Metallophosphite‐Induced Nucleophilic Acylation of α,β‐Unsaturated Amides: Facilitated Catalysis by a Diastereoselective Retro [1,4] Brook Rearrangement.

Abstract

2005 Carboxylic amides Q 0490Metallophosphite-Induced Nucleophilic Acylation of α,β-Unsaturated Amides: Facilitated Catalysis by a Diastereoselective Retro [1,4] Brook Rearrangement.-Synthetically interesting α-silyl-γ-ketoamides of type (IV) are formed with high to moderate anti-selectivity by conjugate addition of a variety of acylsilanes to unsaturated amides. Desilylation of the diastereomeric product mixtures affords γ-ketoamides.-(NAHM, M. R.; LINGHU, X.; POTNICK, J. R.; YATEES, C. M.; WHITE, P. S.; JOHNSON*, J. S.; Angew.