亚磷酸作为还原剂参与的有机反应研究进展

doi:10.6023/cjoc202404015

摘要/Abstract

有机还原反应是最基本的化学反应之一, 被广泛应用于医药、农药、染料以及其它各类精细化学品的合成. 目前常见的还原剂主要包括氢气、金属化物(硼氢化物、氢化铝锂、烷基铝, 及金属等)、活泼金属、硅烷和肼等. 亚磷酸是一种常见的工业化学品, 具有还原性, 且来源丰富, 廉价, 易于保存. 目前使用亚磷酸作为还原剂通常不需要过渡金属参与, 具有成本低,、条件简单以及后处理简便等优势. 然而, 与其它主要还原剂在有机还原反应中的大量应用相比, 亚磷酸作为还原剂参与的有机反应非常有限. 综述了近年来以亚磷酸作为还原剂参与的有机还原反应, 主要从反应类型、底物适用范围以及反应机理等方面进行阐述, 并初步讨论了该领域未来的发展趋势.

关键词: 亚磷酸, 碘, 还原剂, 还原反应, 无金属

Organic reduction reactions are one of the most basic chemical reactions, which are widely used in the synthesis of pharmaceuticals, agriculture chemicals, dye industry and fine chemicals. Common reducing agents mainly include hydrogen, metallic compounds (borohydride, lithium aluminum hydride, alkyl aluminium and low-valence metals, etc.), active metals, silane and hydrazine. Phosphorus acid is a common chemical in industry, it is also cheap, easy to access, and easy to use. At present, reactions using phosphorus acid as reducing agents usually do not require transition-metals, and has the advantages of low-cost, simple conditions and simple work-up procedures. However, compared with the extensive application of those common reducing agents in organic reduction reactions, the organic reactions using phosphorus acid as reducing agent are very limited. Organic reduction reactions which are using phosphorus acid as reducing agent are summarized from aspects of reaction type, the scope of substrate and reaction mechanism. Prospects in this field are also discussed.

Key words: phosphorus acid, iodine, reducing agent, reduction reaction, metal-free

引用此文

肖晶, 谢毓翔, 韩立彪. 亚磷酸作为还原剂参与的有机反应研究进展[J]. 有机化学, 2024, 44(12): 3702-3712.

Jing Xiao, Yuxiang Xie, Libiao Han. Advances in Organic Reactions Using Phosphorus Acid as Reducing Agent[J]. Chinese Journal of Organic Chemistry, 2024, 44(12): 3702-3712.

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图/表 22

图式1. 亚磷酸的互变异构及其作为还原剂的优点

Scheme 1. Tautomerization of phosphorus acid and its advan- tages as a reducing agent

图式2. 醇羟基的脱氧还原

Scheme 2. Deoxygenation of alcohols

图式3. 芳香酮化合物的脱氧还原

Scheme 3. Deoxygenation of aromatic ketones

图式4. 芳香酮化合物的脱氧还原机理

Scheme 4. Mechanism of deoxygenation of aromatic ketones

图式5. 苯乙酮酸的脱氧还原

Scheme 5. Deoxygenation of phenylglyoxylic acid

图式6. 芳香醛化合物的脱氧还原

Scheme 6. Deoxygenation of aromatic aldehydes

图式7. 芳香醛化合物的还原碘化

Scheme 7. Reductive iodination of aromatic aldehydes

图式8. 硝基芳烃的脱氧还原

Scheme 8. Deoxygenation of nitroarenes

图式9. 磷氧(硫)化合物的还原

Scheme 9. Reduction of phosphine oxides and phosphine chalcogenides

图式10. 双磷氧化合物的选择性还原

Scheme 9. Selective reduction of bidentate phosphine oxides

图式11. 磷氧化合物还原的可能历程

Scheme 11. Plausible reaction paths of the reduction phosphine oxides

图式12. 亚砜的脱氧还原

Scheme 12. Deoxygenation of sulfoxide

图式13. 苄卤还原及其反应历程

Scheme 13. Mechanism of the dehalogenation of benzyl halides

图式14. 苄卤参与的芳烃苄基化反应

Scheme 14. Benzylation of arenes with benzyl halides

图式15. 芳醛参与的芳烃苄基化反应

Scheme 15. Benzylation of arenes involving aromatic aldehydes

图式16. 芳醛脱氧还原分子内偶联反应

Scheme 16. Intromolecular coupling reaction via deoxygenation of aromatic aldehydes

图式17. 芳醛还原偶联制备N-苄基苯并杂环酮

Scheme 17. Preparation of N-benzyl benzo heterocyclic ketones from aromatic aldehydes

图式18. 反应历程

Scheme 18. Reaction path

图式19. 醛与P(O)-H试剂还原偶联制备三价膦

Scheme 19. Preparation of phosphines from the reductive coupling of aldehydes and P(O)-H compounds

图式20. 三价膦制备反应机理

Scheme 20. Mechanism of preparation of phosphines

图式21. 醛与P(O)-H试剂还原偶联制备膦氧化合物

Scheme 21. Preparation of phosphine oxides from the reductive coupling of aldehydes and P(O)-H compounds

图式22. 亚磷酸作为还原剂实现辅酶NAD＋的还原

Scheme 22. Reduction of coenzyme NAD＋ with phosphorus acid

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