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

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.