Application of Manganese Catalysts in Coupling Reactions in Organic Synthesis

doi:10.6023/cjoc202412002

Abstract

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

Cite this article

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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Fig. & Tab. 29

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

Scheme 2. Reaction of methanol with amines to formamide

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

Scheme 4. Reaction of alcohol to ammonia to amide

Scheme 5. Hydrogen storage system of methanol and diamine compounds

Scheme 6. Reaction of alcohol coupling into esters

Scheme 7. Reaction of alcohol coupling into esters

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

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

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

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

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

Scheme 13. Mn-catalysed branched hydroalkenylation of terminal alkynes

Scheme 14. Mn-catalyzed cross-coupling reactions

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

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

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

Scheme 18. Manganese-catalyzed azide peroxidation of olefins

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

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

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

Scheme 22. Combined catalytic reaction of manganese and cobalt

Scheme 23. Reaction of alkyl pyridine salts with aryl bromide

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

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

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

Scheme 27. Mn(Ⅲ)-induced radical reactions

Scheme 28. Manganese-catalysed olefin hydrogenation radical reaction

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

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