Reactions of tetracyclic γ-sultones with N-nucleophiles. Novel synthesis of 3,4-disubstituted homoadamantanes

•Reactions of tetracyclic γ-sultones with N-nucleophiles were studied.•Skeletal rearrangement was found.•The derivatives of sulfonic acids were synthesized.•Carbanion pyramidal inversion was found.

Derivatives of (homo)adamantane sulfonic acids are synthesized through the reaction of tetracyclic γ-sultones with ammonia and hydrazine hydrate. In the presence of a strong base and prolonged heating the reactions of γ-sultones with ammonia or hydrazine hydrate occur through CO cleavage and lead to products with a modified carbon skeleton. Ring opening of trans-γ-sultones proceeds with inversion of configuration of the carbon atom linked to sulfur. The reaction of bromomethyl sultones with secondary amines proceeds through dehydrohalogenation and leads to products of Michael addition.

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