Vinyl halides with Grignard reagents

In 1971, a year before the groups of Corriu and Kumada [5] independently reported the groundbreaking work on the topic of nickel-catalyzed cross-coupling reactions of aryl and vinyl halides with Grignard reagents, Tamura and Kochi described an iron-catalyzed vinylation reaction of Grignard reagents with vinyl halides (Scheme 5.1) [6]. 

The cross-coupling reaction of vinyl halides with Grignard reagents to provide corresponding alkenes was also promoted by a ruthenium catalyst such as RuCl2(PPh3)3 [12]. 

Tetrakis(triphenylphosphine)palladium couples vinyl halides with Grignard reagents and organolithium reagents. 

In 1982, JnUa s group showed that vinyl snUones react with Grignard reagents in the presence of iron salts to afford moderate yields of conpling product (Scheme 25). The reaction is stereoselective but its scope is limited. Thus, with secondary alkylmagnesium halides, only the reduction product is formed. 

Asymmetric coupling of a vinyl halide with a Grignard reagent. 1-Phenylethyl-magnesium chloride couples with vinyl bromide in the presence of a nickelcatalyst (1) composed of NiCl, and (-)-norphos to give (S)-3-phenyl-l-butene (2) in 67% enantiomeric excess.1... 

Sml2 (stoichiometric amount) promotes alkylation of ketones in THF by alkyl hromidcs, iodides, or tosylates. The reaction is slow, but can be accelerated by a catalytic amount of FcClj. This reaction is analogous to reaction of ketones with Grignard reagents. Vinylic and aryl halides do not undergo this alkylation.1... 

Stereospecific synthesis of alkenes. This Pd(0) complex is an efficient catalyst for the cross-coupling of vinylic halides with a variety of Grignard reagents. The resulting alkenes are obtained in 97% isomeric purity and in yields of 75-90%. This reaction is particularly useful for preparation of pure 1,3-dienes (equation I). ... 

Oxidative addition to Pd(0) is an important step in many C—C bond-forming reactions catalyzed by Pd. These include the cross-coupling of vinyl or aryl halides or triflates with Grignard reagents or organostannanes ... 

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