Electronic configuration and nucleophilicity of carbon free radicals. α-Alkoxyalkyl, α-alkoxycarbonyl, and cycloalkyl radicals

Abstract

The nucleophilicity of carbon free radicals is strongly affected by the hybridization of the orbital occupied by the odd electron. An α-alkoxy-group increases the nucleophilicity of π-type alkyl radicals and decreases that of σ-type acyl radicals. The cyclopropyl radical, which has the highest s character, is the least nucleophilic of the cycloalkyl radicals. The general behaviour is discussed in terms of a transition state similar to a charge-transfer complex.