Palladium-catalyzed decarboxylative allylation of vinyloxazolidin-2-ones with sodium sulfinates: stereoselective assembly of highly functionalized (Z)-allylic amines.

Abstract

We report a general approach to highly functionalized (Z)-allylic amines by decarboxylative allylation of vinyloxazolidin-2-ones. This process engages sodium sulfinates as nucleophiles to form a new carbon-sulfur bond, utilizing a palladium catalyst generated from Pd(OAc)2 and diphosphine ligand dpppe. The scope of the protocol is illustrated by the synthesis of 30 representative allylic amines with high regio- and stereoselectivity. Mechanistic studies show that the Z-selectivity of the reaction stems from the formation of a palladacycle intermediate through Pd-N chelation. The synthetic utility of this method was further exemplified by the gram-scale synthesis and subsequent transformations to various compounds.