Cu(I)/Chiral Bisoxazoline-Catalyzed Enantioselective Sommelet-Hauser Rearrangement of Sulfonium Ylides.

Abstract

Catalytic asymmetric thia-Sommelet-Hauser rearrangement of sulfonium ylides remains a great challenge due to its multistep reaction mechanism involving metal carbene formation, proton transfer, and [2,3]-sigmatropic rearrangement. In particular, the key problem of such reactions is the differentiation of the enantiotopic lone pair electrons of sulfur, which generates the sulfonium ylide intermediate bearing chirality on the sulfur atom. With a modified chiral bisoxazoline ligand, we developed a Cu(I)-catalyzed asymmetric thia-Sommelet-Hauser rearrangement with good to excellent enantioselectivities. Mechanistic studies provide insights into the details of the reaction mechanism.