PhLi CC(CH 3 ) 3
65%
(Continued)