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过渡金属催化惰性C-H键的膦化反应研究
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Abstract:
C-H键直接膦化反应是构建有机膦化合物的高效策略，近年来在过渡金属催化、光/电催化及无金属催化领域取得了显著进展。本文系统综述了C(sp2)-H与C(sp3)-H键膦化反应的研究现状与发展趋势。导向基团辅助的贵金属(Pd, Rh)催化体系可实现高区域选择性的邻位C-H键膦化，但受限于导向基的引入与移除；自由基介导的廉价金属(Mn, Fe, Cu)催化体系则无需导向基，适用于富电子芳烃、杂环及苄位和未活化烷烃的C-H膦化，展现出良好的底物普适性与绿色可持续潜力。光/铜协同催化、电化学锰催化及铁/LMCT光催化等新兴策略，分别在苄位C(sp3)-H不对称膦化、无氧化剂芳烃膦化及未活化烷烃C(sp3)-H选择性膦化方面取得了突破。此外，无金属催化与机器学习辅助配体设计为未来高效、高选择性C-P键构筑提供了新方向。本文总结了不同催化机制的优势与局限，并展望了不对称催化、电化学与光催化融合以及计算辅助催化剂开发等前沿方向。
Direct C-H phosphonylation has emerged as a powerful strategy for the construction of organophosphorus compounds. Significant progress has been made in transition-metal catalysis, photo/electrocatalysis, and metal-free systems. This review systematically summarizes the current status and development trends in C(sp2)-H and C(sp3)-H phosphonylation. Directed C-H phosphonylation using noble metals (Pd, Rh) achieves high regioselectivity but suffers from the requirement of directing group installation and removal. In contrast, radical-mediated phosphonylation using inexpensive metals (Mn, Fe, Cu) enables undirected C-H functionalization of electron-rich arenes, heterocycles, benzylic sites, and even unactivated alkanes, offering broad substrate scope and sustainable potential. Emerging strategies such as photo/copper dual catalysis, electrochemical manganese catalysis, and iron/LMCT photocatalysis have achieved breakthroughs in asymmetric benzylic C(sp3)-H phosphonylation, oxidant-free arene phosphonylation, and selective C(sp3)-H phosphonylation of unactivated alkanes. Furthermore, metal-free approaches and machine-learning-assisted ligand design open new avenues for efficient and highly selective C-P bond formation. This review highlights the advantages and limitations of different catalytic mechanisms and discusses future directions including asymmetric catalysis, integration of photo/electrochemistry, and computational catalyst development.
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