反应详情

To a solution of 14 (1.48 g, 1.52 mmol) in THF (30 mL), was added dimethyl amine (15.2 mL, 2M in THF, 30.4 mmol) at 0° C. This reaction was allowed to reach room temperature and stirred for 2 h. At this time, the reaction mixture was concentrated in vacuo. To the yellowish solid was added DCM (30 mL) and DMF (5 mL). To this solution, was added Boc-Lys(Z)—OH (0.608 g, 1.60 mmol), then HOBt (0.216 g, 1.60 mmol), then EDC.HCl (0.3063 g, 1.60 mmol). This solution was allowed to stir for 8 h at which time the organic solution was washed with 1N HCl (3×15 mL), then saturated NaHCO3 (3×15 mL), and finally H2O (3×15 mL). The organic layer was dried over MgSO4 and concentrated in vacuo to yield a white solid. Column chromatography (2% MeOH, CHCl3) afforded the product 15 (1.0 g, 59% yield): 1H NMR (500 MHz, CDCl3) δ 8.15 (br s, 1H), 8.03 (br s, 1H), 7.88 (br s, 1H), 7.45-7.28 (m, 10H), 7.12 (br s, 1H), 6.65 (br s, 1H), 5.08 (s, 1H), 4.45-4.35 (m, 3H), 4.05 (br s, 1H), 3.67 (s, 3H), 3.11 (br s, 1H), 3.01 (br s, 1H), 1.90-1.60 (m, 8H), 1.60-1.38 (m, 44); 13C NMR (125 MHz, CDCl3) δ 173.3, 173.2, 172.7, 172.3, 157.2, 156.6, 138.4, 129.0, 128.4, 79.0, 78.1, 66.0, 55.7, 53.8, 53.4, 53.0, 52.2, 41.1, 40.9, 40.8, 32.7, 32.5, 31.6, 29.8, 29.6, 28.6, 23.7, 23.5; ESMS (FAB) m/z calcd for C66H88N8O15 (M+H)+ 1113.65, found 1113.52.

1. customto reach room temperature
2. concentrationAt this time, the reaction mixture was concentrated in vacuo
3. additionTo the yellowish solid was added DCM (30 mL) and DMF (5 mL)
4. stirringto stir for 8 h at which time the organic solution
5. washwas washed with 1N HCl (3×15 mL)
6. dry with materialThe organic layer was dried over MgSO4
7. concentrationconcentrated in vacuo
8. customto yield a white solid