Transition-Metal Catalyzed Coupling Reactions of gem-Dibromovinyl Derivatives

doi:10.6023/cjoc202110026

Abstract

gem-Dibromovinyl derivatives are valuable synthetic tools in organic chemistry, which have been widely applied in the construction of founctionalized molecules. In the past few years, metal-catalyzed (such as Pd, Cu, Ag, Au and Ni) transformations with gem-dibromovinyl derivatives have been developed and become a powerful tool for the synthesis of alkynes, chromenes, indoles, benzindole, benzothiophene and other benzo-fused heterocycles with important physiological activity. The progresses in transition-metal-catalyzed transformations of gem-dibromoviny derivatives since 2013 are summarized.

Key words: gem-dibromovinyl derivative, alkynyl intermediate, transition metal catalysis, coupling reaction

Cite this article

Luqi Liang, Lizhi Zhang, Yongli Peng, Hui Liu. Transition-Metal Catalyzed Coupling Reactions of gem-Dibromovinyl Derivatives[J]. Chinese Journal of Organic Chemistry, 2022, 42(4): 1033-1060.

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Fig. & Tab. 67

Scheme 1. Synthesis of pyrrolo-/indolo-/naphtho-[1,2-a]quinolines

Scheme 2. Mechanism for the synthesis of pyrrolo[1,2-a]quinolines

Scheme 3. Synthesis of N-arylsulfonyl-1,2,3-triazoles from 1,1-dibromo-2-arylethylenes

Scheme 4. Synthesis of 2-arylbenzofuran scaffold through direct involvement of 1,1-dibromoalkene and phenol

Scheme 5. Two-step one-pot synthesis of benzofurans

Scheme 6. Mechanistic pathway for the formation of benzofuran from 1,1-dibromide and phenol

Scheme 7. Scope of potassium alkynyl carboxylates and 1,1-dibromoalkenes

Scheme 8. Synthesis of pyrole derivatives

Scheme 9. Synthesis of gem-dihaloenynes

Scheme 10. Suzuki-Miyaura coupling of gem-dibromoenynes

Scheme 11. Synthesis of butatrienes

Scheme 12. Direct alkynylation between various N(3)-protected-6-bromo-3H-imidazo[4,5-b]pyridines and dibromoalkenes

Scheme 13. Direct alkynylation between various N(3)-MEM-3H-imidazo[4,5-b]pyridines and dibromoalkenes

Scheme 14. Mechanism for the direct alkynylation of 3H-imidazo[4,5-b]pyridines

Scheme 15. Synthesis of internal alkynes

Scheme 16. Synthesis of diaryl alkynes from gem-dibromoalkenes and 1-chloro-4-nitrobenzene

Scheme 17. Synthesis of various 3-arylpropynamides

Scheme 18. Pathways involved in the Pd-catalyzed cross-coupling of 1,1-dibromo-1-alkenes with isocyanides

Scheme 19. Synthesis of diynes from 1-(2,2-dibromovinyl)-2-(phenylethynyl)benzene and imidazole/benzimidazole

Scheme 20. Scope of substituted imidazoles used in the Cu/Pd-co-catalysed cascade reaction

Scheme 21. Direct C-3 alkynylation of indolizines with (2,2-dibromovinyl)arenes[14]

Scheme 22. Synthesis of various derivatives of 2-amidoindoles

Scheme 23. Mechanism for the formation of 2-amidoindoles and tetrahydroindolo[1,2-a]quinazolines

Scheme 24. Scope of the Pd(0)-catalyzed synthesis of 2-cyano- indoles from gem-dibromides

Scheme 25. Mechanism for the reaction

Scheme 26. One-pot derivatization to afford the corresponding tetrazole

Scheme 27. Optimization study on the formation of 3-cyano- 1H-indole and 9H-pyrimido[4,5-b]indole

Scheme 28. Substrate scope for the synthesis of 3-cyanoindoles

Scheme 29. Substrate scope for the synthesis of 9H-pyri- mido[4,5-b]indoles

Scheme 30. Substrate scope for the synthesis of 9H-pyrido[2,3-b]indoles

Scheme 31. Mechanism for the formation of 3-cyano-1H-indole

Scheme 32. Mechanism for the formation of 2,4-diphenyl-9H-pyrimido[4,5-b]indole

Scheme 33. Mechanism for the formation of 2-methyl-9H-pyrido[2,3-b]indole

Scheme 34. Three-component sequential synthesis of synthon in one pot

Scheme 35. Scope for chemoselective O- and N-cyclization

Scheme 36. Mechanism for the chemoselectivity

Scheme 37. Scope of N-tosylhydrazones selenophenes and gem-dibromovinylaniline derivatives

Scheme 38. Possible mechanism of tandem reaction

Scheme 39. Synthesis of 2-substituted indoles and 1,2-disubstituted indoles

Scheme 40. Scope of the trifluoromethylthiolation of dibromovinyl phenols, thiophenols and anilines with (bpy)CuSCF3

Scheme 41. Scope of the trifluoromethylselenolation of dibromovinyl phenols, thiophenols and anilines with [(bpy)CuSeCF3]

Scheme 42. Synthesis of 2-bromobenzo[b]chalcogenophenes

Scheme 43. Synthesis of 2-alkynyl-benzo[b]selenophenes

Scheme 44. Mechanism for the forming 2-alkynyl-benzo[b]- selenophenes

Scheme 45. Optimization of copper-catalyzed intramolecular coupling

Scheme 46. Optimization of palladium-catalyzed C—H activation

Scheme 47. Synthesis of 6H-isoindolo[2,1-a]indol-6-ones

Scheme 48. Synthetic routes to regioisomeric imidazoindoles

Scheme 49. Substrate scope for the formation of 105

Scheme 50. Synthesis of racemic imidazoindoles 106 by domino C—N, C—N cyclization

Scheme 51. Synthesis of tetracyclic imidazoindoles

Scheme 52. Two-step one-pot strategy for the synthesis of racemic regioisomeric imidazolindoles 108

Scheme 53. Two-step one-pot strategy for the synthesis of nonracemic regioisomeric imidazolindole 108

Scheme 54. Mechanisms for the synthesis of imidazoindoles

Scheme 55. Scope of the synthesis of trisubstituted 1,3,5-triazines

Scheme 56. Mechanism of formation 2,4-diamino-1,3,5-triazines

Scheme 57. Substrates scope of the domino reaction

Scheme 58. Catalytic cycle for the domino reaction

Scheme 59. Substrate scope for the preparation of (2H-chromen-2-ylidene)-acetates

Scheme 60. Substrate scope for the preparation of (2H-chromen-2-ylidene)ethanones

Scheme 61. Reaction pathway accounting for the formation of (Z)-2-(3-phenyl-2H-chromen-2-ylidene)acetate

Scheme 62. Scope of N-(quinolin-8-yl) benzamides and dibromoalkenes

Scheme 63. Mechanism for the forming 3-methylene isoindolin-1-one product

Scheme 64. Reaction of gem-dibromoalkenes with P(O)H compounds

Scheme 65. Mechanistic pathway

Scheme 66. Tandem Sonogashira coupling/lactonization of 2-(2',2'-dibromovinyl)benzoate with terminal alkynes

Scheme 67. Reaction mechanism of forming 3-alkynyl isocoum

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