光诱导醇的直接脱羟基衍生化研究进展

doi:10.6023/cjoc202303036

摘要/Abstract

由于C_sp3—O键键能大的特点, 传统还原裂解醇类的方法多涉及间接的活化过程, 在温和条件下对醇C_sp3—O键直接裂解是一个巨大的挑战. 近年来通过光诱导条件直接对其裂解进行脱羟基还原、脱羟基衍生化的策略取得了重大的突破, 这些策略相较于传统方法不需要预活化步骤, 也能避免传统当量氧化还原剂的使用, 具有更好的原子经济性、步骤经济性以及氧化还原经济性. 该主题综述文献较少, 在此重点综述了光诱导下醇C_sp3—O键直接裂解还原及衍生化的进展, 从而进一步推动该领域的蓬勃发展.

关键词: 醇, 还原, 烷基化, 脱羟基, 光化学

Conventional methods for the reduction of alcohols mainly deal with the indirect cleavages of C_sp3—O bond involving tedious activated steps. In contrast, the more straightforward direct reduction of naturally abundant aliphatic alcohols to alkanes or other reductive derivatives poses a challenge to organic chemists due to the inherently stable and less reactive C_sp3—O bond. The development of direct reductive strategies induced by light is of utmost importance due to their atom economy, step economy and redox economy, and many progresses have been made in this area these years. However, very few reviews on this topic has been reported so far. Herein, the recent progress in the light-driven direct deoxygenation of alcohols with emphasis on important advances last ten years is reviewed, which is expected to further promote the vigorous development of this field.

Key words: alcohols, reduction, alkylation, dehydroxylation, photochemistry

引用此文

鄢伯钰, 吴阶良, 邓金飞, 陈丹, 叶秀深, 姚秋丽. 光诱导醇的直接脱羟基衍生化研究进展[J]. 有机化学, 2023, 43(9): 3055-3066.

Boyu Yan, Jieliang Wu, Jinfei Deng, Dan Chen, Xiushen Ye, Qiuli Yao. Recent Progress in Light-Driven Direct Dehydroxylation and Derivation of Alcohols[J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3055-3066.

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图/表 26

图式1. 光诱导醇的一锅脱氧反应

Scheme 1. Photoinduced one-pot deoxygenation of alcohols

图式2. 光及金催化剂诱导下醇的脱氧反应

Scheme 2. Photocatalytic deoxygenation of alcohols via gold catalyst

图式3. 光诱导烯丙醇的氢转移还原

Scheme 3. Photocatalytic transfer hydrogenolysis of allylic alcohols

图式4. Ir催化剂介导苄醇的还原

Scheme 4. Reduction of benzylic alcohols via Ir catalyst

图式5. 光诱导、无金属参与下苄醇的脱氧还原

Scheme 5. Light-driven metal-free direct deoxygenation of ben- zyl alcohols

图式6. 光诱导无金属参与下苄醇的羧化反应

Scheme 6. Light-driven metal-free direct carboxylation of benzyl alcohols

图式7. 硼自由基介导苄醇的羧化反应

Scheme 7. Carboxylation of benzylic alcohols via boryl radical

图式8. 光氧化还原剂及镍双重催化下烯丙醇的直接羧化反应

Scheme 8. Direct carboxylation of allylic alcohols by photoredox/nickel dual catalysis

图式9. 光催化剂促进醇的卤代反应

Scheme 9. Photocatalytic halogenation of alcohols

图式10. 光催化剂促进糖的溴代反应

Scheme 10. Photocatalytic bromination of saccharides

图式11. 可见光驱动醇的碘代反应

Scheme 11. Transformation of alcohol to iodide under visible light

图式12. NBS或NCS介导醇的直接卤代反应

Scheme 12. Halogenation of alcohols via NBS or NCS

图式13. NBS或NCS介导醇的直接卤代反应

Scheme 13. Halogenation of alcohols via NBS or NCS

图式14. 光诱导醇脱羟基烷基化反应

Scheme 14. Photoinduced deoxyalkylation with alcohols

图式15. 可见光诱导醇的脱氧烷基化反应

Scheme 15. Visible light induced deoxyalkylation with alcohols

图式16. 自旋中心转移策略于醇与醛的不对称苄基化反应

Scheme 16. Spin-center shift-enabled enantioselective benzylation of aldehydes with alcohols

图式17. NHC介导醇与卤代烃的偶联反应

Scheme 17. NHC-mediated coupling of alcohols with aryl halide

图式18. NHC介导醇与羧酸衍生物的偶联反应

Scheme 18. NHC-mediated coupling of alcohols with carboxylic acid derivatives

图式19. 醇的直接三氟甲基化反应

Scheme 19. Direct trifluoromethylation of alcohols

图式20. 醇与Michael受体的烷基化反应

Scheme 20. Alkylation with alcohols and Michael acceptors

图式21. 醇与Michael受体的脱羟基加成反应

Scheme 21. Dehydroxylative addition of alcohols with Michael acceptors

图式22. 无催化剂条件下醇与不饱和物的脱羟基烷基化反应

Scheme 22. Catalyst-free dehydroxylative alkylation of unsaturated compounds with alcohols

图式23. 受阻路易斯酸碱对介导醇或硫醇的直接烷基化反应

Scheme 23. Direct alkylation with alcohols and thiols via frustrated Lewis pairs

图式24. 紫外光诱导醇参与的甲基化反应

Scheme 24. UV-light induced methylation with alcohols

图式25. 可见光诱导醇参与合成喹唑啉酮衍生物

Scheme 25. Visible-light induced synthesis of quinazolinone derivatives with alcohols

图式26. 可见光诱导醇参与合成二氢喹啉酮或喹唑啉酮衍生物

Scheme 26. Visible-light induced synthesis of dihydroquinazolinone or quinazolinone derivatives with alcohols

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