Recent Advances in Low-Valent Tungsten-Catalyzed Organic Reactions

doi:10.6023/cjoc202509012

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (3): 759-772.DOI: 10.6023/cjoc202509012 Previous Articles Next Articles

REVIEWS

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)

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 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

References 40

[1]	Brown, T.; Pitfield, P. In Critical Metals Handbook, Chapter 16, Ed.: Gunn, G., Wiley-Blackwell, Weinheim, Germany, 2013, p. 385.
[2]	Hoffmann, R.; Beier, B. F.; Muetterties, E. L.; Rossi, A. R. Inorg. Chem. 1977, 16, 511.
[3]	Adrjan, B.; Szymańska-Buzar, T. J. Organomet. Chem. 2008, 693, 2163.
[4]	Handzlik, J.; Kochel, A.; Szymańska-Buzar, T. Polyhedron 2012, 31, 622.
[5]	Handzlik, J.; Szymańska-Buzar, T. J. Organomet. Chem. 2014, 769, 136.
[6]	Liebov, B. K.; Harman, W. D. Chem. Rev. 2017, 117, 13721.
[7]	Fajardo, J. Jr.; Barth, A. T.; Morales, M.; Takase, M. K.; Winkler, J. R.; Gray, H. B. J. Am. Chem. Soc. 2021, 143, 19389.
[8]	Schrock, R. R. Angew. Chem., nt. Ed. 2006, 45, 3748.
[9]	Cui, M.; Jia, G. J. Am. Chem. Soc. 2022, 144, 12546.
[10]	Masuda, T.; Higashimura, T. Acc. Chem. Res. 1984, 17, 51.
[11]	Nezakati, T.; Seifalian, A.; Tan, A.; Seifalian, A. M. Chem. Rev. 2018, 118, 6766.
[12]	Ravelli, D.; Fagnoni, M.; Fukuyama, T.; Nishikawa, T.; Ryu, I. ACS Catal. 2018, 8, 701.
[13]	Ravelli, D.; Protti, S.; Fagnoni, M. Acc. Chem. Res. 2016, 49, 2232.
[14]	Smith, J. A.; Wilson, K. B.; Sonstrom, R. E.; Kelleher, P. J.; Welch, K. D.; Pert, E. K.; Westendorff, K. S.; Dickie, D. A.; Wang, X.; Pate, B. H.; Harman, W. D. Nature 2020, 581, 288.
[15]	Trost, B. M.; Hung, M. H. J. Am. Chem. Soc. 1983, 105, 7757.
[16]	Trost, B. M.; Hung, M. H. J. Am. Chem. Soc. 1984, 106, 6837.
[17]	Trost, B. M.; Tometzki, G. B.; Hung, M. H. J. Am. Chem. Soc. 1987, 109, 2176.
[18]	Lloyd-Jones, G. C.; Pfaltz, A. Angew. Chem., nt. Ed. Engl. 1995, 34, 462.
[19]	Trost, B. M.; Hachiya, I. J. Am. Chem. Soc. 1998, 120, 1104.
[20]	For tungsten-catalyzed allylic substitutions review, see: Moberg, C. Top. Organomet. Chem. 2012, 38, 209.
[21]	Xu, Y.; Salman, M.; Khan, S.; Zhang, J.; Khan, A. J. Org. Chem. 2020, 85, 11501.
[22]	Xu, W. Synlett 2025, 36, 407.
[23]	Xu, W. Org. Biomol. Chem. 2024, 22, 8625.
[24]	Adams, R. D.; Perrin, J. L. J. Am. Chem. Soc. 1999, 121, 3984.
[25]	Chen, Z.; Zhou, Y.; Hu, T.; Xiong, H.-Y.; Zhang, G. J. Org. Chem. 2021, 86, 7714.
[26]	Chakraborty, S.; Blacque, O.; Fox, T.; Berke, H. Chem.-Asian J. 2014, 9, 328.
[27]	Chakraborty, S.; Berke, H. ACS Catal. 2014, 4, 2191.
[28]	Vielhaber, T.; Heizinger, C.; Topf, C. J. Catal. 2021, 404, 451.
[29]	Song, H.; Xiao, Y.; Wei, J.; Liu, Y.; Yang, L.; Bai, P.; Yang, F.; Yu, K.; Xu, C.; Cai, X. Chem. Commun. 2024, 60, 5026.
[30]	Liu, Y.; Zhai, X.; Yang, L.; Cai, X.; Yang, F.; Xu, C.; Song, H. Org. Lett. 2024, 26, 11067.
[31]	Cheng, B.; Xv, J.; Ren, X.; Li, Y.; Ji, X.; Lu, Z. Org. Chem. Front. 2025, 12, 3306.
[32]	Lan, X.-B.; Ye, Z.; Yang, C.; Li, W.; Liu, J.; Huang, M.; Liu, Y.; Ke, Z. ChemSusChem 2021, 14, 860.
[33]	Song, H.; Shen, Y.; Zhou, H.; Ding, D.; Yang, F.; Wang, Y.; Xu, C.; Cai, X. J. Org. Chem. 2022, 87, 5303.
[34]	Jankins, T. C.; Bell, W. C.; Zhang, Y.; Qin, Z.-Y.; Chen, J. S.; Gembicky, M.; Liu, P.; Engle, K. M. Nat. Chem. 2022, 14, 632.
[35]	Jankins, T. C.; Martin-Montero, R.; Cooper, P.; Martin, R.; Engle, K. M. J. Am. Chem. Soc. 2021, 143, 14981.
[36]	Chen, Y.; Yang, H.; Zhang, J.; Hu, W.; Zheng, J. J. Catal. 2025, 443, 115976.
[37]	Cai, X.; Shen, Y.; Li, W.; Zhan, W.; Zhang, F.; Xu, C.; Song, H. Org. Lett. 2023, 25, 240.
[38]	Li, C.; Chen, Y.; Ye, F.; Chen, J.; Zheng, J. Molecules 2023, 28, 8071.
[39]	Li, C.; Chen, Y.; Huang, X.; Chen, J.; Ye, F.; Chen, L. ChemistrySelect 2024, 9, e202304891.
[40]	Ye, F.; Lu, L.; Huang, Z.; Huang, Y.; Huang, L.; Li, C.; Li, X. Molecules 2024, 29, 5305.

