Vinylmagnesium Bromide1

[1826-67-1]  · C2H3BrMg  · Vinylmagnesium Bromide  · (MW 131.26)

(introduction of a vinyl unit)

Form Supplied in: widely available in solution in THF (1.0 M).

Preparative Methods: prepared in situ from vinyl bromide and Magnesium in THF.3

Handling, Storage, and Precautions: the solution in THF must be handled with care since it is flammable and may ignite on contact with moisture and air. It should be stored and handled in an inert atmosphere (argon or nitrogen) and measured or transferred by means of a hypodermic syringe or cannula. The solution may deteriorate with time and the concentration of the reagent should be titrated before use.2

General Discussion.

Vinylmagnesium bromide reacts with various electrophiles (e.g. aldehydes, ketones, esters, lactones, anhydrides, acid chlorides, carboxylic acids, nitriles, amides, epoxides, allyl halides) (eq 1).1,3,4

Complexation of vinylmagnesium bromide with TDA-1 [N(CH2CH2OCH2CH2OMe)3] gives a powder which can react as the conventional Grignard reagent in hydrocarbon solvents (toluene, cyclohexane) (eq 2).5

Vinylmagnesium bromide reacts with a silyl ketone to give a tertiary allylic alcohol, which is a useful intermediate for the synthesis of 2-substituted 1,3-dienes (eq 3).6 A fluorinated 1,3-butadiene bearing a siloxy group is prepared by treatment of a trifluoroacetylsilane with vinylmagnesium bromide (eq 4).7

An organocerium reagent, prepared from vinylmagnesium bromide and anhydrous Cerium(III) Chloride, reacts with easily enolizable ketones to afford addition products in good yield (eq 5).8 Under copper catalysis, vinylmagnesium bromide undergoes conjugate addition to a,b-unsaturated ketones very efficiently (eqs 6 and 7).9-11

In the presence of copper(I) salts (2-10%) in THF, vinylmagnesium bromide reacts with alkyl halides (eq 8)12 and epoxides. In the latter case, pure Copper(I) Iodide (or Copper(I) Bromide-dimethyl sulfide) is needed for the ring opening of cyclohexene oxide with high stereospecificity (eq 9).13

In the presence of nickel or palladium complexes, vinylmagnesium bromide couples efficiently with aryl halides (eq 10),14 vinyl halides (eqs 11 and 12),15,16 and vinyl carbamates (eq 13).17 The transmetalation of vinylmagnesium bromide occurs easily to give useful vinyl metals (eqs 14 and 15).18,19

Related Reagents.

Isopropenylmagnesium Bromide; Vinyllithium; Vinylmagnesium Bromide-Copper(I) Iodide; Vinylmagnesium Bromide-Methylcopper; Vinylmagnesium Chloride-Copper(I) Chloride.

1. (a) Normant, H. Adv. Org. Chem. 1960, 2, 1. (b) Ioffe, S. T.; Nesmeyanov, A. N. Methods of Elemento-Organic Chemistry; North-Holland: Amsterdam, 1967; Vol. 2, p 1. (c) Negishi, E. I. Organometallics in Organic Synthesis; Wiley: New York, 1980. (d) Brandsma, L.; Verkruijsse, H. D. Preparative Polar Organometallic Chemistry; Springer: 1987; Vol. 1, p 46. (e) Erdik, E. T 1984, 40, 641.
2. Watson, S. C.; Eastham, J. F. JOM 1967, 9, 165.
3. Normant, H. BSF(2) 1957, 728.
4. (a) Normant, H.; Ficini, J. BSF(2) 1956, 1441. (b) Cuvigny, T.; Normant, H. BSF(2) 1961, 2423. (c) Ficini, J.; Normant, H. BSF(2) 1964, 1294. (d) Normant, J. BSF(2) 1963, 1888. (e) Seyferth, D.; Vaughan, L. G. JOM 1963, 1, 138. (f) Kuwajima, I.; Kato, M. CC 1979, 708. (g) Holt, D. A. TL 1981, 22, 2243. (h) Gadwood, R. C.; Lett, R. M. JOC 1982, 47, 2268.
5. Boudin, A.; Cerveau, G.; Chuit, C.; Corriu, J. P.; Reye, C. T 1989, 45, 171.
6. Brown, P. A.; Bonnert, R. V.; Jenkins, P. R.; Lawrence, N. J.; Selim, M. R. JCS(P1) 1991, 1893.
7. (a) Jin, F.; Xu, Y.; Huang, W. JCS(P1) 1993, 795. (b) Jin, F.; Xu, Y.; Huang, W. CC 1993, 814.
8. Imamoto, T.; Takiyama, N.; Nakamura, K.; Hatajima, T.; Kamiya, Y. JACS 1989, 111, 4392.
9. (a) Posner, G. H. OR 1972, 19, 1. (b) Posner, G. H. OR 1975, 22, 253. (c) Normant, J. F. S 1972, 63. (d) Lipshutz, B. H. S 1987, 325. (e) Lipshutz, B. H. COS 1991, 1, 107. (f) Lipshutz, B. H.; Sengupta, S. OR 1992, 41, 135.
10. (a) Harayama, T.; Cho, H.; Inubushi, Y. TL 1977, 3273. (b) House, H. O.; Chu, C.-Y. Phillipps, W. V.; Sayer, T. S. B.; Yau, C. C. JOC 1977, 42, 1709.
11. Matsuzawa, S.; Horiguchi, Y.; Nakamura, E.; Kuwajima, I. T 1989, 45, 349.
12. Derguini-Boumechal, F.; Linstrumelle, G. TL 1976, 3225.
13. Henin, F.; Muzart, J. SC 1984, 14, 1355.
14. Nugent, W. A.; McKinney, R. J. JOC 1985, 50, 5370.
15. (a) Ratovelomanana, V.; Linstrumelle, G. BSF(2) 1987, 174 (CA 1988, 108, 5773n). (b) Dang, H. P.; Linstrumelle, G. TL 1978, 191.
16. Murahashi, S. I.; Yamamura, M.; Yanagisawa, K. I.; Mita, N.; Kondo, K. JOC 1979, 44, 2408.
17. Tsukazaki, M.; Snieckus, V. TL 1993, 34, 411.
18. Seyferth, D. OSC 1963, 4, 258.
19. Wallace, R. H.; Zong, K. K. TL 1992, 33, 6941.

Gérard Linstrumelle & Mouâd Alami

Ecole Normale Supérieure, Paris, France

Copyright 1995-2000 by John Wiley & Sons, Ltd. All rights reserved.