Alkyl halides vinyl Grignard reagents

Reaction with Alkyl Halides. The Grignard reagent (1) can be alkylated by allyl halides to afford the homoallylsilane. The use of a nickel(II) catalyst facilitates coupling of the Grignard reagent (1) to vinyl halides and aryl halides, triflates and O-carbamates and provides a useful method for the preparation of allyl- andbenzylsilanes (eq 7). Palladium catalysis is also effective to couple (1) with vinyl halides. 

CO2). A partial solution to this problem is reaction of the vinyl Grignard reagent with alkyl halides in the presence of cuprous iodide [Cu(I)I], which does little for the initial loss of stereochemistry upon formation of... 

The order of halide reactivity is I > Br > Cl > F and alkyl halides are more reac tive than aryl and vinyl halides Indeed aryl and vinyl chlorides do not form Grignard reagents m diethyl ether When more vigorous reaction conditions are required tetrahy drofuran (THF) is used as the solvent... 

Polarization also occurs in coupling and disproportionation reactions of Grignard reagents with alkyl halides. The vinyl protons of isobutene produced in the reaction of t-butylmagnesium chloride with t-butyl bromide show A/E polarization as do the methyl protons of isobutane (Ward et al., 1970). Similar results arise in the reaction of diethyl-magnesium with organic halides (Kasukhin et al., 1972). 

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