Page 702 - Advanced Organic Chemistry Part B - Reactions & Synthesis

678 Table 8.1. Mixed-Ligand Organocopper Reagents

CHAPTER 8 Mixed ligand reagent Reactivity and properties Reference
Reactions Involving
Transition Metals [R′C C Cu R]Li Conjugate addition to α,β-unsaturated a
ketones and certain esters
[ArS Cu R]Li Nucleophilic substitution and conjugate b,c
addition to unsaturated ketones; ketones
from acyl chlorides
Nucleophilic substitution and conjugate b
[(CH ) CO Cu R]Li
3 3
addition to α,β-unsaturated ketones
Normal range of nucleophilic reactivity; d
[(c-C H ) N Cu R]Li improved thermal stability
6 11 2
[Ph P Cu R]Li Normal range of nucleophilic reactivity; d
2
improved thermal stability
O
e
Normal range of nucleophilic reactivity;
[CH SCH 2 Cu R]Li improved thermal stability
3
f
[N C Cu R]Li Efficient opening of epoxides
[N C CuR ]Li 2 Nucleophilic substitution, conjugate g
2
addition
Nucleophilic substitution, conjugate h
Cu – R
S addition and epoxide ring-opening
i
[(CH ) CCH Cu R]Li Conjugate addition
2
3 3
j
[(CH ) SiCH Cu R]Li High reactivity, thermal stability
2
3 3
j
{[(CH ) Si] N Cu R]}Li High reactivity, thermal stability
3 3
2
BF 3 Cu R Conjugate addition, including acrylate k
2′
esters and acrylonitrile; S N
substitution of allylic halides
a. H. O. House and M. J. Umen, J. Org. Chem., 38, 3893 (1973); E. J. Corey, D. Floyd, and B. H. Lipshutz, J. Org.
Chem. 43, 3418 (1978).
b. G. H. Posner, C. E. Whitten, and J. J. Sterling, J. Am. Chem. Soc., 95, 7788 (1973).
c. G. H. Posner and C. E. Whitten, Org. Synth., 58, 122 (1975).
d. S. H. Bertz, G. Dabbagh, and G. M. Villacorta, J. Am. Chem. Soc., 104, 5824 (1982).
e. C. R. Johnson and D. S. Dhanoa, J. Org. Chem., 52, 1885 (1987).
f. R. D. Acker, Tetrahedron Lett., 3407 (1977); J. P. Marino and N. Hatanaka, J. Org. Chem., 44, 4667 (1979).
g. B. H. Lipshutz and S. Sengupta, Org. React., 41, 135 (1992).
h. H. Malmberg, M. Nilsson, and C. Ullenius, Tetrahedron Lett., 23, 3823 (1982); B. H. Lipshutz, M. Koernen, and
D. A. Parker, Tetrahedron Lett., 28. 945 (1987).
i. C. Lutz, P. Jones, and P. Knochel, Synthesis, 312 (1999).
j. S. H. Bertz, M. Eriksson, G. Miao, and J. P. Snyder, J. Am. Chem. Soc., 118, 10906 (1996).
k. K. Maruyama and Y. Yamamoto, J. Am. Chem. Soc., 99, 8068 (1977); Y. Yamamoto and K. Maruyama, J. Am. Chem.
Soc., 100, 3240 (1978).