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Organomanganese‐Mediated Radical Reactions
Book chapter

Organomanganese‐Mediated Radical Reactions

Gregory K Friestad
PATAI'S Chemistry of Functional Groups
John Wiley & Sons, Ltd
12/15/2009
DOI: 10.1002/9780470682531.pat0532

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Abstract

Free radical reactions offer functional group compatibility which complements that of carbanion reagents. A variety of synthetically useful transformations proceeding via free radicals, including reductions, carbonylations , reductive additions, cyclizations and polymerizations , may be induced by organomanganese reagents. These generate carbon‐centered radicals from organic halides; photolysis with dimanganese decacarbonyl leads to halogen atom abstraction, or triorganomanganate reagents effect electron transfer followed by loss of halide ion. Synthetic methods employing these reagents are reviewed, with emphasis on carbon‐carbon bond construction, stereoselectivity, and applications in natural product synthesis. Reductive dehalogenation , Wurtz coupling, intermolecular radical additions and carbonylations , radical cyclizations including atom transfer methods, and radical addition to imino compounds are discussed in the context of recent developments using organomanganese reagents.
Radical, Carbenes & Carbenoids Catalysis Reactions of the Group

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