Nickel-catalyzed imine cation intramolecular amide alkylation reaction method
A technology for catalyzing imine cations and ionic molecules, applied in organic chemistry and other directions, can solve problems such as harsh reaction conditions, and achieve the effects of mild reaction conditions, simple raw materials and reagents, and high reaction yields
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Embodiment 1
[0023]
[0024] Add 2.53g (10mmol) compound I-1, 0.26g (1mmol) solid Ni(ClO 4 ) 2 , and finally 50 mL of dry 1,2-dichloroethane was added, and the resulting mixture was stirred at 80° C. for 10 hours. After the reaction mixture was cooled to room temperature, it was poured into ice water, extracted with 50mL×3 methylene chloride, and the extracted organic phases were combined, washed once with saturated brine, anhydrous Na 2 SO 4 Dry, concentrate and remove the solvent to obtain the crude product, which is separated by column chromatography to obtain the pure product of compound II-1. White solid, 2.23g, yield 95%. 1 H NMR (400MHz, CDCl 3 )δ: 7.87(dd, J=7.5Hz, 2.7Hz, 2H), 7.68–7.56(m, 2H), 7.49(t, J=7.5Hz, 1H), 7.33–7.15(m,3H), 5.67( s,1H),4.43(dt,J=12.7Hz,5.2Hz,1H),3.59–3.38(m,1H),3.07(ddd,J=15.5Hz,9.1Hz,6.1Hz,1H),2.88(dt ,J=15.9Hz,4.5Hz,1H); 13 C NMR (CDCl 3 ,100MHz)δ:167.94,144.25,134.82,134.37,132.87,131.52,129.32,128.50,127.46,126.72,125.24,123.88,123.49,59.15,...
Embodiment 2
[0026]
[0027] Add 2.67g (10mmol) compound I-2, 0.52g (2mmol) solid Ni(ClO 4 ) 2 , and finally 25 mL of dry 1,2-dichloroethane was added, and the resulting mixture was stirred at 80° C. for 7 hours until the reaction was complete. The reaction mixture was cooled to room temperature, poured into water, stirred, extracted with 50mL×3 dichloromethane, combined and extracted organic phases, washed once with saturated brine, anhydrous Na 2 SO 4 Dry, concentrate and remove the solvent to obtain the crude product, which is separated by column chromatography to obtain the pure product of compound II-1. White solid, 2.45g, yield 98%. 1 H NMR (400MHz, CDCl 3 )δ: 7.88(dd, J=7.5Hz, 3.6Hz, 2H), 7.62(t, J=7.5Hz, 1H), 7.50(t, J=7.5Hz, 1H), 7.42(s, 1H), 7.07 (dd,J=18.1Hz,7.7Hz,2H),5.64(s,1H),4.45–4.37(m,1H),3.51–3.41(m,1H),3.01(dd,J=9.1Hz,6.4Hz ,1H),2.88–2.79(m,1H),2.37(s,3H); 13 C NMR (100MHz, CDCl 3 )δ: 167.96, 144.30, 136.35, 134.18, 132.87, 131.72, 131.49, 129.16, 128.46, 128....
Embodiment 3
[0029]
[0030] Add 2.87g (10mmol) of compound I-3, 0.32g (1.5mmol) of solid NiBr in a 100mL round bottom flask 2 , and finally 25 mL of dry DMF was added, and the resulting mixture was stirred vigorously at 100 °C for 5 hours. After the reaction mixture was cooled to room temperature, it was poured into water, stirred, extracted with 50mL×3 dichloromethane, combined and extracted organic phases were washed once with saturated brine, anhydrous Na 2 SO 4 Dry, concentrate and evaporate the solvent to obtain the crude product, and purify by column chromatography to obtain the pure product of compound II-3. White solid, 2.37g, yield 88%. 1 H NMR (400MHz, CDCl 3 )δ: 7.87(dd, J=12.1Hz, 7.7Hz, 2H), 7.65(t, J=7.5Hz, 1H), 7.59(s, 1H), 7.53(t, J=7.5Hz, 1H), 7.21 (dd,J=8.2Hz,1.4Hz,1H),7.14(d,J=8.2Hz,1H),5.63(s,1H),4.42(dt,J=12.8Hz,5.2Hz,1H),3.55– 3.41(m,1H),3.03(ddd,J=15.5Hz,9.1Hz,6.2Hz,1H),2.87(dt,J=15.8Hz,4.5Hz,1H); 13C NMR (CDCl 3 ,100MHz)δ:167.87,143.51,136.10,133.28,132.73...
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