低价钨催化的有机反应研究进展

Recent Advances in Low-Valent Tungsten-Catalyzed Organic Reactions

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 29

References 40

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Zening Huang, Kaicheng Zuo, Tao Hu, Chengyang Zhang, Jinlong Zhang, Gaoxi Jiang. Phosphoric Acid-Catalyzed Double/Triple Pictet-Spengler Annulation/Oxidative Aromatization for Construction of C₂- and C₃-Symmetrical Quinazolinones [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 1070-1077.
[2]	Yu Sun, Yantao Zhu, Dong Zhang, Chunjie Ni. Nickel-Catalyzed Annulation of Alkynyl with Trifluoroacetimidoyl Chlorides and H₂O: Facile Access to 2‑(Trifluoromethyl)indole Derivatives [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 1017-1026.
[3]	Nana Wei, Wanzhen Guo, Xing Lu, Zhiqiang Ren, Haojie Ma, Yuqi Zhang, Jijiang Wang, Bo Han. Magnesium-Promoted Selectively Reduction of Unprotected Indoles and Quinoxalines [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 1027-1038.
[4]	Jinyu Zhang, Zhigang Lu, Zhe Liu, Cong Wang. Transition Metal-Catalyzed Hydrosilylation and Boration of Methylenecyclopropanes [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 806-816.
[5]	Shunli Zhou, Ji Liu, Ting Lei, Binquan Yang, Shizhi Jiang. Advances in Chiral Synthesis of 2-Aryl-2H-chromene Derivatives [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 773-785.
[6]	Qichang Yang, Xiaorui Zhang, Jian Lv, Shuang-Xi Gu. Advances in Selective Oxidation of Carbohydrates [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 743-758.
[7]	Chunnian Xia, Kailin Chen, Nuoqi Jin, Xinghui Nan, Bingyang Wang, Xinyi Wu, Qiangsheng Sun, Wei Sun. Efficient Oxidation of Alcohols Using a Bioinspired Tetradentate Aminopyridine Manganese Catalyst with H₂O₂: Batch and Continuous Flow Studies [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 986-992.
[8]	Xinyu Liang, Chunchun Mi, Fujun Guo, Wenbin Xie, Qinqin Shi, Hui Huang. Desulfinative Cross-Coupling of Aryl Sodium Sulfinate with Aryl Sulfonium Salts [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 1000-1007.
[9]	Yanhui Guo, Hongen Qu, Pei Liang. Recent Advances in Synthesis of Chiral Organoselenium Compounds [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 786-805.
[10]	Xiaoxiang Xi, Ming Gao, Libiao Han. Rhodium-Catalyzed Reduction of RS—SR to Thiophenols/Thiols with H₂ [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 859-865.
[11]	Yingjie Liu, Laisheng Min, Ruirong Yang, Dongxue Song, Rui Peng, Deqiang Liang. CuI-Catalyzed C—C Bond Coupling Reaction for the Construction of 2-Carbonyl-1,4-diketones [J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 603-611.
[12]	Yunyi Zhang, Hanbing Yan, Xianjin Zhu, Yongjia Shi, Junxin Li, Daoshan Yang, Xufeng Li. Nickel-Catalyzed Reductive Cascade Arylalkylation of Alkenes with Cyclosulfonium Salts [J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 653-663.
[13]	Yiling Zeng, Fangpeng Liang, Hui Li, Rongrong Liu, Shiqing Li. Multi-component C—H Annulation of α-Oxocarboxylic Acids, Allynes and Primary Amines to Yield Isoquinolinium Skeletons [J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 554-563.
[14]	Huiyang Liu, Du Chen, Yijin Su, Peng Zhang, Chao Liu. Rapid and Controlled Reduction of Acyl Chlorides to Aldehydes Using Pinacolborane [J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 564-569.
[15]	Mengdie Li, Zihan Wang, Taoyan Lin. Recent Progress in Copper-Catalyzed Remote Yne-Allylic Substitution Reaction [J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 356-378.