Recent Advances in the Double Hydrophosphination and Hydrophosphinylation of Alkynes

doi:10.6023/cjoc202603007

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (9): 3546-3558.DOI: 10.6023/cjoc202603007 Previous Articles Next Articles

REVIEW

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
通讯作者: 朱能波, 鲍红丽
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: Nengbo Zhu, Hongli Bao
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)

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

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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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Fig. & Tab. 14

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

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

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

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

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

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

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

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

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

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

Figure 2. Structure of the dimeric magnesium complex

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

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

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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