锰催化的有机合成偶联反应进展

doi:10.6023/cjoc202412002

摘要/Abstract

近年来, 使用丰富、廉价且低毒的锰催化有机偶联反应受到了广泛关注. 综述了锰在偶联反应中的应用进展, 重点研究其在碳-碳键及碳-杂键形成中的表现. 通过分析锰催化脱氢偶联反应、交叉偶联反应及其与其他金属的联合催化, 展示了锰催化在合成复杂分子中的潜力. 总结了锰的多种偶联反应机制, 并探讨了添加剂在反应中的关键作用. 研究表明, 锰催化剂具有高效、选择性好和环境友好等特点, 尤其在无受体脱氢偶联反应中表现出优异的催化活性, 但其机理探索和添加剂的优化仍具广阔的发展空间. 锰作为一种可持续资源, 未来在有机合成中的应用前景广阔.

关键词: 锰催化剂, 偶联反应, 脱氢偶联, 交叉偶联, 有机合成

In recent years, the use of abundant, cheap and less toxic manganese as catalysts for coupling reactions in organic synthesis has attracted widespread attention. This article aims to review the application of manganese catalysts in coupling reactions, focusing on their performance in the formation of carbon-carbon bond and carbon-heteroatom bond. By analyzing the manganese-catalyzed dehydrogenative coupling reactions, cross-coupling reactions and their combined catalysis with other metals, the potential of manganese catalysis in the synthesis of complex molecules is demonstrated. This article summarizes the various coupling reaction mechanisms of manganese reagents and explores the key role of additives in the reaction. Studies have shown that manganese catalysts have the characteristics of high efficiency, good selectivity and environmental friendliness, especially in the acceptor-free dehydrogenative coupling reaction, which shows excellent catalytic activity although there is still a broad space for development in its mechanism exploration and additive optimization. As a sustainable resource, manganese has broad prospects for application in organic synthesis in the future.

Key words: manganese catalysis, dehydrogenative coupling, cross coupling, organic synthesis

引用此文

王超, 陈洪平, 米明众, 李澳文, 齐燕, 刘永军. 锰催化的有机合成偶联反应进展[J]. 有机化学, 2025, 45(7): 2326-2334.

Chao Wang, Hongping Chen, Mingzhong Mi, Aowen Li, Yan Qi, Yongjun Liu. Application of Manganese Catalysts in Coupling Reactions in Organic Synthesis[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2326-2334.

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图/表 29

图式1. 醇(酯)与胺合成酰胺的反应

Scheme 1. Reaction of alcohols (esters) with amine synthetic amides

图式2. 甲醇与胺合成甲酰胺的反应

Scheme 2. Reaction of methanol with amines to formamide

图式3. 二元醇与胺合成酰亚胺的反应

Scheme 3. Reaction of diols with amines to synthesis of amino acid

图式4. 醇与氨气合成酰胺的反应

Scheme 4. Reaction of alcohol to ammonia to amide

图式5. 甲醇与二胺化合物的储氢体系

Scheme 5. Hydrogen storage system of methanol and diamine compounds

图式6. 醇偶联合成酯的反应

Scheme 6. Reaction of alcohol coupling into esters

图式7. 醇偶联合成酯的反应

Scheme 7. Reaction of alcohol coupling into esters

图式8. 锰催化仲醇偶联合成醇(酮)

Scheme 8. Manganese-catalysed coupling of secondary alcohols for the synthesis of alcohols (ketones)

图式9. 二烷基镁配合物与邻代苯甲酰氯的串联交叉偶联

Scheme 9. Tandem cross-coupling of dialkyl magnesium complexes with o-benzoyl chloride

图式10. N-杂环氯化物与格氏试剂的交叉偶联反应

Scheme 10. Coupling reaction of N-heterocyclochloride with Grignard reagent

图式11. 非活化烯基卤化物与芳基格氏试剂的立体特异性交叉偶联

Scheme 11. Stereospecific cross-coupling of inactivated alkenyl halides to aryl Grignard reagents

图式12. Mn(I)催化烯烃的氢烯化反应

Scheme 12. Mn(I) catalyzes the hydrogenylation of olefins

图式13. Mn催化的末端炔烃的支链氢烯化反应

Scheme 13. Mn-catalysed branched hydroalkenylation of terminal alkynes

图式14. Mn或Pd催化的交叉偶联反应

Scheme 14. Mn-catalyzed cross-coupling reactions

图式15. 使用空气作为氧化剂的锰催化格氏试剂交叉偶联

Scheme 15. Manganese-catalyzed cross-coupling of Grignard reagents using air as an oxidizing agent

图式16. 锰催化格氏试剂与空气氧化交叉偶联

Scheme 16. Manganese-catalyzed extension of the heterocouplement of Grignard reagent to air oxidation

图式17. 锰催化C—B键形成交叉偶联反应

Scheme 17. Manganese catalyzes the formation of C-B bonds in cross-coupling reactions

图式18. 锰催化的烯烃叠氮过氧化反应

Scheme 18. Manganese-catalyzed azide peroxidation of olefins

图式19. Mn(PDP)/ClCH2COOH催化叔碳氢羟基化的反应

Scheme 19. Mn(PDP)/ClCH2COOH catalyzes tertiary hydrocarbonylation

图式20. 锰催化异芳烃和丙炔碳酸酯的反应

Scheme 20. Manganese catalyzes the reaction of isoaromatic hydrocarbons and propynyl carbonates

图式21. 烯基碲化物与芳基格氏试剂的交叉偶联

Scheme 21. Cross-coupling of alkenyl telluride with aryl Grignard reagent

图式22. 锰和钴的联合催化反应

Scheme 22. Combined catalytic reaction of manganese and cobalt

图式23. 烷基吡啶盐与芳基溴的反应

Scheme 23. Reaction of alkyl pyridine salts with aryl bromide

图式24. Mn(I)/Ag(I)继电器催化的反应

Scheme 24. Mn(I)/Ag(I) relay catalyzed reaction

图式25. Ni/Ti/Mn体系下苄基醇与卤代烷烃的反应

Scheme 25. Reaction of benzyl alcohols and haloalkanes in Ni/ Ti/Mn system

图式26. 锰催化的Friedel-Crafts烷基化反应

Scheme 26. Mn-catalyzed Friedel-Crafts alkylation reactions (a) MnBr(CO)3-catalysed Friedel-Crafts alkylation; (b) Manganese(I)- catalyzed Friedel-Crafts alkylation

图式27. 三价锰引发的自由基反应

Scheme 27. Mn(Ⅲ)-induced radical reactions

图式28. 锰催化烯烃加氢自由基反应

Scheme 28. Manganese-catalysed olefin hydrogenation radical reaction

图式29. 锰催化氯甲基苯腈与格式试剂的自由基反应

Scheme 29. Manganese-catalyzed radical reaction of chloromethyl benzonitrile with Grignard reagents

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