Conformational Locking Induced Enantioselective Diarylcarbene Insertion into B−H and O−H Bonds Using a Cationic Rh(I)/Diene Catalyst

Abstract Transition‐metal‐catalyzed enantioselective transformations of aryl/aryl carbene are inherently challenging due to the difficulty in distinguishing between two arene rings in the reaction process thus remain largely less explored. The few successful examples reported so far, without exception, have all been catalyzed by Rh(II)‐complexes. Herein, we describe our successful development of a novel cationic Rh(I)/chiral diene catalytic system capable of efficient enantioselective B−H and O−H insertions with diaryl diazomethanes, allowing the access to a broad range of gem ‐diarylmethine boranes and gem ‐diarylmethine ethers in good yields with high enantioselectivities. Notably, previously unattainable asymmetric diarylcarbene insertion into the O−H bond was achieved for the first time. A remarkable feature of this newly designed Rh(I)/diene catalyst bearing two ortho ‐amidophenyl substitutents is that it can distinguish between two arene rings of the diaryl carbene through a stereochemically selective control of π–π stacking interactions. DFT calculations indicate that the rotation‐restricted conformation of Rh(I)/diene complex played an important role in the highly enantioselective carbene transformations. This work provides an interesting and unprecedented stereocontrol mode in diaryl metal carbene transformations.