Silver-Catalyzed Fragmentation of All-Carbon Quaternary Centers from sp 3 to sp 2 Carbon via C-C Bond Cleavage

Abstract

A silver-catalyzed C-C bond cleavage/functionalization of highly functionalized acyclic all-carbon quaternary centers has been developed. This protocol enables the efficient conversion of sp³hybridized carbon centers into sp²-hybridized carbon moieties under mild reaction conditions, delivering CF₃-substituted indolizines and β-azido-ketones in good yields. Preliminary mechanistic studies suggest a reaction pathway consisting of silvercatalyzed intramolecular cyclization and subsequent retro-Michael addition.