Synergistic Dual Directing Groups-Enabled Diastereoselective C-H Cyclopropylation via Rh(III)-Catalyzed Couplings with Cyclopropenyl Alcohols

Org Lett. 2020 Feb 21;22(4):1295-1300. doi: 10.1021/acs.orglett.9b04608. Epub 2020 Feb 4.

Abstract

By using a synergistic dual directing group-assisted C-H activation strategy and simply modifying the reaction conditions, we realized a robust and general Cp*Rh(III)-catalyzed C-H cyclopropylation of N-acetoxybenzamides with cyclopropenyl alcohols, providing regio-, chemo-, and diastereoselective access to ortho trans- and cis-1,1-dimethylcyclopropane-functionalized benzamides in a redox-neutral and controllable manner. Experimental and density functional theory studies clarify the roles of the NH-OAc and OH groups and deduce two distinct Rh(III)-Rh(V)-Rh(III) pathways for presenting such selectivity.

Publication types

  • Research Support, Non-U.S. Gov't