Radical Reactions of Allenes

Abstract

Allenes, which contain the functional group of 1,2-propadiene, are highly reactive. In this paper, we review some free-radical reactions of allenes. The application in natural product synthesis is also described. Substituted allenes undergo rather facile radical chain addition reactions. Attack by a radical speciescan occur at either the central or the terminal C atom. In the case of addition, the preferred route is generally that forming the possibly more stable free-radical intermediates. The steric effect, electronegativity and solvent effect shoulde also be considered. In general, carbon-centered free radicalssuch as CH₃· and CCl₃· add mostly to the terminal carbon atom while heteroatom-based free radicals such as Br·, RS·, ArSO₂· and R₃Sn· add preferentially to the central carbon atom. Substituted allenes can undergo a varietyof [2+2] cycloaddition reactions with alkenes, allenes, enynes and ketenes and also undergo a cyclopropanation with carbenes via a biradical mechanism.

Key words: allene, radical, addition reaction, cycloaddition, synthetic application

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PAN Feng, FU Chun-Ling, MA Sheng-Ming. Radical Reactions of Allenes[J]. Chinese Journal of Organic Chemistry, 2004, 24(10): 1168-1190.

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