Recent Advances in Radical-Based Dehydroxylation of Hydroxyl Groups via Oxalates

doi:10.6023/A23070339

Abstract

Alcohols are among the most synthetically versatile, operationally convenient, and commercially abundant functional groups in modern organic chemistry, which are widely present in a variety of drugs, natural products, agrochemicals, and fine chemicals. Alkyl radicals are the most important building blocks in radical chemistry. Traditionally, the alkyl radicals can be generated from the alcohols through the Barton-McCombie radical deoxygenation reaction. Despite the importance of this reaction, one of the several limitations of this strategy is the requirement of stoichiometric quantities of hazardous reagents. Another limitation is that the generated alkyl radical can abstract a hydrogen atom from tributyltin hydride to deliver an alkane. Therefore, development of a convenient and compatible method for generation of alkyl radicals from alcohols has synthetic appeal, yet it represents a long-term challenge and urgent demand. With the development of organic chemistry, much efforts have been devoted to the development of this transformation. This paper reviews the recent advances in dehydroxylation of hydroxyl groups via oxalates, focuses on the design principles and concepts of these strategies, compares the reaction mechanisms, and summarizes the generalities and differences of these methods. It is divided into three sections consisting of the radical-based dehydroxylation of hydroxyl groups via N‑phthalimidoyl oxalates, oxalate monoester salts and oxalates. The future and trend of radical-based dehydroxylation of hydroxyl groups in organic chemistry were prospected.

Key words: photocatalysis, free radicals, dehydroxylation, alcohols, oxalates

Cite this article

Jianqiang Chen, Gangguo Zhu, Jie Wu. Recent Advances in Radical-Based Dehydroxylation of Hydroxyl Groups via Oxalates[J]. Acta Chimica Sinica, 2023, 81(11): 1609-1623.

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Fig. & Tab. 28

Figure 1. Photocatalyzed fragmentation of alkyl N?phthalimidoyl oxalates

Figure 2. Photocatalyzed alkynylation of alkyl N?phthalimidoyl oxalates

Figure 3. Electro-induced deoxygenation of alcohols

Figure 4. Photocatalyzed fragmentation of alkyl oxalates

Figure 5. Total syntheses of Cheloviolenes A and B, Dendrillolide A and C and Macfarlandin C

Figure 6. 1,6-Addition of tertiary carbon radicals

Figure 7. Radical alkylation of electron-deficient heteroarenes

Figure 8. Alkylation of N-heteroarenes

Figure 9. Phenanthrene-catalyzed coupling of oxalates with aromatic nitriles

Figure 10. Photocatalyzed alkynylation of alkyl oxalates

Figure 11. Photocatalyzed deoxyalkynylation

Figure 12. Metallaphotoredox catalyzed cross-coupling of oxalates with aryl halides

Figure 13. Metallaphotoredox catalyzed alkylarylation of terminal alkynes

Figure 14. Metallaphotoredox catalyzed alkylarylation of terminal alkenes

Figure 15. Metallaphotoredox catalyzed multicomponent radical cascade

Figure 16. Photocatalyzed deoxyhalogenation

Figure 17. Ag-catalyzed deoxyfluorination

Figure 18. Photoredox-catalyzed gem-difluoroallylation

Figure 19. Ni-catalyzed reductive coupling of benzyl oxalates with alkyl bromides

Figure 20. Zn-mediated fragmentation of oxalates

Figure 21. Ni-catalyzed arylation of oxalates

Figure 22. Fe-catalyzed reductive vinylation of oxalates

Figure 23. Fe or Zn-mediated C—O bond fragmentation of oxalates

Figure 24. Photoredox-catalyzed deoxygenative borylation of alcohols

Figure 25. Catalyst-free photo-induced deoxygenative borylation of alcohols

Figure 26. Ni-catalyzed arylation of benzyl alcohols

Figure 27. Ni-catalyzed reductive coupling reaction

Figure 28. Radical annulation toward bicyclo[3.2.1]octanes

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