反应详情

To 1.25 g (2.7 mmol) of chloroformate 6-1 in THF was added 1.2 mL (8.1 mmol) of triethylamine, 590 mg (3.0 mmol) of amine 7-1 (Supplier: High Force Research Ltd.), and a catalytic amount of DMAP. After stirring overnight at room temperature, the mixture was partitioned between EtOAc and saturated NaHCO3, the layers were separated, the organic phase was washed with water, 10% KHSO4, brine, dried over MgSO4, and concentrated by rotary evaporation. The residue was purified by column chromatography on silica gel with EtOAc/hexanes to provide a colorless oil. This material (1.32 g, 2.1 mmol) was dissolved in anhydrous THF and N2 was bubbled through the solution for 5 minutes. To this mixture was then added 320 mg (8.4 mmol) of NaBH4, 835 μL (8.4 mmol) of piperidine, and 122 mg (0.10 mmol) of tetrakistriphenylphosphine palladium(0). After stirring for 2 h at room temperature, the reaction was quenched with saturated NaHCO3, poured into EtOAc and the layers were separated. The organic phase was washed with water, brine, dried over MgSO4, and concentrated by rotary evaporation. The residue was purified by column chromatography on silica gel with EtOAc/hexanes to provide 7-2 as an off-white solid. Data for 7-2: 1HNMR (500 MHz, CDCl3) δ 7.4-7.2 (m, 5H), 7.1-6.9 (m, 3H), 6.35 (s, 1H), 4.8 (m, 1H), 4.7-4.6 (m, 2H), 4.45 (m, 1H), 3.6 (m, 1H), 3.1 (m, 2H) 2.75 (s, 3H), 2.7-2.6 (m, 2H), 2.05 (bs, 1H), 1.8-1.6 (m, 4H), 0.8 (s, 9H), 0.04 (s, 3H), 0.02 (s, 3H) ppm. HRMS (ES) calc'd M+H for C30H41F2N3O2Si: 542.3009. Found: 542.2999.

1. customthe mixture was partitioned between EtOAc and saturated NaHCO3
2. customthe layers were separated
3. washthe organic phase was washed with water, 10% KHSO4, brine
4. dry with materialdried over MgSO4
5. concentrationconcentrated by rotary evaporation
6. customThe residue was purified by column chromatography on silica gel with EtOAc/hexanes
7. customto provide a colorless oil
8. customN2 was bubbled through the solution for 5 minutes
9. stirringAfter stirring for 2 h at room temperature
10. customthe reaction was quenched with saturated NaHCO3
11. additionpoured into EtOAc
12. customthe layers were separated
13. washThe organic phase was washed with water, brine
14. dry with materialdried over MgSO4
15. concentrationconcentrated by rotary evaporation
16. customThe residue was purified by column chromatography on silica gel with EtOAc/hexanes