[(2S,3R,4S,5R)-2-[(2S,3R,4S,5S)-3-乙酰氧基-2-[[(3R,8S,9R,10R,13S,14R,16R,17S)-3,17-二羟基-10,13-二甲基-17-[(2S)-6-甲基-3-氧代庚烷-2-基]-1,2,3,4,7,8,9,11,12,14,15,16-十二氢环戊烯并[a]菲-16-基]氧基]-5-羟基四氢吡喃-4-基]氧基-4,5-二羟基四氢吡喃-3-基]4-甲氧基苯甲酸酯合成路线 （共 58 条）
→
145075-81-6[(2S,3R,4S,5R)-2-[(2S,3R,4S,5S)-3-乙酰氧基-2-[[(3R,8S,9R,10R,13S,14R,16R,17S)-3,17-二羟基-10,13-二甲基-17-[(2S)-6-甲基-3-氧代庚烷-2-基]-1,2,3,4,7,8,9,11,12,14,15,16-十二氢环戊烯并[a]菲-16-基]氧基]-5-羟基四氢吡喃-4-基]氧基-4,5-二羟基四氢吡喃-3-基]4-甲氧基苯甲酸酯
反应条件
1.1: 82 percent / 2,6-lutidine / nitromethane / 12 h / 25 °C
2.1: 99 percent / NaOMe; H2O / methanol / 1 h / 25 °C
3.1: NaH / tetrahydrofuran; various solvent(s) / 0.17 h / 25 °C
3.2: 98 percent / tetrabutylammonium iodide / tetrahydrofuran; various solvent(s) / 4 h / Heating
4.1: ZnCl2 / CH2Cl2; diethyl ether / 1 h / -60 - 0 °C
5.1: 3.4 g / NaOMe / methanol / 4 h / 25 °C
6.1: 97 percent / DMAP; Et3N / CH2Cl2 / 48 h / 25 °C
7.1: 88 percent / NBS; H2O / CH2Cl2 / 1 h / 25 °C
8.1: 95 percent / DBU / CH2Cl2 / 12 h / 25 °C
9.1: 93 percent / BF3*Et2O; molecular sieves 4 Angstroem / CH2Cl2 / -78 - -20 °C
10.1: 81 percent / NBS; H2O / CH2Cl2 / 2 h / 25 °C
11.1: 88 percent / DBU / CH2Cl2 / 12 h / 25 °C
12.1: 89 percent / TMSOTf; molecular sieves 4 Angstroem / CH2Cl2 / 5 h / -20 °C
13.1: DDQ / CH2Cl2; H2O / 12 h / 25 °C
13.2: 81 percent / Pd(CN)2Cl2 / acetone; H2O / 2 h / 25 °C
View Scheme
参考文献
Yu; Jin
Journal of the American Chemical Society, 2001 , vol. 123, # 14 p. 3369 - 3370
→
145075-81-6[(2S,3R,4S,5R)-2-[(2S,3R,4S,5S)-3-乙酰氧基-2-[[(3R,8S,9R,10R,13S,14R,16R,17S)-3,17-二羟基-10,13-二甲基-17-[(2S)-6-甲基-3-氧代庚烷-2-基]-1,2,3,4,7,8,9,11,12,14,15,16-十二氢环戊烯并[a]菲-16-基]氧基]-5-羟基四氢吡喃-4-基]氧基-4,5-二羟基四氢吡喃-3-基]4-甲氧基苯甲酸酯
反应条件
1: 31 percent / HCl gas / Ambient temperature
2: 65 percent / pyridine / -35 - 20 °C
3: 93 percent / imidazole, DMAP / dimethylformamide / 1 h
4: 76 percent / Et3N, H2 / Pd/C / ethyl acetate / 24 h / 50 °C / 760 Torr
5: 79 percent / DBU / CH2Cl2 / 3 h / Ambient temperature
6: 1.) BF3*OEt2, 4A MS, 2.) 2,6-lutidine / 1.) CH2Cl2, -60 deg C, 30 min, 2.) CH2Cl2, -20 deg C, 1 h
7: 50 percent / H2, Et3N / Pd/C / ethyl acetate; ethanol / 72 h / 50 °C / 38000 Torr
8: 65 percent / DBU / CH2Cl2 / 6 h / Ambient temperature
9: 69 percent / 4A MS, TMSOTf / CH2Cl2 / 0.33 h / -20 °C
