低价钨催化的有机反应研究进展

doi:10.6023/cjoc202509012

有机化学 ›› 2026, Vol. 46 ›› Issue (3): 759-772.DOI: 10.6023/cjoc202509012 上一篇下一篇

综述与进展

低价钨催化的有机反应研究进展

许嘉龙^a, 孔泉^a, 陈建辉^b^,^*(), 张明月^a, 姬小明^a^,^*(), 程彪^a^,^*()

^a 河南农业大学烟草学院郑州 450046
^b 温州大学化学与材料工程学院浙江温州 325035

收稿日期:2025-09-09 修回日期:2025-11-01 发布日期:2025-12-09
通讯作者: 陈建辉, 姬小明, 程彪
基金资助:
国家自然科学基金(22301063); 河南农业大学拔尖人才基金(30501288); 及河南省高等学校重点科研(23A210022)

Recent Advances in Low-Valent Tungsten-Catalyzed Organic Reactions

Jialong Xu^a, Quan Kong^a, Jianhui Chen^b^,^*(), Mingyue Zhang^a, Xiaoming Ji^a^,^*(), Biao Cheng^a^,^*()

^a College of Tobacco Science, Henan Agricultural University, Zhengzhou 450046
^b College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035

Received:2025-09-09 Revised:2025-11-01 Published:2025-12-09
Contact: Jianhui Chen, Xiaoming Ji, Biao Cheng
Supported by:
National Natural Science Foundation of China(22301063); Top-Notch Personnel Fund of Henan Agricultural University(30501288); Key Research Project of Higher Education Institutions in Henan Province(23A210022)

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摘要/Abstract

低价钨凭借其独特的氧化还原活性、多变的配位几何构型及高路易斯酸性, 在高效高选择性的有机转化中展现出显著潜力. 综述了该领域在反应设计、机理研究及底物适用范围等方面的关键进展, 阐明低价钨催化体系可作为传统贵金属催化策略的一种互补且可持续的替代方案, 旨在为相关领域研究人员提供有价值的参考, 并推动低价钨催化在有机合成及相关领域的深入发展与应用创新.

关键词: 低价钨, 催化, 烯丙基取代反应, 还原反应, 异构化-官能团化反应

Low-valent tungsten catalysts have emerged to enable selective and efficient organic transformations, leveraging their unique redox flexibility, variable coordination geometries, and high Lewis acidity. The key developments in reaction design, mechanistic insights, and substrate scope expansion are summarized, positioning low-valent tungsten catalytic systems as a complementary and sustainable approach to conventional noble-metal systems. The aim is to provide valuable reference for researchers and stimulate further innovation in the development and application of low-valent tungsten catalysis in organic synthesis and related fields.

Key words: low-valent tungsten, catalysis, allylic substitution, reduction, isomerization-functionalization

引用此文

许嘉龙, 孔泉, 陈建辉, 张明月, 姬小明, 程彪. 低价钨催化的有机反应研究进展[J]. 有机化学, 2026, 46(3): 759-772.

Jialong Xu, Quan Kong, Jianhui Chen, Mingyue Zhang, Xiaoming Ji, Biao Cheng. Recent Advances in Low-Valent Tungsten-Catalyzed Organic Reactions[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 759-772.

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图/表 29

Figure 1. Fundamental properties of tungsten

Figure 2. High- and low-valent tungsten catalysts

Scheme 1. Stoichiometric reactions promoted by low-valent tungsten

Scheme 2. Regio-, stereo- and chemo-selectivities of W-catalyzed allylic alkylations

Scheme 3. Model for the regiochemistry of tungsten-catalyzed allylic alkylation

Scheme 4. Chemoselectivity for difunctional allylic alkylating agents

Scheme 5. Asymmetric allylic substitution reactions by Pfaltz

Scheme 6. Asymmetric allylic substitution reactions by Trost

Scheme 7. Tungsten-catalyzed allylic sulfonylation

Scheme 8. Regioselective allylic amination with amines

Scheme 9. Decarboxylative allylic amination of allylic alcohols with isocyanates

Scheme 10. Transformations of vinylthiiranes to 3,6-dihydro- 1,2-dithiins

Scheme 11. 1,3-Dipolar cycloaddition

Scheme 12. Homogeneous hydrogenation of imine

Scheme 13. Homogeneous hydrogenation of nitriles

Scheme 14. Homogeneous hydrogenation of quinolines

Scheme 15. Hydroboration of nitriles

Scheme 16. Hydroboration of esters

Scheme 17. Deoxygenative reduction of amides by Song

Scheme 18. Deoxygenative reduction of amides by Cheng

Scheme 19. N‑Alkylation of anilines with alcohols

Scheme 20. Alkenes amination of boronic acids with nitroaromatics

Scheme 21. Isomerization-carbonylativefunctionalization of alkenes

Scheme 22. Isomerization-hydroboration of alkenes

Scheme 23. Stereoselective isomerization of N-allyl amides to enamides

Scheme 24. Intermolecular oxidative dehydrogenative C—N coupling

Scheme 25. Intramolecular oxidative dehydrogenative C—N coupling

Scheme 26. Oxidative cross-dehydrogenative coupling

Scheme 27. Coupling carbonylation reactions

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低价钨催化的有机反应研究进展

Recent Advances in Low-Valent Tungsten-Catalyzed Organic Reactions

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