Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (8): 2926-2948.DOI: 10.6023/cjoc202602018 Previous Articles     Next Articles

REVIEWS

铑和手性磷酸参与的卡宾不对称催化反应研究进展

朱晓宇, 罗宜铭, 孙墁, 李文泽*()   

  1. 沈阳化工大学 辽宁省稀土化学及应用重点实验室 沈阳 110142
  • 收稿日期:2026-02-21 修回日期:2026-05-06 发布日期:2026-05-27
  • 通讯作者: 李文泽
  • 基金资助:
    辽宁省教育厅基金(LJKMZ20220795)

Recent Advances in Asymmetric Carbene Catalytic Reactions Mediated by Rhodium and Chiral Phosphoric Acid

Xiaoyu Zhu, Yiming Luo, Man Sun, Wenze Li*()   

  1. Liaoning Key Laboratory of Rare Earth Chemistry and Application, Shenyang University of Chemical Technology, Shenyang 110142
  • Received:2026-02-21 Revised:2026-05-06 Published:2026-05-27
  • Contact: Wenze Li
  • Supported by:
    Liaoning Provincial Department of Education Fund(LJKMZ20220795)

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