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0 202602018 - 202602018

DOI: https://doi.org/10.6023/cjoc202602018

综述与进展

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
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  • 辽宁省稀土化学及应用重点实验室 沈阳化工大学 沈阳 110142

收稿日期: 2026-02-21

  修回日期: 2026-05-06

  网络出版日期: 2026-05-27

基金资助

辽宁省教育厅基金(No. LJKMZ20220795)资助项目.

收起

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

  • Zhu Xiaoyu ,
  • Luo Yiming ,
  • Sun Man ,
  • Li Wenze
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  • Liaoning Key Laboratory of Rare Earth Chemistry and Application, Shenyang University of Chemical Technology, Shenyang 110142

Received date: 2026-02-21

  Revised date: 2026-05-06

  Online published: 2026-05-27

Supported by

Liaoning Provincial Department of Education Fund (No. LJKMZ20220795)

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摘要

铑配合物因其独特的电子构型和多样的氧化态, 在过渡金属催化领域占据核心地位, 尤其是具有“桨轮”结构的双核铑(II)配合物, 能够高效介导重氮化合物的分解并生成高活性的铑卡宾中间体, 进而参与多种重要的卡宾转移反应. 然而, 在传统的单一手性铑催化的不对称卡宾转移反应中, 当经历分步机理时,金属中心往往在立体选择性决定步骤之前发生解离, 导致产物的对映选择性难以得到有效控制. 为克服这一挑战, 化学家们发展了铑与手性磷酸协同作用的双催化策略. 手性磷酸作为一种优异的双功能有机小分子催化剂, 能够通过其独特的空间位阻效应与氢键供体能力, 在不依赖金属中心配位的情况下精准控制反应的立体选择性. 本文系统综述了2014年以来铑与手性磷酸共同参与的卡宾不对称催化反应的研究进展, 重点从协同催化、接力催化以及手性磷酸铑配合物催化三个方面展开讨论, 梳理该领域的发展脉络, 为复杂手性分子的构建提供新的思路.

关键词： 铑催化; 手性磷酸; 协同催化; 接力催化

本文引用格式

朱晓宇 , 罗宜铭 , 孙墁 , 李文泽 . 铑和手性磷酸参与的卡宾不对称催化反应研究进展[J]. 有机化学, 0 : 202602018 -202602018 . DOI: 10.6023/cjoc202602018

Abstract

Rhodium complexes occupy a central position in transition-metal catalysis owing to their unique electronic configurations 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 provide new insights for the synthesis of complex chiral molecules.

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

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