Enantioselective Synthesis of Axially Chiral Biaryls via Cu-Catalyzed Acyloxylation of Cyclic Diaryliodonium Salts

Abstract

We report here a Cu-catalyzed enantioselective acyloxylation of cyclic diaryliodonium salts. With readily available cyclic diaryliodonium salts and ubiquitous aliphatic or (hetero)aromatic carboxylic acids as the starting materials, various axially chiral acyloxylated 2-iodobiaryls were prepared in excellent yield and with excellent enantioselectivity (mostly 99% yield and 99% ee). Density functional theory calculations were conducted to reveal the stereo- and regioselectivities. This simple reaction protocol can be employed for the late-stage modification of some drug molecules. Finally, by diversity-oriented transformations, these acyloxylated 2-iodobiaryl products can be easily transformed into diverse valuable functionalized biaryls that could be used as chiral ligands or functional materials.