Abstract
Allylic gallium and indium reagents are found to mediate radical allylation reactions
of α-iodo or α-bromo carbonyl compounds. Treatment of benzyl bromoacetate with allylgallium,
prepared from allylmagnesium chloride and gallium trichloride, in the presence of
triethylborane provided benzyl 4-pentenoate in excellent yield. Addition of water
as a co-solvent improved the yields of allylated products. Allylic indium reagents
are also useful and can replace the gallium reagents. A diallylborane reagent can
allylate an α-iodo ester in good yield. Alkenylation reactions of α-halo carbonyl
compounds with alkenylindium proceeded via a radical process in the presence of triethylborane.
Unactivated alkene moieties and styryl groups were introduced by this method. The
carbon-carbon double bond geometry of the alkenylindiums was retained during the alkenylation.
Preparation of an alkenylindium via a hydroindation of 1-alkyne and subsequent radical
alkenylation established an efficient one-pot strategy. Radical alkynylations and
phenylations with organoindium reagents are disclosed herein.
Keywords
allylation - vinylation - radical reaction - gallium - indium
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