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

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.

Automated summary

We present a general method for synthesizing highly functionalized (Z)-allylic amines through decarboxylative allylation of vinyloxazolidin-2-ones. This process utilizes sodium sulfinates as nucleophiles to form a new carbon-sulfur bond, facilitated by a palladium catalyst generated from Pd(OAc)(2) and diphosphine ligand dpppe. The versatility of this approach is demonstrated by the synthesis of 30 representative allylic amines with excellent regio- and stereoselectivity. Mechanistic studies reveal that the Z-selectivity of the reaction is attributed to the formation of a palladacycle intermediate via Pd-N chelation. The synthetic utility of this method is further showcased by its successful gram-scale synthesis and subsequent transformations to diverse compounds.