Page 722 - Advanced Organic Chemistry Part B - Reactions & Synthesis

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Scheme 8.6. Generation and Reactions of Alkenylcopper Reagents from Alkynes
CHAPTER 8 H H
1 a C 2 5 Cu C 2 5
Reactions Involving H +
4
9
Transition Metals C H MgBr + CuBr + C H C CH C C C CH 2
5
2
C H H C H 82%
4 9
4 9
2 b C 2 H 5 Cu C 2 H 5 I
I 2
C H Cu(SMe )MgBr +C H C CH C C C C
2
6
13
2
5
2
C H 13 H C 6 H 13 H 63%
6
3 c CH (CH ) Cu CH (CH ) I
2 3
3
3
2 3
I
[(n – C H ) Cu]Li+ HC CH C C 2 C C
4 9 2
H H H H 65–75%
4 d (CH ) CH Cu (CH ) CH C N
3 2
3 2
(CH ) CHCuMgBr + C H C CH C C Cl C N C C
3 2 2 4 9
C H H C H H
4 9 4 9
92%
H
C 5 11 Cu H CO C H
5 e HC CCO C H 2 2 5
5
(C H ) CuLi + HC CH C C 2 2 5 C H 11 C C
11 2
5
H H C C H
H H 78%
6 f C 2 H 5 Cu C 2 H 5 CH CH CH 2
2
H 2 C CHCH 2 Br
C H Cu(SMe )MgBr C C C C
2 5 2 2
+C H C CH C H 13 H C H 13 H 85%
6
6
13
6
7 g C 3 H 7 Cu C 3 H 7 CH CH OH
LiC CC H 2 2
C H Cu(SMe )MgBr + CH C CH C C 3 7 C C
3 7 2 2 3
O
H CH H
CH 3 3 95%
8 h CH 3 OPMB
CH CuBr-S(CH ) CH 3
3 2
2
MgBr + CH C CH +
3
CH 2 Cu CH 3
CH 3 O
OPMB
CH 2
CH 3
CH
CH 3 3 HO
76%
a. J. F. Normant, G. Cahiez, M. Bourgain, C. Chuit, and J. Villerias, Bull. Chim. Soc. Fr., 1656 (1974).
b. N. J. LaLima, Jr., and A. B. Levy, J. Org. Chem., 43, 1279 (1978).
c. A. Alexakis, G. Cahiez, and J. F. Normant, Org. Synth., 62, 1 (1984).
d. H. Westmijze and P. Vermeer, Synthesis, 784 (1977).
e. A. Alexakis, J. Normant, and J. Villeras, Tetrahedron Lett., 3461 (1976).
f. R. S. Iyer and P. Helquist, Org. Synth., 64, 1 (1985).
g. P. R. McGuirk, A. Marfat,and P. Helquist, Tetrahedron Lett., 2465 (1978).
h. M. Valluri, R. M. Hindupur, P. Bijou, G. Labadie, J.-C. Jung, and M. A. Avery, Org. Lett., 3, 3607 (2001).