炔烃双氢膦(酰)化反应的研究进展

doi:10.6023/cjoc202603007

有机化学 ›› 2026, Vol. 46 ›› Issue (9): 3546-3558.DOI: 10.6023/cjoc202603007 上一篇下一篇

综述与进展

炔烃双氢膦(酰)化反应的研究进展

成东婷^a^,^b, 朱能波^b^,^*(), 鲍红丽^a^,^b^,^c^,^d^,^*()

^a 福建师范大学化学与材料学院福州 350007
^b 中国科学院福建物质结构研究所结构化学全国重点实验室福州 350002
^c 中国科学院大学福建学院福州 350002
^d 福州大学化学学院福州 350108

收稿日期:2026-03-05 修回日期:2026-04-18 发布日期:2026-05-18
基金资助:
国家自然科学基金(22225107); 福建省自然科学基金(2025J01249)

Recent Advances in the Double Hydrophosphination and Hydrophosphinylation of Alkynes

Dongting Cheng^a^,^b, Nengbo Zhu^b^,^*(), Hongli Bao^a^,^b^,^c^,^d^,^*()

^a College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007
^b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002
^c Fujian College, University of Chinese Academy of Sciences, Fuzhou 350002
^d College of Chemistry, Fuzhou University, Fuzhou 350108

Received:2026-03-05 Revised:2026-04-18 Published:2026-05-18
Contact:
^* E-mail: hlbao@fjirsm.ac.cn;
zhunengbo@fjirsm.ac.cn
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
Supported by:
National Natural Science Foundation of China(22225107); Natural Science Foundation of Fujian Province(2025J01249)

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摘要/Abstract

双齿膦配体因其能够协同调控过渡金属中心的电子结构与空间构型, 在催化反应中发挥着重要作用. 近年来, 通过炔烃双氢膦(酰)化反应构建各类双膦配体的方法取得了长足发展, 该反应在选择性调控及底物适用范围等方面取得了显著进展. 从过渡金属催化与模板促进体系、非过渡金属体系以及自由基与光催化体系三个方面, 综述了不同类型炔烃双氢膦(酰)化反应的研究进展, 对比1,1-与1,2-二膦骨架构建中的区域与立体选择性规律, 分析催化剂失活等关键问题, 并对该领域发展前景进行展望.

关键词: 双氢膦化, P—C键构筑, 双齿膦配体, 选择性调控, 催化剂失活

Bidentate phosphine ligands play an important role in catalysis because they can cooperatively regulate the electronic properties and steric environment of transition metal centers. In recent years, significant progress has been made in methods for constructing various diphosphine ligands through the double hydrophosphination (hydrophosphinylation) of alkynes. Considerable advances have been achieved in selectivity control and substrate scope. This review summarizes recent progress in alkyne double hydrophosphination (hydrophosphinylation) from three aspects: transition metal-catalyzed and template-promoted systems, non-transition-metal systems, and radical and photocatalytic systems. The regioselectivity and stereoselectivity in the formation of 1,1- and 1,2-diphosphine frameworks are analyzed. Key issues, such as catalyst deactivation, are also discussed. Finally, the future prospects of this field are outlined.

Key words: double hydrophosphination, P—C bond construction, bidentate phosphine ligand, selectivity control, catalyst deactivation

引用此文

成东婷, 朱能波, 鲍红丽. 炔烃双氢膦(酰)化反应的研究进展[J]. 有机化学, 2026, 46(9): 3546-3558.

Dongting Cheng, Nengbo Zhu, Hongli Bao. Recent Advances in the Double Hydrophosphination and Hydrophosphinylation of Alkynes[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3546-3558.

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图/表 14

图1. 炔烃双氢膦(酰)化反应构建1,2-与1,1-双膦骨架的合成策略

Figure 1. Synthetic strategies for constructing 1,2- and 1,1-bisphosphine scaffolds via double hydrophosphination (hydrophosphinylation) of alkynes

图式1. 双氢膦化过程中铑-NHC络合物上的化学计量反应

Scheme 1. Stoichiometric reactions on Rh-NHC complexes involved in the double hydrophosphination process

图式2. Pd(PPh3)4催化末端炔烃与二苯基膦氧化物的双氢膦酰化反应

Scheme 2. Pd(PPh3)4-catalyzed double hydrophosphinylation of terminal alkynes with diphenylphosphine oxide

图式3. 手性钯模板体系促进的末端炔烃与二苯基膦的双氢膦化反应

Scheme 3. Chiral palladium template-promoted double hydrophosphination of terminal alkynes with diphenylphosphine

图式4. 铁催化体系下末端芳基炔烃与二苯基膦的双氢膦化反应

Scheme 4. Iron-catalyzed double hydrophosphination of terminal aryl alkynes with diphenylphosphine

图式5. 铜催化体系下的炔烃与二苯基膦的双氢膦化反应

Scheme 5. Copper-catalyzed double hydrophosphination of alkynes with diphenylphosphine

图式6. 叔丁醇锂催化末端炔烃与二级膦氧化合物的双氢膦酰化反应

Scheme 6. t-BuOLi-catalyzed double hydrophosphinylation of terminal alkynes with secondary phosphine oxides

图式7. KHMDS催化乙基丙炔酸酯与二苯基膦的双氢膦化反应的可能催化循环

Scheme 7. Proposed catalytic cycle for the KHMDS-catalyzed double hydrophosphination of ethyl propiolate with diphenylphosphine

图式8. 碱金属预催化剂促进末端炔烃与二苯基膦氧化物的双氢膦酰化反应

Scheme 8. Alkali metal precatalyst-promoted double hydrophosphinylation of terminal alkynes with diphenylphosphine oxide

图式9. 三价膦催化炔酸酯与二级膦氧化物的双氢膦酰化反应机理

Scheme 9. Proposed mechanism for the trivalent phosphine-catalyzed double hydrophosphinylation of alkynoates with secondary phosphine oxides

图2. 二聚镁配合物结构

Figure 2. Structure of the dimeric magnesium complex

图式10. 镧系金属催化的炔烃与二苯基膦氧化物的单、双氢膦酰化反应

Scheme 10. Lanthanide-catalyzed mono- and double hydrophosphinylation of alkynes with diphenylphosphine oxide

图式11. 镧系金属催化的内炔与二苯基膦氧化物的双氢膦酰化反应机理

Scheme 11. Proposed reaction mechanism for the lanthanide- catalyzed double hydrophosphinylation of internal alkynes with diphenylphosphine oxide

图式12. 空气诱导的末端炔烃与二级膦氧化物的双氢膦酰化反应

Scheme 12. Air-initiated double hydrophosphinylation of terminal alkynes with secondary phosphine oxides

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炔烃双氢膦(酰)化反应的研究进展

Recent Advances in the Double Hydrophosphination and Hydrophosphinylation of Alkynes

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