Chiral Bis(binaphthyl)\nCyclopentadienyl Ligands for\nRhodium-Catalyzed Desymmetrization of Diarylmethanes via Selective\nArene Coordination

Owing to substantial advances in the past several decades,\ntransition-metal-catalyzed\nasymmetric reactions have garnered considerable attention as pivotal\nmethods for constructing chiral molecules from abundant, readily available\nachiral counterparts. These advances are largely attributed to the\ndevelopment of chiral ligands that control stereochemistry through\nsteric repulsion and other noncovalent interactions between the ligands\nand functional groups or prochiral centers on the substrates. However,\nstereocontrol weakens dramatically with increasing distance between\nthe reaction site and the functional group or prochiral center. Herein,\nwe report a symphonic strategy for remote stereocontrol of Rh(III)-catalyzed\nasymmetric benzylic C–H bond addition reactions of diarylmethanes\nin which the two aryl motifs differ at the <i>meta</i> and/or <i>para</i> position. Specifically, catalysts bearing a new type\nof chiral cyclopentadienyl (Cp) ligand differentiate between the two\naromatic rings of the diarylmethane by arene-selective η<sup>6</sup> coordination, setting up an opportunity for ligand-controlled\nstereoselective benzylic deprotonation and subsequent stereoselective\naddition to the 1,1-bis(arylsulfonyl)ethylene.