Enantioselective Formation of All-Carbon Quaternary Stereocenters in <i>gem</i>-Difluorinated Cyclopropanes via Rhodium-Catalyzed Stereoablative Kinetic Resolution

Abstract

Herein, we report an effective method to offer chiral gem-difluorinated cyclopropanes containing an all-carbon quaternary stereocenter by rhodium-catalyzed stereoablative kinetic resolution. The activation of a sterically hindered all-carbon quaternary C–C bond through oxidative addition with a chiral rhodium complex is proposed as the enantiodetermining step. A wide range of gem-difluorinated cyclopropanes can be obtained with excellent ee values (ee = 87% to >99.9%), which are demonstrated to be useful chiral fluorine-containing building blocks by a series of postfunctionalizations.

Topics & Concepts