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.