Kinetic Resolution via Rh-Catalyzed C-C Activation of Cyclobutanones at Room Temperature

Herein we describe the development of a highly selective kinetic resolution of cyclobutanones via a Rh-catalyzed cut-and-sew reaction with selectivity factor up to 785. This reaction takes place at room temperature with excellent efficiency. Various trans-5,6-fused bicycles and C2-substituted cyclobutanones were obtained with excellent ee's that can be further used as chiral building blocks. DFT calculations reveal the crucial roles of the DTBM-segphos ligand in stabilizing the rate- and enantioselectivity-determining C-C oxidative addition transition state via favorable ligand substrate dispersion interactions.