Enantioselective Synthesis of Complex Carbocycles by Donor/Donor Carbenes C-H insertion

A range of benzene-fused carbocyclic molecules are accessed by the enantioselective C–H insertion of rhodium donor/donor carbenes. The reaction is chemoselective for insertion into carbon centers appended with an electron-donating heteroatom, including a range of ethers, a free hydroxyl group, and a range of nitrogen substituents, including basic amines. DFT calculations support a step-wise mechanism of this process and provide insight into the origin of both stereoselectivity and the preference for C–H versus O–H insertion.