10: 79 percent / Pd(MeCN)2Cl2 / acetone; H2O / Ambient temperature
View Scheme
参考文献
Deng, Shaojiang; Yu, Biao; Lou, Yun; Hui, Yongzheng
Journal of Organic Chemistry, 1999 , vol. 64, # 1 p. 202 - 208
→
145075-81-6[(2S,3R,4S,5R)-2-[(2S,3R,4S,5S)-3-乙酰氧基-2-[[(3R,8S,9R,10R,13S,14R,16R,17S)-3,17-二羟基-10,13-二甲基-17-[(2S)-6-甲基-3-氧代庚烷-2-基]-1,2,3,4,7,8,9,11,12,14,15,16-十二氢环戊烯并[a]菲-16-基]氧基]-5-羟基四氢吡喃-4-基]氧基-4,5-二羟基四氢吡喃-3-基]4-甲氧基苯甲酸酯
反应条件
1: 1.) BF3*OEt2, 4A MS, 2.) 2,6-lutidine / 1.) CH2Cl2, -60 deg C, 30 min, 2.) CH2Cl2, -20 deg C, 1 h
2: 50 percent / H2, Et3N / Pd/C / ethyl acetate; ethanol / 72 h / 50 °C / 38000 Torr
3: 65 percent / DBU / CH2Cl2 / 6 h / Ambient temperature
4: 69 percent / 4A MS, TMSOTf / CH2Cl2 / 0.33 h / -20 °C
5: 79 percent / Pd(MeCN)2Cl2 / acetone; H2O / Ambient temperature
View Scheme
参考文献
Deng, Shaojiang; Yu, Biao; Lou, Yun; Hui, Yongzheng
Journal of Organic Chemistry, 1999 , vol. 64, # 1 p. 202 - 208
→
145075-81-6[(2S,3R,4S,5R)-2-[(2S,3R,4S,5S)-3-乙酰氧基-2-[[(3R,8S,9R,10R,13S,14R,16R,17S)-3,17-二羟基-10,13-二甲基-17-[(2S)-6-甲基-3-氧代庚烷-2-基]-1,2,3,4,7,8,9,11,12,14,15,16-十二氢环戊烯并[a]菲-16-基]氧基]-5-羟基四氢吡喃-4-基]氧基-4,5-二羟基四氢吡喃-3-基]4-甲氧基苯甲酸酯
反应条件
1: 94 percent / aq. HOAc / 1 h / 70 °C
2: 1.) BF3*OEt2, 4A MS, 2.) 2,6-lutidine / 1.) CH2Cl2, -60 deg C, 30 min, 2.) CH2Cl2, -20 deg C, 1 h
3: 50 percent / H2, Et3N / Pd/C / ethyl acetate; ethanol / 72 h / 50 °C / 38000 Torr
4: 65 percent / DBU / CH2Cl2 / 6 h / Ambient temperature
5: 69 percent / 4A MS, TMSOTf / CH2Cl2 / 0.33 h / -20 °C
6: 79 percent / Pd(MeCN)2Cl2 / acetone; H2O / Ambient temperature
View Scheme
参考文献
Deng, Shaojiang; Yu, Biao; Lou, Yun; Hui, Yongzheng
Journal of Organic Chemistry, 1999 , vol. 64, # 1 p. 202 - 208
→
145075-81-6[(2S,3R,4S,5R)-2-[(2S,3R,4S,5S)-3-乙酰氧基-2-[[(3R,8S,9R,10R,13S,14R,16R,17S)-3,17-二羟基-10,13-二甲基-17-[(2S)-6-甲基-3-氧代庚烷-2-基]-1,2,3,4,7,8,9,11,12,14,15,16-十二氢环戊烯并[a]菲-16-基]氧基]-5-羟基四氢吡喃-4-基]氧基-4,5-二羟基四氢吡喃-3-基]4-甲氧基苯甲酸酯
反应条件
1: 93 percent / imidazole, DMAP / dimethylformamide / 1 h
2: 76 percent / Et3N, H2 / Pd/C / ethyl acetate / 24 h / 50 °C / 760 Torr
3: 79 percent / DBU / CH2Cl2 / 3 h / Ambient temperature
4: 1.) BF3*OEt2, 4A MS, 2.) 2,6-lutidine / 1.) CH2Cl2, -60 deg C, 30 min, 2.) CH2Cl2, -20 deg C, 1 h
