Radical Allylation, Vinylation, Alkynylation, and Phenylation Reactions of α-Halo Carbonyl Compounds with Organoboron, Organogallium, and Organoindium Reagents

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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29

This result is attributed mainly to the choice of THF as a solvent. The influence of magnesium salt is not a serious problem. In fact, addition of an equimolar amount of MgBr₂ in the reaction of Scheme [9] did not show a significant effect.

30

In this case, the reaction was performed in THF with β-styryl Grignard reagent in place of β-styryllithium.

31

The same least motion mechanism was proposed in styryl sulfone-mediated reaction. See ref. 27a.