Silver-catalyzed fragmentation of all-carbon quaternary centers from sp3 to sp2 carbon via C-C bond cleavage.

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 sp3-hybridized 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 silver-catalyzed intramolecular cyclization and subsequent retro-Michael addition.