Enantioselective [4+1] Annulation of Benzamide with Cyclopropene via Chiral CpXCo(III) Catalysis: A DFT Perspective

Abstract Asymmetric C–H bond functionalization employing CpXM(III) has gained significant attention in organic synthesis transformations. In this work, the first comprehensive DFT investigation has been performed to gain a better understanding of the origin of enantioselectivity and regioselectivity of Co-catalyzed asymmetric [4+1] annulation of N-chlorobenzamide with cyclopropenes. Our DFT calculations indicate that, although the microkinetic model failed to predict the trans-endo/cis-endo product ratio, the ratio is within the typical intrinsic error margins of DFT calculations. This thorough DFT analysis is a key to advancing the rational design of enantioselective C–H functionalization transformations with chiral CpXM(III) catalysts.