N,N-二甲基甲酰胺: 一个多用途的有机合成试剂

doi:10.6023/cjoc202008054

摘要/Abstract

发展简单有效的方法从价廉易得的原料制备各种功能有机分子一直是合成化学领域追求的目标之一. N,N-二甲基甲酰胺(DMF)是常见的、优良的极性非质子溶剂, 也是一种重要的工业原料和多功能合成反应试剂. 从羰基化、甲酰化、氨基化、氨甲酰化及提供碳源、氢源和氧源几个方面综述DMF作为多功能合成反应试剂的最新进展.

关键词: N,N-二甲基甲酰胺(DMF), 合成转换, 功能源, 多功能试剂

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

引用此文

刁学文, 杨迪, 杨启亮, 蔡小华. N,N-二甲基甲酰胺: 一个多用途的有机合成试剂[J]. 有机化学, 2021, 41(4): 1434-1446.

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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图/表 53

图式1. 脂肪族酰胺和芳香酰胺与DMF的羰基化反应

Scheme 1. Carbonylation of aromatic amide and aliphatic amide

图式2. 芳香酰胺和脂肪族酰胺的羰基化反应可能的机理

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

图式3. N-芳基吡啶-2-胺衍生物的羰基化反应

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

图式4. 11H-吡啶并[2,1b]喹唑啉-11-酮的羰基化反应

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

图式5. 11H-吡啶并[2,1b]喹唑啉-11-酮的羰基化反应可能的机理

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

图式6. DMF参与合成二芳基酮的芳基硼酸羰基化反应

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

图式7. DMF参与合成二芳基酮的芳基硼酸羰基化反应可能的机理

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

图式8. DMF参与的胺甲酰化反应

Scheme 8. Formylation reactions of amines with DMF

图式9. DMF参与胺甲酰化反应可能的机理

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

图式10. 含邻炔基苯胺和DMF合成3-甲酰基吲哚衍生物

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

图式11. 合成3-甲酰基吲哚衍生物可能的机理

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

图式12. DMF与芳基甲酮的甲酰化反应

Scheme 12. Formylation of the aryl ketone with DMF

图式13. DMF与芳基甲酮的甲酰化反应可能的机理

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

图式14. 用DMF直接胺化喹唑啉类化合物

Scheme 14. Direct amination reactions of quinazoline compounds with DMF

图式15. 用DMF直接胺化喹唑啉类化合物建议的机理

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

图式16. DMF参与直接还原氨化醛或酮

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

图式17. 三组分反应合成2-氧代乙酰胺衍生物

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

图式18. 三组分反应合成2-氧代乙酰胺衍生物的机理

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

Scheme 19. 一锅法反应合成苯甲酰胺和苯腈 One pot reaction to form benzamide and benzo-nitriles 4 参与胺甲酰化反应

图式20. 脂肪族烯烃氨基甲酰化反应

Scheme 20. Carbamoylation of aliphatic alkenes

图式21. 脂肪族烯烃氨基甲酰化反应可能的机理

Scheme 21. Possible mechanism for the carbamoylation of aliphatic alkenes

图式22. WCl6诱导生成芳基甲酰胺衍生物的反应

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

图式23. 合成芳基甲酰胺衍生物可能的机理

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

图式24. 选择性合成C3-氰化吲哚

Scheme 24. Selective synthesis of C3-cyanindoles

图式25. 合成C3-氰化吲哚可能的机理

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

图式26. 吲哚和2-苯基吡啶的腈化反应

Scheme 26. Cyanation reaction of indoles and 2-phenylpyridine

图式27. 吲哚腈化反应可能的机理

Scheme 27. Possible mechanism for the cyanation of indoles

图式28. 芳基碘与DMF反应合成腈类化合物

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

图式29. 芳基碘与DMF反应合成腈类化合物可能的机理

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

图式30. 直接腈基化2-苯基吡啶用DMF作为腈源

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

图式31. 以DMF为甲基源合成α-甲基化酮

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

图式32. 合成α-甲基化酮可能的机理

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

图式33. DMF参与芳香甲酮的甲基化

Scheme 33. DMF involved in the methylation of aryl ketones

图式34. 选择性α-甲基化芳基乙腈或芳基乙酰胺

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

图式35. 铜催化制备末端烯烃

Scheme 35. Preparation of terminal olefins catalysed by copper

图式36. DMF作为CH2源制备β-氨基酮

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

图式39. DMF参与合成了3,3'-二吲哚甲烷(DIM)及其衍生物可能的机理

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

图式40. 铜催化活化DMF合成α-氨基腈

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

图式41. 铜催化活化DMF合成α-氨基腈可能的机理

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

图式42. 合成6H-铬[4,3-b]喹啉-6-酮及其衍生物

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

图式43. 合成6H-铬[4,3-b]喹啉-6-酮及其衍生物建议的机理

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

图式44. 肼与DMF合成1,3,4-噁二唑

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

图式45. 咪唑盐酸盐催化制备含氮杂环

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

图式46. 硫代酰肼与DMF合成杂环化合物1,3,4-噻二唑

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

图式47. 合成杂环化合物1,3,4-噻二唑可能的机理

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

图式48. α,β-不饱和酯的不对称转移氢化反应

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

图式49. DMF作为氧源合成α-羟基芳酮

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

图式50. 合成α-羟基芳酮建议可能的机理

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

图式51. DMF参与合成顺二胺烯醇

Scheme 51. Synthesis of cis-diamineenol involved in DMF

图式52. DMF参与合成顺二胺烯醇可能的机理

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

图式53. 合成4-二甲氨基喹啉

Scheme 53. Synthesis of 4-dimethylaminoquinoline

图式54. 合成4-二甲氨基喹啉可能的机理

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

图式55. DMF参与氧化合成嘧啶甲酰胺

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

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