5: 50 percent / H2, Et3N / Pd/C / ethyl acetate; ethanol / 72 h / 50 °C / 38000 Torr
6: 65 percent / DBU / CH2Cl2 / 6 h / Ambient temperature
7: 69 percent / 4A MS, TMSOTf / CH2Cl2 / 0.33 h / -20 °C
8: 79 percent / Pd(MeCN)2Cl2 / acetone; H2O / Ambient temperature
View Scheme
参考文献
Deng, Shaojiang; Yu, Biao; Lou, Yun; Hui, Yongzheng
Journal of Organic Chemistry, 1999 , vol. 64, # 1 p. 202 - 208
→
145075-81-6[(2S,3R,4S,5R)-2-[(2S,3R,4S,5S)-3-乙酰氧基-2-[[(3R,8S,9R,10R,13S,14R,16R,17S)-3,17-二羟基-10,13-二甲基-17-[(2S)-6-甲基-3-氧代庚烷-2-基]-1,2,3,4,7,8,9,11,12,14,15,16-十二氢环戊烯并[a]菲-16-基]氧基]-5-羟基四氢吡喃-4-基]氧基-4,5-二羟基四氢吡喃-3-基]4-甲氧基苯甲酸酯
反应条件
1: 76 percent / Et3N, H2 / Pd/C / ethyl acetate / 24 h / 50 °C / 760 Torr
2: 79 percent / DBU / CH2Cl2 / 3 h / Ambient temperature
3: 1.) BF3*OEt2, 4A MS, 2.) 2,6-lutidine / 1.) CH2Cl2, -60 deg C, 30 min, 2.) CH2Cl2, -20 deg C, 1 h
4: 50 percent / H2, Et3N / Pd/C / ethyl acetate; ethanol / 72 h / 50 °C / 38000 Torr
5: 65 percent / DBU / CH2Cl2 / 6 h / Ambient temperature
6: 69 percent / 4A MS, TMSOTf / CH2Cl2 / 0.33 h / -20 °C
7: 79 percent / Pd(MeCN)2Cl2 / acetone; H2O / Ambient temperature
View Scheme
参考文献
Deng, Shaojiang; Yu, Biao; Lou, Yun; Hui, Yongzheng
Journal of Organic Chemistry, 1999 , vol. 64, # 1 p. 202 - 208
→
145075-81-6[(2S,3R,4S,5R)-2-[(2S,3R,4S,5S)-3-乙酰氧基-2-[[(3R,8S,9R,10R,13S,14R,16R,17S)-3,17-二羟基-10,13-二甲基-17-[(2S)-6-甲基-3-氧代庚烷-2-基]-1,2,3,4,7,8,9,11,12,14,15,16-十二氢环戊烯并[a]菲-16-基]氧基]-5-羟基四氢吡喃-4-基]氧基-4,5-二羟基四氢吡喃-3-基]4-甲氧基苯甲酸酯
反应条件
1: 1.) BF3*OEt2, 4A MS, 2.) 2,6-lutidine / 1.) CH2Cl2, -60 deg C, 30 min, 2.) CH2Cl2, -20 deg C, 1 h
2: 50 percent / H2, Et3N / Pd/C / ethyl acetate; ethanol / 72 h / 50 °C / 38000 Torr
3: 65 percent / DBU / CH2Cl2 / 6 h / Ambient temperature
4: 69 percent / 4A MS, TMSOTf / CH2Cl2 / 0.33 h / -20 °C
5: 79 percent / Pd(MeCN)2Cl2 / acetone; H2O / Ambient temperature
View Scheme
参考文献
Deng, Shaojiang; Yu, Biao; Lou, Yun; Hui, Yongzheng
Journal of Organic Chemistry, 1999 , vol. 64, # 1 p. 202 - 208
→
145075-81-6[(2S,3R,4S,5R)-2-[(2S,3R,4S,5S)-3-乙酰氧基-2-[[(3R,8S,9R,10R,13S,14R,16R,17S)-3,17-二羟基-10,13-二甲基-17-[(2S)-6-甲基-3-氧代庚烷-2-基]-1,2,3,4,7,8,9,11,12,14,15,16-十二氢环戊烯并[a]菲-16-基]氧基]-5-羟基四氢吡喃-4-基]氧基-4,5-二羟基四氢吡喃-3-基]4-甲氧基苯甲酸酯
