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Development of a Pd-Catalyzed Dearomative 1,2-Diarylation of Indoles Using Aryl Boron Reagents

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Stereoselective Heterocycle Synthesis via Alkene Difunctionalization

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Abstract

The Suzuki-Miyaura cross-coupling reaction is undoubtedly one of the most important carbon–carbon bond-forming processes. The extremely broad scope of this transformation has made it one of the most employed carbon–carbon bond-forming reactions in the pharmaceutical industry. This reaction traditionally involves C(sp2)–C(sp2) coupling, however, virtually all permutations of nucleophile and electrophile hybridizations have been explored. Recent effort has been focused on stereospecific and stereoselective Suzuki-Miyaura cross-couplings which allows for the formation of stereodefined carbon–carbon bonds.

Portions of this chapter have appeared in print. See: Ref. [1].

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Notes

  1. 1.

    Reference [2].

  2. 2.

    Aryl iodides, as well as aryl and vinyl tin and zinc reagents have been used to terminate these sequences. See: Refs. [3,4,5,6,7,8,9].

  3. 3.

    Reference [10].

  4. 4.

    References [11,12,13].

  5. 5.

    References [14, 15].

  6. 6.

    References [16, 17].

  7. 7.

    Reference [18].

  8. 8.

    References [19, 20].

  9. 9.

    Reference [21].

  10. 10.

    References [22,23,24,25].

  11. 11.

    Reference [26].

  12. 12.

    Reference [27].

  13. 13.

    Reference [28].

  14. 14.

    Reference [29].

  15. 15.

    References [30, 31].

  16. 16.

    Reference [32].

  17. 17.

    Reference [33].

  18. 18.

    Reference [34].

  19. 19.

    Reference [35].

  20. 20.

    Reference [36].

  21. 21.

    Reference [37].

  22. 22.

    Reference [38].

  23. 23.

    Reference [10].

  24. 24.

    Reference [39].

  25. 25.

    Reference [40].

  26. 26.

    Reference [41].

  27. 27.

    Reference [42].

  28. 28.

    Reference [43].

  29. 29.

    Reference [44].

  30. 30.

    Reference [45].

  31. 31.

    Reference [46].

  32. 32.

    Reference [47].

  33. 33.

    For a review on nucleophilic dearomatization of aromatic compounds, see: Ref. [48].

  34. 34.

    References [49, 50].

  35. 35.

    References [51, 52].

  36. 36.

    For a review on transition metal-mediated dearomatization reaction, see: Ref. [53].

  37. 37.

    For a review on asymmetric hydrogenations of aromatic compounds, see: Ref. [54].

  38. 38.

    Reference [55].

  39. 39.

    Reference [55].

  40. 40.

    Reference [56].

  41. 41.

    For an example of dearomative propargylation of benzyl chlorides, see: Ref. [57].

  42. 42.

    Reference [58].

  43. 43.

    Reference [59].

  44. 44.

    Reference [60].

  45. 45.

    Reference [61].

  46. 46.

    Reference [62].

  47. 47.

    Reference [63].

  48. 48.

    Bedford and co-workers reported a racemic variant involving diarylamines, see: Ref. [64].

  49. 49.

    Reference [65].

  50. 50.

    Reference [66].

  51. 51.

    Reference [67].

  52. 52.

    Reference [68].

  53. 53.

    Reference [69].

  54. 54.

    Reference [70].

  55. 55.

    Reference [71].

  56. 56.

    Reference [72].

  57. 57.

    Portions of this chapter have appeared in print. See: Refs. [73, 74].

  58. 58.

    Reference [75].

  59. 59.

    Zn(CN)2 has a solubility in water of 0.00005 g/L at 20 °C and is insoluble in alcohol. Taken from: Ref. [76].

  60. 60.

    The majority of the boroxines used in this chemistry were prepared and donated by Thomas Johnson, a current Ph.D. student in the Lautens group and Bo Luo, who is a visiting Ph.D. student in the Jinming Gao Group at Northwest Agriculture & Forestry University in China.

  61. 61.

    Reference [77].

  62. 62.

    Reference [78].

  63. 63.

    Reaction attempts using 3.123 were conducted by Masaru Kondo.

  64. 64.

    Reference [79].

  65. 65.

    A small aliquot of the reaction mixture was quenched with D2O and was analyzed by 1H, and no deuterium enrichment at the benzylic center was observed.

  66. 66.

    The stereochemistry of 3.131 was assigned by 1D NOE analysis.

  67. 67.

    Under numerous conditions this substrate only reached low levels of conversion and only the ratio, which was consistent across these runs, is presented.

  68. 68.

    Reference [80].

  69. 69.

    Reference [81].

  70. 70.

    Reference [72].

  71. 71.

    Reference [82].

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  1. David A. Petrone

    Present address: Laboratory for Organic Chemistry, ETH Zürich, Zürich, Switzerland

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    Petrone, D.A. (2018). Development of a Pd-Catalyzed Dearomative 1,2-Diarylation of Indoles Using Aryl Boron Reagents. In: Stereoselective Heterocycle Synthesis via Alkene Difunctionalization. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-319-77507-4_3

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