关键词: 铑催化, 手性磷酸, 协同催化, 接力催化

Rhodium complexes occupy a central position in transition-metal catalysis owing to their unique electronic confi- gurations and diverse oxidation states. Notably, dinuclear rhodium(II) complexes featuring a "paddlewheel" structure can efficiently mediate the decomposition of diazo compounds to generate highly reactive rhodium carbenoid intermediates, which subsequently participate in various significant carbene transfer reactions. However, in traditional asymmetric carbene transfer reactions catalyzed by chiral rhodium complexes alone, the rhodium complex often dissociates prior to the stereo-determining step in a stepwise mechanism, leading to poor enantiocontrol. To address this challenge, chemists have developed cooperative dual-catalysis strategies combining rhodium complexes with chiral phosphoric acids (CPAs). As excellent bifunctional organocatalysts, CPAs exploit their unique steric effects and hydrogen-bonding donor capabilities to precisely control the stereoselectivity of reactions without relying on metal coordination. This review systematically summarizes the research progress in asymmetric carbene catalysis involving the cooperation of rhodium and chiral phosphoric acids since 2014, focusing on three distinct modes: cooperative catalysis, relay catalysis, and chiral phosphate dirhodium complex catalysis. It aims to outline the development of this field and provides new insights for the synthesis of complex chiral molecules.

Key words: rhodium catalysis, chiral phosphoric acid, cooperative catalysis, relay catalysis