Cross-coupling with Grignard

Nickel (II) Catalyzed Cross-Coupling with Grignard Reagents (Kumada Reaction) Pure AppJ. Chem. 1980, 52, 669 Bull Chern. Soc.Jpn. 1976, 49, 1958... 

Aryl mesylates are used for the Ni-catalysed cross-coupling with Grignard, organozinc and organoboron reagents [100]. 

Scheme 11.40 Cross-coupling with Grignard reagent.

Scheme 13 Ruthenium-catalyzed traditional cross-coupling with Grignard reagent 34...

Urushiol analogues with Ci8 alkenyl side chains have been synthesised from 3-bromobenzene and 2,3-acetonylidenebromobenzene by cross coupling with Grignard reagents derived from Cig unsaturated halides [217,243],... 

In a reversal of the functionalities in the reactants, thienyl halides can be cross-coupled with Grignard reagents under Ni" catalysis (Scheme 130). This method has provided access to 3-(co-haloalkyl)thiophenes which can be used as building blocks for functionalized polythiophenes <90AG(E)419>. 

As early as 1972, Kumada and coworkers reported that aryl chlorides could undergo cross-couplings with Grignard reagents catalyzed by a nickel-1,2-bis(diphenylpho sphino)ethane (dppe) complex (Equation 2.2) [9, 10]. 

Cross-coupling with Grignard compds. RHal + HalR R-R ... 

A mixture of p-fluorophenylmagnesium bromide, /7-methoxyphenylethenyl bromide, and 2 mol% Pt-rj -alkene complex (prepared by reacting dichloro[l,T-bis(diphenyl-phosphino)ferrocene]platinum(II) with /7-methoxyphenylethenyl bromide in THF at room temp.) in THF refluxed for 2 days - product. Y 95%. This is the first report of efficient Pt-catalyzed cross-coupling with Grignard reagents. F.e.s. J.M. Brown et al., J. Chem. Soc. Chem. Commun. 1989, 458-60. 

The Kumada Reactions Nickel-Catalyzed Cross-Coupling with Grignard Reagents... 

In common with vinyl and aryl halides, it has now been shown that allenic and propargylic halides cross-couple with Grignard reagents in the presence of palladium catalysts. The product consists predominantly of the substituted allene... 

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