Copper-Catalyzed Intermolecular Asymmetric Transformations of Vinyl Cations via [1,2]-Stevens-Type Rearrangement

Significant advancements have been achieved in the formation of organic sulfides via the [1,2]-Stevens-type rearrangement reaction of sulfur ylides, but the corresponding asymmetric version has been scarcely reported to date. Furthermore, the limited existing results predominantly rely on using diazo compounds as precursors with a limited substrate scope and unsatisfactory enantioselectivity. Herein, we report an efficient asymmetric [1,2]-Stevens rearrangement via vinyl cations by copper-catalyzed diyne cyclization, enabling practical, atom-economical, and divergent access to various chiral S-heterocycles containing two consecutive stereocenters with moderate to high yields and high stereocontrols. Importantly, this protocol features an intermolecular catalytic asymmetric [1,2]-Stevens rearrangement by a nondiazo pathway, and constitutes an asymmetric [1,2]-Stevens rearrangement of 1,3-dithiolanes and thiazolidines.