An Easy and Clean Synthesis of Chiral 3,4-Diaryl-2,5-diazabicyclo[4.4.0]decanes by Reductive Intramolecular Coupling of Chiral Diimines

References

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• Physical constant and spectroscopic data for Schiff bases 2(a–f). 2a:  = −202.0 (c 0.5, CHCl3). M.p.: 98–100°C. 1H NMR (200 MHz CDCl3) δ ppm 8.21 (s, 2H), 7.59 (d, 4H, J = 2.2 Hz), 7.33 (d, 4H, J = 2.2 Hz), 7.29 (m, 2H), 3.42 (m, 2H), 1.86 (sl, 6H), 1.50 (m, 2H). 13C NMR (50 MHz CDCl3) δ ppm 160.94, 136.33, 130.16, 128.32, 127.87, 73.76, 32.93, 24.46. Mass (FAB+) m/z (relative intensity): 291 (M+H+, 100). 2b:  = −266.0 (c 1.2, CHCl3). M.p.: 124–126°C. 1H NMR (200 MHz CDCl3) δ ppm 8.11 (s, 2H), 7.44 (s, 8H), 3.38 (m, 2H), 1.86 (m, 6H), 1.49 (m, 2H). 13C NMR (50 MHz CDCl3) δ ppm 159.74, 135.15, 131.67, 129.32, 124.69, 73.77, 32.81, 24.42. Mass (FAB+) m/z (relative intensity): 499 (M+H+, 100). 2c:  = −291.0 (c 1.0, CHCl3). M.p.: 105–107°C. 1H NMR (200 MHz CDCl3) δ ppm 8.12 (s, 2H), 7.52 (d, 4H, J = 8.8 Hz), 6.81 (d, 4H, J = 8.8 Hz), 3.77 (s, 6H), 3.35 (m, 2H), 1.84 (m, 6H), 1.48 (m, 2H). 13C NMR (50 MHz CDCl3) δ ppm 161.28, 160.32, 129.46, 113.78, 73.82, 55.28, 33.15, 24.63. Mass (FAB+) m/z (relative intensity): 351 (M+H+, 100). 2d:  = −318.0 (c 1.0, CHCl3). M.p.: 118–120°C. 1H NMR (200 MHz CDCl3) δ ppm 8.22 (s, 2H), 7.97 (d, 4H, J = 8.3 Hz), 7.63 (d, 4H, J = 8.3 Hz), 3.89 (s, 6H), 3.44 (m, 2H), 1.88 (m, 6H), 1.51 (m, 2H). 13C NMR (50 MHz CDCl3) δ ppm 166.71, 160.23, 140.20, 131.63, 129.80, 127.82, 73.98, 52.26, 32.81, 24.44. Mass (FAB+) m/z (relative intensity): 407 (M+H+, 100). 2e:  = −440.0 (c 0.5, CHCl3). M.p.: 173–175°C. 1H NMR (200 MHz, CDCl3) δ ppm 8.12 (s, 2H), 7.49 (d, 4H, J = 8.2 Hz), 7.39 (d, 4H, J = 8.2 Hz), 3.39 (m, 2H), 1.88 (m, 6H), 1.49 (m, 2H), 0.24 (s, 18H). 13C NMR (50 MHz, CDCl3) δ ppm 160.52, 136.14, 132.09, 127.69, 125.03, 104.82, 96.06, 73.86, 32.87, 24.50, −0.02. Mass (FAB+) m/z (relative intensity): 483 (M+H+, 80). 2f (racemic): 1H NMR (200 MHz, CDCl3) δ ppm 8.50 (s, 2H), 7.91 (d, 2H, J = 2.6 Hz), 7.36 (dd, 2H, J = 8.8 and 2.6 Hz), 6.67 (d, 2H, J = 8.8 Hz), 3.73 (s, 6H), 3.39 (m, 2H), 1.82 (m, 6H), 1.47 (m, 2H). 13C NMR (50 MHz, CDCl3) δ ppm 157.79, 156.22, 133.85, 129.83, 113.28, 112.78, 73.90, 55.84, 32.92, 24.53. Mass (FAB+) m/z (relative intensity): 509 (M+H+, 40)
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• General experimental procedure for compounds 3(a–f): To a mixture of the diimine (1–5 mmoles) and zinc (10 equivalents) in dry THF (10 mL/mmole of diimine), acid (5 equivalents) was added under an N2 atmosphere at 0°C. The ice bath was removed and the reaction mixture was stirred for 12 h at room temperature. It was quenched with saturated NaHCO3 until basic pH, the mixture was diluted with CHCl3 and filtered through a pad of celite. The organic phase was washed with brine and dried over MgSO4 before concentration. The crude products 3(a–f) gave satisfactory analytical data and can be used without further purification in a next step
