將200 mg LiOH溶解于3 mL水中, 在加入10 mL甲醇.攪拌下將該溶液倒入含有160 mg MPPa (1b, 0.292 mmol)的15 mL二氯甲烷中, 室溫條件下避光攪拌4 h, 用乙酸將反應(yīng)液的pH值調(diào)至3, 在加入20 mL水和20 mL二氯甲烷分層, 水相用二氯甲烷萃取(15 mL×3), 合并有機(jī)層并水洗, 用無水硫酸鈉干燥.減壓濃縮, 剩余物硅膠柱層析分離[洗脫劑: V(石油醚):V(乙酸乙酯)＝4:1], 得到46 mg暗紅色固體11(0.082 mmol, 28%).將其溶解于含有0.1 mL吡啶的15 mL四氫呋喃, 在0 ℃劇烈攪拌下, 將溶解在2 mL四氫呋喃中的24 mg OsO4 (0.094 mmol)慢慢滴加到反應(yīng)液中, 保持溫度并攪伴30 min.再于室溫下攪拌反應(yīng)2 h.加入20 mL在50%甲醇中飽和的NaHSO3溶液, 攪拌20 min, 過濾除去OsO3的紅褐色沉淀.劇烈攪拌下向反應(yīng)液中加入1 g硅膠, 然后將溶解于5 mL水中的200 mg NaIO4 (0.935 mmol)倒入反應(yīng)體系, 顏色迅速由墨綠色變?yōu)殂~色, 30 min后加入100 mL水和80 mL二氯甲烷淬滅反應(yīng), 過濾, 分出有機(jī)層, 干燥后用重氮甲烷甲基化.減壓除盡溶劑, 剩余物經(jīng)硅膠柱層析分離[洗脫劑: V(丙酮):V(甲苯)＝1:10], 得到25 mg紅色固體12 (0.043 mmol), 產(chǎn)率53%. m.p. 233~235 ℃; UV-vis (CH2Cl2)λmax [ε/(L?mol－1?cm－1)]: 421 (11.30×104), 513 (7.91×103), 546 (3.05×104), 666 (2.71×104), 693 (4.97×104) nm; 1H NMR (400 MHz. CDCl3) δ: －0.43 (br s, 1H, NH), 0.58 (br s, 1H, NH), 1.58 (t, J＝7.6 Hz, 3H, 8-CH3), 1.81 (d, J＝7.2 Hz, 3H, 18-CH3), 1.87~2.08 (m, 1H, 17a+17b-H), 2.18~2.43 (m, 2H, 17a+17b-H), 2.54~2.78 (m, 1H, 17a+17b-H), 3.04, 3.61, 3.65 (each s, each 3H, CH3+OCH3), 3.45 (q, J＝7.6 Hz, 2H, 8a-H), 4.16 (d, J＝8.4 Hz, 1H, 17-H), 4.36 (q, J＝7.2 Hz, 1H, 18-H), 5.03 (d, J＝20.0 Hz, 1H, 132-H), 5.20 (d, J＝20.0 Hz, 1H, 132-H), 8.49, 9.42, 9.68 (each s, each 1H, meso-H), 11.29 (s, 1H, 3-CHO), 11.33 (s, 1H, 12-CHO); 13C NMR (CDCl3) δ: 204.2, 204.0, 199.8, 174.5, 172.7, 170.6, 170.3, 146.0, 145.9, 142.5, 138.6, 137.4, 136.9, 133.3, 129.7, 129.1, 123.6, 105.6, 98.1, 62.5, 61.5, 56.2, 51.6, 51.2, 31.9, 31.4, 24.4, 24.2, 23.6, 23.4, 13.7, 13.0, 12.1; IR (KBr) v: 3449 (N—H), 2924 (C—H), 1742~1708 (C＝O), 1686 (C＝C), 1560 (chlorin skeleton), 1457, 1341, 1082, 1040, 971 cm－1. EI-MS m/z: 565.4 (M+H+). Anal. calcd for C33H32N4O5: C 70.20, H 5.71, N 9.92; found C 70.40, H 5.84, N 9.87.
化學(xué)慧定制合成事業(yè)部摘錄
