Reaction of linear push-pull enamines at the β′-position

Enamine tautomerism is often the main cause of regioselectivity problems in the chemistry of enamines derived from ketones. Linear push-pull tertiary enamines featuring a methyl (methylene) group at the alpha-position do not experience such tautomerism; nevertheless, a number of reactions proceed with participation of the methyl (methylene) group. It was our objective to analyze all known reactions of this type and show their high synthetic potential. 1 Introduction 2 Electrophilic Functionalization of Preformed Lithiated or Silylated Enamines 3 Uncatalyzed Reactions of Monoelectrophilic Reagents at the Methyl (Methylene) Group 4 Reactions Proceeding at Both the beta- and beta'-Carbon of the Enamine 5 Reactions Proceeding at the alpha-Methyl (Methylene) Group and beta-Functional Group 6 Conclusion.