Metallophosphite-induced nucleophilic acylation of α,β- unsaturated amides: Facilitated catalysis by a diastereoselective retro [1,4] brook rearrangement

Abstract

(Chemical Equation Presented) Intermolecular alkene acylation reactions between acyl silanes and α,β-unsaturated amides with metallophosphite catalysis afford α-silyl-γ-ketoamides with high diastereoselectivities (see scheme). These can be converted into the corresponding γ-ketoamides and α-bromo-γ-ketoamides. Asymmetric catalysis of the acylation delivers the γ-ketoamide in the highest enantioselectivity yet reported for an intermolecular Stetter-type reaction. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.