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• Physical constant and spectroscopic data for compounds 3(a–f) 3a:  = −72.0 (c 0.5, CHCl3). M.p.: 64–66°C. 1H NMR (200 MHz CDCl3) δ ppm 7.12 (s, 10H), 3.84 (s, 2H), 2.61 (m, 2H), 1.80 (m, 6H), 1.42 (m, 2H). 13C NMR (50 MHz CDCl3): δ ppm 141.40, 128.07, 127.75, 127.08, 68.48, 61.50, 31.78, 24.91. Mass (FAB+) m/z (relative intensity): 293 (M+H+, 100). 3b:  = −126.0 (c 1.1, CHCl3). M.p.: 149–151°C. 1H NMR (200 MHz CDCl3) δ ppm 7.26 (d, 4H, J = 8.4 Hz), 6.96 (d, 4H, J = 8.4 Hz), 3.72 (s, 2H), 2.57 (m, 2H), 1.73 (m, 6H), 1.39 (m, 4H). 13C NMR (50 MHz CDCl3): δ ppm 140.23, 131.06, 129.81, 121.12, 67.96, 61.40, 31.76, 24.88. Mass (FAB+) m/z (relative intensity): 451 (M+H+, 85). 3c:  = −102.0 (c 0.5, CHCl3). M.p.: 105–107°C. 1H NMR (200 MHz CDCl3) δ ppm 7.03 (d, 4H, J = 8.6 Hz), 6.86 (d, 4H, J = 8.6 Hz), 3.75 (s, 2H), 3.72 (s, 6H), 2.59 (sl, 2H), 1.73 (m, 6H), 1.40 (m, 4H). 13C NMR (50 MHz CDCl3): δ ppm 158.48, 133.86, 129.04, 113.12, 67.76, 61.54, 55.05, 31.77, 24.90. Mass (FAB+) m/z (relative intensity): 353 (M+H+, 40). 3d:  = −148.0 (c 0.5, CHCl3). M.p.: 173–175°C. 1H NMR (200 MHz CDCl3) δ ppm 7.76 (d, 4H, J = 8.3 Hz), 7.12 (d, 4H, J = 8.3 Hz), 3.85 (s, 8H), 2.61 (sl, 2H), 1.88 (sl, 2H), 1.73 (m, 4H), 1.40 (m, 4H). 13C NMR (50 MHz CDCl3): δ ppm 166.93, 146.22, 129.25, 128.11, 68.44, 61.39, 52.01, 31.76, 24.90. Mass (FAB+) m/z (relative intensity): 409 (M+H+, 100). 3e:  = −232.0 (c 0.5, CHCl3). M.p.: 217–219°C. 1H NMR (200 MHz CDCl3) δ ppm 7.22 (d, 4H, J = 8.2 Hz), 6.99 (d, 4H, J = 8.2 Hz), 3.75 (s, 2H), 2.61 (m, 2H), 1.70 (m, 6H), 1.39 (m, 4H), 0.23 (m, 12H). 13C NMR (50 MHz CDCl3): δ ppm 141.66, 131.56, 127.97, 121.95, 105.17, 93.87, 68.38, 61.38, 31.76, 24.92, 0.04. Mass (FAB+) m/z (relative intensity): 485 (M+H+, 40). 3f (racemic): 1H NMR (200 MHz CDCl3) δ ppm 7.60 (d, 2H, J = 2.5 Hz), 7.13 (dd, 2H, J = 8.7 and 2.5 Hz), 6.42 (d, 2H, J = 8.7 Hz), 4.28 (s, 2H), 3.47 (s, 6H), 2.52 (s, 2H), 1.74 (m, 6H), 1.35 (m, 4H). 13C NMR (50 MHz CDCl3): δ ppm 155.88, 133.74, 130.43, 112.57, 111.70, 61.72, 55.38, 31.90, 25.06. Mass (FAB+) m/z (relative intensity): 511 (M+H+, 100)
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• Selected spectroscopical data for compound 4a: 1H NMR (200 MHz CDCl3) δ ppm 7.50–7.25 (m, 10H), 5.77 (s, 2H), 4.27 (t, 2H), 3.80 (q, 12H, J = 7.0 Hz), 3.10 (m, 4H), 2.70 (m, 2H), 1.70 (m, 8H), 1.46 (m, 4H), 1.22 (t, 18H, J = 7.0 Hz), 0.51 (m, 4H). 13C NMR (50 MHz CDCl3): δ ppm 159.63, 140.94, 128.89, 127.54, 125.89, 61.61, 58.44, 56.74, 42.93, 32.50, 24.80, 23.54, 18.35, 7.59. νmax (KBr)/cm−1 3442, 2977, 2930, 2888, 1654, 1508, 1102, 1078
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