反应条件
1: 50 percent / H2, Et3N / Pd/C / ethyl acetate; ethanol / 72 h / 50 °C / 38000 Torr
2: 65 percent / DBU / CH2Cl2 / 6 h / Ambient temperature
3: 69 percent / 4A MS, TMSOTf / CH2Cl2 / 0.33 h / -20 °C
4: 79 percent / Pd(MeCN)2Cl2 / acetone; H2O / Ambient temperature
View Scheme
参考文献
Deng, Shaojiang; Yu, Biao; Lou, Yun; Hui, Yongzheng
Journal of Organic Chemistry, 1999 , vol. 64, # 1 p. 202 - 208
→
145075-81-6[(2S,3R,4S,5R)-2-[(2S,3R,4S,5S)-3-乙酰氧基-2-[[(3R,8S,9R,10R,13S,14R,16R,17S)-3,17-二羟基-10,13-二甲基-17-[(2S)-6-甲基-3-氧代庚烷-2-基]-1,2,3,4,7,8,9,11,12,14,15,16-十二氢环戊烯并[a]菲-16-基]氧基]-5-羟基四氢吡喃-4-基]氧基-4,5-二羟基四氢吡喃-3-基]4-甲氧基苯甲酸酯
反应条件
1: 65 percent / pyridine / -35 - 20 °C
2: 93 percent / imidazole, DMAP / dimethylformamide / 1 h
3: 76 percent / Et3N, H2 / Pd/C / ethyl acetate / 24 h / 50 °C / 760 Torr
4: 79 percent / DBU / CH2Cl2 / 3 h / Ambient temperature
5: 1.) BF3*OEt2, 4A MS, 2.) 2,6-lutidine / 1.) CH2Cl2, -60 deg C, 30 min, 2.) CH2Cl2, -20 deg C, 1 h
6: 50 percent / H2, Et3N / Pd/C / ethyl acetate; ethanol / 72 h / 50 °C / 38000 Torr
7: 65 percent / DBU / CH2Cl2 / 6 h / Ambient temperature
8: 69 percent / 4A MS, TMSOTf / CH2Cl2 / 0.33 h / -20 °C
9: 79 percent / Pd(MeCN)2Cl2 / acetone; H2O / Ambient temperature
View Scheme
参考文献
Deng, Shaojiang; Yu, Biao; Lou, Yun; Hui, Yongzheng
Journal of Organic Chemistry, 1999 , vol. 64, # 1 p. 202 - 208
→
145075-81-6[(2S,3R,4S,5R)-2-[(2S,3R,4S,5S)-3-乙酰氧基-2-[[(3R,8S,9R,10R,13S,14R,16R,17S)-3,17-二羟基-10,13-二甲基-17-[(2S)-6-甲基-3-氧代庚烷-2-基]-1,2,3,4,7,8,9,11,12,14,15,16-十二氢环戊烯并[a]菲-16-基]氧基]-5-羟基四氢吡喃-4-基]氧基-4,5-二羟基四氢吡喃-3-基]4-甲氧基苯甲酸酯
反应条件
1: TsOH*H2O / dimethylformamide / 5 h / Ambient temperature
2: pyridine / Ambient temperature
3: 94 percent / aq. HOAc / 1 h / 70 °C
4: 1.) BF3*OEt2, 4A MS, 2.) 2,6-lutidine / 1.) CH2Cl2, -60 deg C, 30 min, 2.) CH2Cl2, -20 deg C, 1 h
5: 50 percent / H2, Et3N / Pd/C / ethyl acetate; ethanol / 72 h / 50 °C / 38000 Torr
6: 65 percent / DBU / CH2Cl2 / 6 h / Ambient temperature
7: 69 percent / 4A MS, TMSOTf / CH2Cl2 / 0.33 h / -20 °C
8: 79 percent / Pd(MeCN)2Cl2 / acetone; H2O / Ambient temperature
View Scheme
参考文献
Deng, Shaojiang; Yu, Biao; Lou, Yun; Hui, Yongzheng
Journal of Organic Chemistry, 1999 , vol. 64, # 1 p. 202 - 208
