Research Progress of Carbonyl α-Position Amination

doi:10.6023/cjoc202301005

Abstract

α-Amino carbonyl derivatives are an important class of molecular backbones found in many pharmaceuticals and natural product molecules, meanwhile, they are also an essential kind of intermediates for the synthesis of many organic molecules. To develop simple and efficient method for the synthesis of structurally diversity α-amino carbonyl derivatives of great importance, the amination reactions of carbonyl α-position hydrocarbon bond in recent decades are classified and summarized based on the different activation patterns experienced by the reactions. These reactions are mainly divided into four categories: electrophilic amination, oxidative amination, halide mediated amination, and electrochemical amination.

Key words: α-aminoketone, α-aminoaldehyde, carbonyl compound, electrophilic amination, oxidative amination

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Wenqian Wu, Chunxia Chen, Jinsong Peng, Zhanyu Li. Research Progress of Carbonyl α-Position Amination[J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2743-2763.

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Fig. & Tab. 86

Figure 1. Drugs with α-amino carbonyl structure

Scheme 1. Synthesis of α-amino ketones

Scheme 2. Electrophilic amination reactions promoted by LDA and MeZnBr

Scheme 3. Electrophilic amination promoted by LiHMDS

Scheme 4. Enantioselective amination of β-ketoesters catalyzed by lithium

Scheme 5. Electrophilic amination catalyzed by bis(sulfona- mide) magnesium complex 2

Scheme 6. Electrophilic amination catalyzed by bis(oxazoline) copper(Ⅱ) complex 3

Scheme 7. Electrophilic amination catalyzed by bis(oxazoline) copper(Ⅱ) complex 4

Scheme 8. One-pot copper- and palladium-catalyzed asymmetric tandem cyclization reactions

Scheme 9. Proposed mechanism of asymmetric tandem cyclization reaction

Scheme 10. Enantioselective α-amination of β-keto esters and β-keto amides catalyzed by copper

Scheme 11. Enantioselective α-amination of cyclic β-keto esters catalyzed by rare metal

Scheme 12. Enantioselective α-amination of acyclic β-keto esters catalyzed by rare metal

Scheme 13. Enantioselective α-amination of cyclic β-keto esters catalyzed by zinc

Scheme 14. Electrophilic amination catalyzed by L-proline

Scheme 15. Self-inductive coupling mechanism proposed by Blackmond group

Scheme 16. Electrophilic amination catalyzed by α,α-diaryl- prolinol silyl ether 11

Scheme 17. Electrophilic amination of dihydroindene catalyzed by proline

Scheme 18. Electrophilic amination catalyzed by quinoline-derived primary amine

Scheme 19. Electrophilic amination catalyzed by ion pair

Scheme 20. Amination of indolones at the 3-position catalyzed by chiral amine derived from quinoline

Scheme 21. Electrophilic amination catalyzed by chiral primary amine 15

Scheme 22. Asymmetric amination of β-ketone esters catalyzed by chiral amine

Scheme 23. Electrophilic amination catalyzed by chiral phosphoric acid

Scheme 24. Proposed mechanism of chiral phosphoric acid- catalyzed electrophilic amination reactions

Scheme 25. Electrophilic amination catalyzed by guanidine- diurea bifunctional organic 18

Scheme 26. Asymmetric amination catalyzed by Lewis acid/ Br?nsted base

Scheme 27. Electrophilic amination catalyzed by boron

Scheme 28. Enantioselective amination of carboxylic acid derivatives catalyzed by isothiourea

Scheme 29. Electrophilic amination catalyzed by cinchona alkaloid

Scheme 30. Electrophilic amination catalyzed by tertiary amine thiourea 24

Scheme 31. Electrophilic amination catalyzed by tertiary amine thiourea 25

Scheme 32. Electrophilic amination catalyzed by triazole bromide 26

Scheme 33. Proposed mechanism of the electrophilic amination catalyzed by triazole bromide

Scheme 34. Electrophilic amination catalyzed by Sc(OTf)3

Scheme 35. Proposed mechanism of the electrophilic amination catalyzed by Sc(OTf)3

