[(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: 95 percent / NaOMe / methanol / 6 h / 25 °C
2.1: CSA / CH2Cl2 / 12 h / 25 °C
3.1: DMAP; Et3N / CH2Cl2 / 2 h / 25 °C
4.1: 5.1 g / Amberlite IR-118H / methanol / 12 h / 25 °C
5.1: 90 percent / lutidine / CH2Cl2 / 2 h / -70 - -60 °C
6.1: 93 percent / BF3*Et2O; 4 Angstroem molecular sieves / CH2Cl2 / -78 - -20 °C
7.1: NBS; H2O / CH2Cl2 / 2 h / 25 °C
7.2: 98 percent / DBU / CH2Cl2 / 12 h / 25 °C
8.1: 71 percent / TMSOTf; 4 Angstroem molecular sieves / CH2Cl2 / 5 h / -20 °C
9.1: DDQ; H2O / CH2Cl2 / 12 h / 25 °C
9.2: 81 percent / Pd(CN)2Cl2; H2O / acetone / 2 h / 25 °C
View Scheme
参考文献
Yu, Wensheng; Jin, Zhendong
Journal of the American Chemical Society, 2002 , vol. 124, # 23 p. 6576 - 6583
→
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: 93 percent / BF3*Et2O; 4 Angstroem molecular sieves / CH2Cl2 / -78 - -20 °C
2.1: NBS; H2O / CH2Cl2 / 2 h / 25 °C
2.2: 98 percent / DBU / CH2Cl2 / 12 h / 25 °C
3.1: 71 percent / TMSOTf; 4 Angstroem molecular sieves / CH2Cl2 / 5 h / -20 °C
4.1: DDQ; H2O / CH2Cl2 / 12 h / 25 °C
4.2: 81 percent / Pd(CN)2Cl2; H2O / acetone / 2 h / 25 °C
View Scheme
参考文献
Yu, Wensheng; Jin, Zhendong
Journal of the American Chemical Society, 2002 , vol. 124, # 23 p. 6576 - 6583
→
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: 97 percent / DMAP; Et3N / CH2Cl2 / 48 h / 25 °C
2.1: 88 percent / NBS; H2O / CH2Cl2 / 1 h / 25 °C
3.1: 555 mg / DBU / CH2Cl2 / 12 h / 25 °C
4.1: 93 percent / BF3*Et2O; 4 Angstroem molecular sieves / CH2Cl2 / -78 - -20 °C
5.1: NBS; H2O / CH2Cl2 / 2 h / 25 °C
5.2: 98 percent / DBU / CH2Cl2 / 12 h / 25 °C
6.1: 71 percent / TMSOTf; 4 Angstroem molecular sieves / CH2Cl2 / 5 h / -20 °C
7.1: DDQ; H2O / CH2Cl2 / 12 h / 25 °C
7.2: 81 percent / Pd(CN)2Cl2; H2O / acetone / 2 h / 25 °C
View Scheme
参考文献
Yu, Wensheng; Jin, Zhendong
Journal of the American Chemical Society, 2002 , vol. 124, # 23 p. 6576 - 6583
→
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: 3.4 g / NaOMe / methanol / 4 h / 25 °C
2.1: 97 percent / DMAP; Et3N / CH2Cl2 / 48 h / 25 °C
3.1: 88 percent / NBS; H2O / CH2Cl2 / 1 h / 25 °C
4.1: 555 mg / DBU / CH2Cl2 / 12 h / 25 °C
5.1: 93 percent / BF3*Et2O; 4 Angstroem molecular sieves / CH2Cl2 / -78 - -20 °C
6.1: NBS; H2O / CH2Cl2 / 2 h / 25 °C
6.2: 98 percent / DBU / CH2Cl2 / 12 h / 25 °C
7.1: 71 percent / TMSOTf; 4 Angstroem molecular sieves / CH2Cl2 / 5 h / -20 °C
8.1: DDQ; H2O / CH2Cl2 / 12 h / 25 °C
8.2: 81 percent / Pd(CN)2Cl2; H2O / acetone / 2 h / 25 °C
View Scheme
参考文献
Yu, Wensheng; Jin, Zhendong
Journal of the American Chemical Society, 2002 , vol. 124, # 23 p. 6576 - 6583
→
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: ZnCl2 / CH2Cl2 / -60 - 0 °C
2.1: 3.4 g / NaOMe / methanol / 4 h / 25 °C
3.1: 97 percent / DMAP; Et3N / CH2Cl2 / 48 h / 25 °C
4.1: 88 percent / NBS; H2O / CH2Cl2 / 1 h / 25 °C
5.1: 555 mg / DBU / CH2Cl2 / 12 h / 25 °C
6.1: 93 percent / BF3*Et2O; 4 Angstroem molecular sieves / CH2Cl2 / -78 - -20 °C
7.1: NBS; H2O / CH2Cl2 / 2 h / 25 °C
7.2: 98 percent / DBU / CH2Cl2 / 12 h / 25 °C
8.1: 71 percent / TMSOTf; 4 Angstroem molecular sieves / CH2Cl2 / 5 h / -20 °C
