[(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: pyridine / Ambient temperature
2: 94 percent / aq. HOAc / 1 h / 70 °C
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
toluene-4-sulfonic acid in 1,4-dioxane
T=80°C;
参考文献
Morzycki, Jacek W.; Wojtkielewicz, Agnieszka; Wolczynski, Slawomir
Bioorganic and Medicinal Chemistry Letters, 2004 , vol. 14, # 12 p. 3323 - 3326
→
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: 59 percent / TMSOTf; 4 Angstroem molecular sieves / CH2Cl2 / 0.5 h / -68 °C
2: 86 percent / H2; Et3N / Pd/C / ethyl acetate; ethanol / 50 °C / 38000 Torr
3: 100 percent / pyridinium dichromate / CH2Cl2 / 1 h
4: 74 percent / PdCl2 / acetonitrile; acetone; H2O / 60 h / 20 °C
View Scheme
参考文献
Morzycki, Jacek W; Wojtkielewicz, Agnieszka
Carbohydrate research, 2002 , vol. 337, # 14 p. 1269 - 1274
→
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: 86 percent / H2; Et3N / Pd/C / ethyl acetate; ethanol / 50 °C / 38000 Torr
2: 100 percent / pyridinium dichromate / CH2Cl2 / 1 h
3: 74 percent / PdCl2 / acetonitrile; acetone; H2O / 60 h / 20 °C
View Scheme
参考文献
Morzycki, Jacek W; Wojtkielewicz, Agnieszka
Carbohydrate research, 2002 , vol. 337, # 14 p. 1269 - 1274
→
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: pyridinium dichromate
2: aq. p-TsOH / dioxane / 80 °C
View Scheme
参考文献
Morzycki, Jacek W.; Wojtkielewicz, Agnieszka; Wolczynski, Slawomir
Bioorganic and Medicinal Chemistry Letters, 2004 , vol. 14, # 12 p. 3323 - 3326
→
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: 100 percent / imidazole / dimethylformamide / Ambient temperature
2: 75 percent / BF3*OEt2 / CH2Cl2 / 0.17 h / Ambient temperature
3: 86 percent / Dess-Martin periodinane / CH2Cl2 / 3 h / Ambient temperature
4: 96 percent / diethyl ether / 1 h / Ambient temperature
5: 83 percent / pyridinium dichromate, 4A MS / CH2Cl2; dimethylformamide / 2 h / Ambient temperature
6: 96 percent / CH(OEt)3, TsOH*H2O / CH2Cl2 / 96 h / Ambient temperature
7: 95 percent / TBAF / tetrahydrofuran / 10 h / Ambient temperature
8: 96 percent / imidazole / dimethylformamide / Ambient temperature
9: 41 percent / OsO4, pyridine / diethyl ether / 3 h / -20 - 20 °C
10: 78 percent / (COCl)2, DMSO, Et3N / CH2Cl2 / -78 - 20 °C
11: 93 percent / CeCl3*7H2O, NaBH4 / tetrahydrofuran / 3 h / 0 °C
12: 69 percent / 4A MS, TMSOTf / CH2Cl2 / 0.33 h / -20 °C
13: 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: 96 percent / imidazole / dimethylformamide / Ambient temperature
2: 41 percent / OsO4, pyridine / diethyl ether / 3 h / -20 - 20 °C
3: 78 percent / (COCl)2, DMSO, Et3N / CH2Cl2 / -78 - 20 °C
4: 93 percent / CeCl3*7H2O, NaBH4 / tetrahydrofuran / 3 h / 0 °C
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: 41 percent / OsO4, pyridine / diethyl ether / 3 h / -20 - 20 °C
2: 78 percent / (COCl)2, DMSO, Et3N / CH2Cl2 / -78 - 20 °C
3: 93 percent / CeCl3*7H2O, NaBH4 / tetrahydrofuran / 3 h / 0 °C
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: 75 percent / BF3*OEt2 / CH2Cl2 / 0.17 h / Ambient temperature
2: 86 percent / Dess-Martin periodinane / CH2Cl2 / 3 h / Ambient temperature
3: 96 percent / diethyl ether / 1 h / Ambient temperature
4: 83 percent / pyridinium dichromate, 4A MS / CH2Cl2; dimethylformamide / 2 h / Ambient temperature
5: 96 percent / CH(OEt)3, TsOH*H2O / CH2Cl2 / 96 h / Ambient temperature
6: 95 percent / TBAF / tetrahydrofuran / 10 h / Ambient temperature
7: 96 percent / imidazole / dimethylformamide / Ambient temperature
8: 41 percent / OsO4, pyridine / diethyl ether / 3 h / -20 - 20 °C
9: 78 percent / (COCl)2, DMSO, Et3N / CH2Cl2 / -78 - 20 °C
10: 93 percent / CeCl3*7H2O, NaBH4 / tetrahydrofuran / 3 h / 0 °C
11: 69 percent / 4A MS, TMSOTf / CH2Cl2 / 0.33 h / -20 °C
12: 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: 86 percent / Dess-Martin periodinane / CH2Cl2 / 3 h / Ambient temperature
2: 96 percent / diethyl ether / 1 h / Ambient temperature
3: 83 percent / pyridinium dichromate, 4A MS / CH2Cl2; dimethylformamide / 2 h / Ambient temperature
4: 96 percent / CH(OEt)3, TsOH*H2O / CH2Cl2 / 96 h / Ambient temperature
5: 95 percent / TBAF / tetrahydrofuran / 10 h / Ambient temperature
6: 96 percent / imidazole / dimethylformamide / Ambient temperature
7: 41 percent / OsO4, pyridine / diethyl ether / 3 h / -20 - 20 °C
8: 78 percent / (COCl)2, DMSO, Et3N / CH2Cl2 / -78 - 20 °C
9: 93 percent / CeCl3*7H2O, NaBH4 / tetrahydrofuran / 3 h / 0 °C
10: 69 percent / 4A MS, TMSOTf / CH2Cl2 / 0.33 h / -20 °C
11: 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