Scheme 36. Electrophilic amination catalyzed by CuCl and Cu(OTf)2

Scheme 37. Proposed mechanism of the electrophilic amina-tion catalyzed by CuCl and Cu(OTf)2

Scheme 38. Electrophilic amination catalyzed by ferrous chloride

Scheme 39. Proposed mechanism of the electrophilic amination catalyzed by ferrous chloride

Scheme 40. Azidation reactions involving trimethylsilylazide

Scheme 41. Proposed mechanism of azidation reactions involving trimethylsilyl azide

Scheme 42. Azidation reactions involving sodium azide

Scheme 43. Tetrabutylammonium iodide mediated amination

Scheme 44. Proposed mechanism of tetrabutylammonium iodide-mediated amination reaction

Scheme 45. Polyazide reactions involving sodium azide

Scheme 46. Proposed mechanism of polyazide reactions

Scheme 47. Iodine-mediated amination

Scheme 48. Proposed mechanism of iodine-mediated amination

Scheme 49. Oxidative amination reactions catalyzed by ammonium iodide

Scheme 50. Proposed mechanism of the oxidative amination reactions catalyzed by ammonium iodide

Scheme 51. Oxidative amination reactions catalyzed by tetra- n-butylammonium iodide

Scheme 52. Proposed mechanism of the oxidative amination reactions catalyzed by tetra-n-butylammonium iodide

Scheme 53. Intramolecular oxidative α-amination to synthesize spiroindolyloxindole

Scheme 54. Iodine-promoted oxidative amination of dimethyl methylmalonate

Scheme 55. Iodine-promoted synthesis of α-Amino ketones, esters and imidazoles

Scheme 56. Oxidative amination catalyzed by rhodium

Scheme 57. Proposed mechanism of rhodium-catalyzed oxidative amination

Scheme 58. Oxidative amination reactions catalyzed by Cu(OTf)2

Scheme 59. Proposed mechanism of Cu(OTf)2-catalyzed oxidative amination

Scheme 60. Chemoselective α-amination of acylpyrazoles catalyzed by copper

Scheme 61. Oxidative amination reactions catalyzed by copper bromide

Scheme 62. Proposed mechanism of the oxidative amination reactions catalyzed by copper bromide

Scheme 63. Oxidative amination reactions catalyzed by copper chloride

Scheme 64. Proposed mechanism of the oxidative amination reactions catalyzed by copper chloride

Scheme 65. Oxidative amination reactions catalyzed by Cu(Ⅱ) complex

Scheme 66. Oxidative amination reactions catalyzed by copper-based MOF

Scheme 67. Proposed mechanism of the oxidative amination reactions catalyzed by copper-based MOF

Scheme 68. Oxidative amination reactions catalyzed by α-CDCuBr2

Scheme 69. Oxidative amination reactions catalyzed by zinc

Scheme 70. Proposed mechanism of zinc-catalyzed oxidative amination reactions

Scheme 71. Azidation reactions involving azidoiodane

Scheme 72. Oxidative amination reactions catalyzed by ferric chloride

Scheme 73. Proposed mechanism of the oxidative amination reactions catalyzed by ferric chloride

Scheme 74. Oxidative amination reactions catalyzed by cobalt

Scheme 75. Proposed mechanism of oxidative amination reactions catalyzed by cobalt

Scheme 76. Oxidative amination reactions facilitated by acid

Scheme 77. Proposed mechanism of acid-promoted oxidative amination reactions

Scheme 78. Oxidative amination reactions facilitated by DDQ

Scheme 79. NBS-mediated amination

Scheme 80. Proposed mechanism of NBS-mediated amination reactions

Scheme 81. Improved NBS-mediated amination reactions

Scheme 82. Proposed mechanism of improved NBS-mediated amination reactions

Scheme 83. NIS-mediated amination

Scheme 84. Electrochemical amination

Scheme 85. Proposed mechanism of electrochemical amination

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羰基α-位胺化反应研究进展