9.1: DDQ; H2O / CH2Cl2 / 12 h / 25 °C
9.2: 81 percent / Pd(CN)2Cl2; H2O / acetone / 2 h / 25 °C
View Scheme
参考文献
Yu, Wensheng; Jin, Zhendong
Journal of the American Chemical Society, 2002 , vol. 124, # 23 p. 6576 - 6583
→
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: tert-BuLi; CuCN; LiCl / diethyl ether; tetrahydrofuran / 0.75 h / -78 °C
1.2: tetrahydrofuran / -78 - 25 °C
2.1: t-BuOK / tetrahydrofuran / 0.17 h / 0 °C
2.2: tetrahydrofuran / -30 - 25 °C
3.1: 1.274 g / PPTS / CH2Cl2 / 3 h / 25 °C
4.1: KO-t-Bu / tetrahydrofuran / 0.17 h / 0 °C
4.2: 76 percent / Davis reagent / -78 °C
5.1: 97 percent / LiAlH4 / tetrahydrofuran / 1 h / -78 °C
6.1: 71 percent / TMSOTf; 4 Angstroem molecular sieves / CH2Cl2 / 5 h / -20 °C
7.1: DDQ; H2O / CH2Cl2 / 12 h / 25 °C
7.2: 81 percent / Pd(CN)2Cl2; H2O / acetone / 2 h / 25 °C
View Scheme
参考文献
Yu, Wensheng; Jin, Zhendong
Journal of the American Chemical Society, 2002 , vol. 124, # 23 p. 6576 - 6583
→
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: 88 percent / NBS; H2O / CH2Cl2 / 1 h / 25 °C
2.1: 555 mg / DBU / CH2Cl2 / 12 h / 25 °C
3.1: 93 percent / BF3*Et2O; 4 Angstroem molecular sieves / CH2Cl2 / -78 - -20 °C
4.1: NBS; H2O / CH2Cl2 / 2 h / 25 °C
4.2: 98 percent / DBU / CH2Cl2 / 12 h / 25 °C
5.1: 71 percent / TMSOTf; 4 Angstroem molecular sieves / CH2Cl2 / 5 h / -20 °C
6.1: DDQ; H2O / CH2Cl2 / 12 h / 25 °C
6.2: 81 percent / Pd(CN)2Cl2; H2O / acetone / 2 h / 25 °C
View Scheme
参考文献
Yu, Wensheng; Jin, Zhendong
Journal of the American Chemical Society, 2002 , vol. 124, # 23 p. 6576 - 6583
→
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: LiAlH4
2: TMSOTf
3: pyridinium dichromate
4: 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
1.1: 82 percent / 2,6-lutidine / nitromethane / 12 h / 25 °C
2.1: NaOMe / methanol / 3 h / 25 °C
3.1: NaH / tetrahydrofuran / 0 °C
3.2: 5.14 g / tetrabutylammonium chloride / tetrahydrofuran / 4 h / Heating
4.1: ZnCl2 / CH2Cl2 / -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: 555 mg / DBU / CH2Cl2 / 12 h / 25 °C
9.1: 93 percent / BF3*Et2O; 4 Angstroem molecular sieves / CH2Cl2 / -78 - -20 °C
10.1: NBS; H2O / CH2Cl2 / 2 h / 25 °C
10.2: 98 percent / DBU / CH2Cl2 / 12 h / 25 °C
11.1: 71 percent / TMSOTf; 4 Angstroem molecular sieves / CH2Cl2 / 5 h / -20 °C
12.1: DDQ; H2O / CH2Cl2 / 12 h / 25 °C
12.2: 81 percent / Pd(CN)2Cl2; H2O / acetone / 2 h / 25 °C
View Scheme
参考文献
Yu, Wensheng; Jin, Zhendong
Journal of the American Chemical Society, 2002 , vol. 124, # 23 p. 6576 - 6583
→
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: 97 percent / DMAP; Et3N / CH2Cl2 / 48 h / 25 °C
2.1: 88 percent / NBS; H2O / CH2Cl2 / 1 h / 25 °C
3.1: 555 mg / DBU / CH2Cl2 / 12 h / 25 °C
4.1: 93 percent / BF3*Et2O; 4 Angstroem molecular sieves / CH2Cl2 / -78 - -20 °C
5.1: NBS; H2O / CH2Cl2 / 2 h / 25 °C
5.2: 98 percent / DBU / CH2Cl2 / 12 h / 25 °C
6.1: 71 percent / TMSOTf; 4 Angstroem molecular sieves / CH2Cl2 / 5 h / -20 °C
7.1: DDQ; H2O / CH2Cl2 / 12 h / 25 °C
7.2: 81 percent / Pd(CN)2Cl2; H2O / acetone / 2 h / 25 °C
View Scheme
参考文献
Yu, Wensheng; Jin, Zhendong
Journal of the American Chemical Society, 2002 , vol. 124, # 23 p. 6576 - 6583
