Cu(I)/Chiral Bisoxazoline-Catalyzed Enantioselective Doyle-Kirmse Reaction of Allenyl Sulfides with α-Diazoesters.

Abstract

Herein, a Cu(I)-catalyzed enantioselective Doyle-Kirmse reaction of allenyl sulfides and α-diazoesters is reported, which provides an efficient synthetic route to enantio-enriched chiral tertiary homopropargylic sulfides. This reaction features high enantioselectivities (up to 96 % ee) and good functional group tolerance. The alkyl substituted α-diazoester has also been demonstrated as the efficient substrates in the asymmetric Doyle-Kirmse reaction. Mechanistic studies, including kinetic experiments, were conducted to gain insights into the details of the reaction pathway. The potential synthetic utility of this protocol has also been demonstrated.