N,N-Dimethylformamide: An Versatile Organic Synthetic Reagent

doi:10.6023/cjoc202008054

Abstract

The development of simple and efficient strategies for the preparation of various functional molecules from low cost and readily available starting substrates is one of significant goal in the field of synthetic chemistry. N,N-Dimethyl- formamide (DMF) is not only a common and excellent no-proton polar solvent, but also an important industrial raw material and a multipurpose synthetic reagent. The recent progress in the application of DMF as multifunctional reactant in carbonylation, formylation, ammoniation, carbamoylation as well as carbon source, hydrogen source and oxygen source The paper is reviewed.

Key words: N,N-dimethylformamide (DMF), synthetic transformation, functional source, versatile reactant

Cite this article

Xuewen Diao, Di Yang, Qiliang Yang, Xiaohua Cai. N,N-Dimethylformamide: An Versatile Organic Synthetic Reagent[J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1434-1446.

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Fig. & Tab. 53

Scheme 1. Carbonylation of aromatic amide and aliphatic amide

Scheme 2. Possible mechanism for the carbonylation of aromatic amide and aliphatic amide

Scheme 3. Carbonylation of N-aryl pyridine-2-amine derivatives

Scheme 4. Carbonylation of 11H-pyridine [2,1b] quinazoline-11-ketone

Scheme 5. Possible mechanism for the carbonylation of 11H- pyridine[2,1b]quinazoline-11-ketone

Scheme 6. DMF involved in the aryl borate carbonylation of diaryl ketones

Scheme 7. Possible mechanism for the DMF involved in the aryl borate carbonylation of diaryl ketones

Scheme 8. Formylation reactions of amines with DMF

Scheme 9. Possible mechanism for the foremylation reactions of amines with DMF

Scheme 10. Reaction of o-alkynyl aniline and DMF for the synthesis of 3-formylindole derivatives

Scheme 11. Possible mechanism for the synthesis of 3-formylindole derivatives

Scheme 12. Formylation of the aryl ketone with DMF

Scheme 13. Possible mechanism for the formylation of aryl ketone with DMF

Scheme 14. Direct amination reactions of quinazoline compounds with DMF

Scheme 15. Proposed mechanism for the direct amination of quinazoline compounds with DMF

Scheme 16. Direct reduction of ammoniated aldehydes or ketones involving DMF

Scheme 17. Synthesis of 2-oxoacetamide derivatives through three-component reaction

Scheme 18. Possible mechanism for the synthesis of 2-oxoacetamide derivatives

Scheme 20. Carbamoylation of aliphatic alkenes

Scheme 21. Possible mechanism for the carbamoylation of aliphatic alkenes

Scheme 22. Reaction for the formation of aryl formamide derivative induced by WCl6

Scheme 23. Possible mechanism for the synthesis of aryl formamide derivatives

Scheme 24. Selective synthesis of C3-cyanindoles

Scheme 25. Possible mechanism for the synthesis of C3-cya- nindole

Scheme 26. Cyanation reaction of indoles and 2-phenylpyridine

Scheme 27. Possible mechanism for the cyanation of indoles

Scheme 28. Synthesis of nitriles through the reaction of aryl iodine with DMF

Scheme 29. Possible mechanism for the reaction of aryl iodine with DMF

Scheme 30. Direct cyanation of 2-phenylpyridines using DMF as cyanide sources

Scheme 31. Synthesis of α-methylketone using DMF as methyl source

Scheme 32. Possible mechanism for the synthesis of α-methyl- ketones

Scheme 33. DMF involved in the methylation of aryl ketones

Scheme 34. Selective α-methylation of aryl acetonitriles or aryl acetamides

Scheme 35. Preparation of terminal olefins catalysed by copper

Scheme 36. Preparation of β-aminoketones using DMF as CH 2 source

Scheme 39. Possible mechanism for the synthesis of 3,3'-di- indolemethane (DIM) and its derivatives

Scheme 40. Synthesis of α-aminonitriles using copper catalytic activation of DMF

Scheme 41. Possible mechanism for the synthesis of α-amino- nitrile using copper catalytic activation of DMF

Scheme 42. Synthesis of 6H-chromium[4,3-b]quinoline-6-ke- tone and its derivatives

Scheme 43. Possible mechanism for the synthesis of 6H-chro- mium [4,3-b]quinoline-6-ketone derivatives

Scheme 44. Reaction of hydrazine with DMF for the synthesis of 1,3,4-oxadiazole

Scheme 45. Preparation of nitrogen-containing heterocycles catalyzed by imidazole hydrochloride

Scheme 46. Reaction of thionyl hydrazine and DMF for the synthesis of heterocyclic compound 1,3,4-thiadiazoles

Scheme 47. Possible mechanism for the synthesis of heterocyclic 1,3,4-thiadiazoles

Scheme 48. Asymmetric transfer hydrogenation of α,β-unsatu- rated esters

Scheme 49. Synthesis of α-hydroxyaromatic ketones using DMF as oxygen

Scheme 50. Proposed mechanism for the synthesis of α-hy- droxyaromatic ketones

Scheme 51. Synthesis of cis-diamineenol involved in DMF

Scheme 52. Possible mechanism for the synthesis of cis-dia- mineenol involved in DMF

Scheme 53. Synthesis of 4-dimethylaminoquinoline

Scheme 54. Possible mechanism for the synthesis of 4-dime- thylaminoquinoline

Scheme 55. DMF involved in the oxidative synthesis of pyrimidine formamide

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