Recent Advances in Low-Valent Tungsten-Catalyzed Organic Reactions

doi:10.6023/cjoc202509012

Abstract

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.

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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

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