Regio- and diastereoselective Pd-catalyzed aminochlorocyclization of allylic carbamates: scope, derivatization, and mechanism

Abstract

The regio- and diastereoselective synthesis of oxazolidinones via a Pd-catalyzed vicinal C–N/C–Cl bond-forming reaction from internal alkenes of allylic carbamates is reported. The oxazolidinones are obtained in yields of 44 to 95% with high to excellent diastereoselectivities (from 6 : 1 to >20 : 1 dr) from readily available precursors. This process is scalable, and the products are suitable for the synthesis of useful amino alcohols. A detailed theoretical and experimental mechanistic study was carried out to describe that the reaction proceeds through an anti-aminopalladation of the alkene followed by an oxidative C–Pd(II) cleavage with retention of the carbon stereochemistry to yield the major diastereomer. The role of Cu(II) in a C–Cl bond-forming mechanism step has also been proposed.