The correlation of regiochemistry with structure in the S_RN1 reaction of aci-nitronates with p-nitrobenzylic substrates

Abstract

The rate and regiochemistry of the S_RN1 reactions of aci-nitronates with p-nitrobenzylic substrates are profoundly affected by branching at the positions adjacent to the reaction sites (C^β). Definitive rules which predict whether C-alkylation will occur in the association step involving p-nitrobenzylic radicals and aci-nitronate ions are formulated. β-Branching causes O-alkylation or reductive processes to increase. In some cases no recognizable product formation results. Benzylic alcohols, p-nitrophenyl alkyl ketones and/or their oximes, and p-nitrophenol are among the products which result from subsequent reactions of the O-alkylation products, aci esters of benzylic alcohols.