草酸酯类化合物在自由基脱羟基化反应中的研究进展

doi:10.6023/A23070339

摘要/Abstract

羟基作为醇类化合物的基本结构单元, 广泛存在于药物、天然产物、农药以及精细化学品中. 烷基自由基则是自由基化学领域最基础性的合成砌块. 因此, 将醇转化为烷基自由基, 具有基础性的研究价值. 通常醇类化合物可以通过Barton-McCombie反应, 实现自由基形式的脱羟基化反应, 得到烷基自由基. 然而传统脱羟基化反应存在诸多缺陷. 因此发展一种简洁高效的脱羟基化方法具有重要的现实意义. 随着近年来有机化学的发展, 自由基脱羟基化反应取得突破性进展. 本综述节选其中一部分, 着重介绍了草酸酯类化合物在自由基脱羟基化反应中的研究进展和设计原理, 对比不同活化策略的反应机理, 系统性地总结了邻苯二甲酰亚胺类型草酸酯、草酸单酯和草酸酯类化合物在自由基脱羟基化反应中的共性和个性, 展望了自由基脱羟基化反应的未来和趋势.

关键词: 光催化, 自由基, 脱羟基化, 醇, 草酸酯

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

引用此文

陈健强, 朱钢国, 吴劼. 草酸酯类化合物在自由基脱羟基化反应中的研究进展[J]. 化学学报, 2023, 81(11): 1609-1623.

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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图/表 28

图1. 光催化邻苯二甲酰亚胺衍生的烷基草酸酯的碎裂化

Figure 1. Photocatalyzed fragmentation of alkyl N?phthalimidoyl oxalates

图2. 光催化邻苯二甲酰亚胺衍生的烷基草酸酯的炔基化反应

Figure 2. Photocatalyzed alkynylation of alkyl N?phthalimidoyl oxalates

图3. 电化学促进醇的脱羟基化反应

Figure 3. Electro-induced deoxygenation of alcohols

图4. 光催化烷基草酸单酯的碎裂化反应

Figure 4. Photocatalyzed fragmentation of alkyl oxalates

图5. Cheloviolenes A 和 B, Dendrillolide A 和 C 以及Macfarlandin C的天然产物全合成

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

图6. 三级烷基自由基的1,6-加成反应

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

图7. 缺电子杂芳烃的自由基烷基化反应

Figure 7. Radical alkylation of electron-deficient heteroarenes

图8. 氮杂芳环的烷基化反应

Figure 8. Alkylation of N-heteroarenes

图9. 菲催化的草酸酯与芳基腈类底物的偶联反应

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

图10. 光催化草酸酯类化合物的炔基化反应

Figure 10. Photocatalyzed alkynylation of alkyl oxalates

图11. 光促进的脱羟基/炔基化反应

Figure 11. Photocatalyzed deoxyalkynylation

图12. 金属催化与光催化相结合的草酸酯与芳基卤化物的交叉偶联反应

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

图13. 金属催化和光氧化还原催化相结合的端炔的烷基芳基化反应

Figure 13. Metallaphotoredox catalyzed alkylarylation of terminal alkynes

图14. 金属催化和光氧化还原催化相结合的端烯的烷基芳基化反应

Figure 14. Metallaphotoredox catalyzed alkylarylation of terminal alkenes

图15. 金属催化和光氧化还原催化相结合的多组分串联反应

Figure 15. Metallaphotoredox catalyzed multicomponent radical cascade

图16. 光促进的脱羟基卤化反应

Figure 16. Photocatalyzed deoxyhalogenation

图17. 银催化的脱羟基氟化反应

Figure 17. Ag-catalyzed deoxyfluorination

图18. 光促进的偕二氟烯丙基化反应

Figure 18. Photoredox-catalyzed gem-difluoroallylation

图19. 镍催化草酸苄酯与烷基溴化物的还原偶联反应

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

图20. 锌促进的草酸酯类化合物的碎裂化

Figure 20. Zn-mediated fragmentation of oxalates

图21. 镍催化的草酸酯类化合物的芳基化反应

Figure 21. Ni-catalyzed arylation of oxalates

图22. 铁催化的草酸酯类化合物的还原烯基化反应

Figure 22. Fe-catalyzed reductive vinylation of oxalates

图23. 铁或锌促进的草酸酯类化合物的C—O键碎裂化反应

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

图24. 光催化醇的脱羟基硼化反应

Figure 24. Photoredox-catalyzed deoxygenative borylation of alcohols

图25. 无催化剂条件下的光催化醇的脱羟基硼化反应

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

图26. 镍催化苄醇的芳基化反应

Figure 26. Ni-catalyzed arylation of benzyl alcohols

图27. 镍催化还原偶联反应

Figure 27. Ni-catalyzed reductive coupling reaction

图28. 自由基环化合成二环[3.2.1]辛烷

Figure 28. Radical annulation toward bicyclo[3.2.1]octanes

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