(3S,6R,7S,8S,12Z,15S,16E)-1,3,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-7-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七烷基-12,16-二烯-5-酮合成路线 （共 61 条）
→
193146-49-5(3S,6R,7S,8S,12Z,15S,16E)-1,3,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-7-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七烷基-12,16-二烯-5-酮
反应条件
1: 1) LDA / 1) THF, 0 deg C, 8 h, 2) THF, -100 deg C -> -20 deg C, 10 h
2: 80 percent / monoperoxyphthalic acid magnesium salt / methanol / 1 h / 0 °C
3: 82 percent / DIBAL / toluene / 1 h / -78 °C
4: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
View Scheme
参考文献
Nicolaou; Ninkovic; Sarabia; Vourloumis; He; Vallberg; Finlay; Yang
Journal of the American Chemical Society, 1997 , vol. 119, # 34 p. 7974 - 7991
→
193146-49-5(3S,6R,7S,8S,12Z,15S,16E)-1,3,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-7-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七烷基-12,16-二烯-5-酮
反应条件
1: 83 percent / Ph3P, CCl4 / 24 h / 100 °C
2: 99 percent / LiEt3BH / tetrahydrofuran / 1 h / 0 °C
3: 91 percent / 9-BBN / tetrahydrofuran / 2 h / 0 °C
4: 92 percent / I2, imidazole, Ph3P / diethyl ether; acetonitrile / 0.5 h / 0 °C
5: 1) LDA / 1) THF, 0 deg C, 8 h, 2) THF, -100 deg C -> -20 deg C, 10 h
6: 80 percent / monoperoxyphthalic acid magnesium salt / methanol / 1 h / 0 °C
7: 82 percent / DIBAL / toluene / 1 h / -78 °C
8: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
View Scheme
参考文献
Nicolaou; Ninkovic; Sarabia; Vourloumis; He; Vallberg; Finlay; Yang
Journal of the American Chemical Society, 1997 , vol. 119, # 34 p. 7974 - 7991
→
193146-49-5(3S,6R,7S,8S,12Z,15S,16E)-1,3,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-7-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七烷基-12,16-二烯-5-酮
反应条件
1: 99 percent / LiEt3BH / tetrahydrofuran / 1 h / 0 °C
2: 91 percent / 9-BBN / tetrahydrofuran / 2 h / 0 °C
3: 92 percent / I2, imidazole, Ph3P / diethyl ether; acetonitrile / 0.5 h / 0 °C
4: 1) LDA / 1) THF, 0 deg C, 8 h, 2) THF, -100 deg C -> -20 deg C, 10 h
5: 80 percent / monoperoxyphthalic acid magnesium salt / methanol / 1 h / 0 °C
6: 82 percent / DIBAL / toluene / 1 h / -78 °C
7: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
View Scheme
参考文献
Nicolaou; Ninkovic; Sarabia; Vourloumis; He; Vallberg; Finlay; Yang
Journal of the American Chemical Society, 1997 , vol. 119, # 34 p. 7974 - 7991
→
193146-49-5(3S,6R,7S,8S,12Z,15S,16E)-1,3,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-7-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七烷基-12,16-二烯-5-酮
反应条件
1: 98 percent / DIBAL / tetrahydrofuran; CH2Cl2 / 3 h / -78 °C
2: 83 percent / Ph3P, CCl4 / 24 h / 100 °C
3: 99 percent / LiEt3BH / tetrahydrofuran / 1 h / 0 °C
4: 91 percent / 9-BBN / tetrahydrofuran / 2 h / 0 °C
5: 92 percent / I2, imidazole, Ph3P / diethyl ether; acetonitrile / 0.5 h / 0 °C
6: 1) LDA / 1) THF, 0 deg C, 8 h, 2) THF, -100 deg C -> -20 deg C, 10 h
7: 80 percent / monoperoxyphthalic acid magnesium salt / methanol / 1 h / 0 °C
8: 82 percent / DIBAL / toluene / 1 h / -78 °C
9: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
View Scheme
参考文献
Nicolaou; Ninkovic; Sarabia; Vourloumis; He; Vallberg; Finlay; Yang
Journal of the American Chemical Society, 1997 , vol. 119, # 34 p. 7974 - 7991
→
193146-49-5(3S,6R,7S,8S,12Z,15S,16E)-1,3,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-7-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七烷基-12,16-二烯-5-酮
反应条件
1: 82 percent / DIBAL / toluene / 1 h / -78 °C
2: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
View Scheme
参考文献
Nicolaou; Ninkovic; Sarabia; Vourloumis; He; Vallberg; Finlay; Yang
Journal of the American Chemical Society, 1997 , vol. 119, # 34 p. 7974 - 7991
→
193146-49-5(3S,6R,7S,8S,12Z,15S,16E)-1,3,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-7-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七烷基-12,16-二烯-5-酮
反应条件
1: 80 percent / monoperoxyphthalic acid magnesium salt / methanol / 1 h / 0 °C
2: 82 percent / DIBAL / toluene / 1 h / -78 °C
3: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
View Scheme
参考文献
Nicolaou; Ninkovic; Sarabia; Vourloumis; He; Vallberg; Finlay; Yang
Journal of the American Chemical Society, 1997 , vol. 119, # 34 p. 7974 - 7991
→
193146-49-5(3S,6R,7S,8S,12Z,15S,16E)-1,3,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-7-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七烷基-12,16-二烯-5-酮
反应条件
lithium diisopropyl amide
1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min; Yield given. Multistep reaction. Yields of byproduct given;
参考文献
Nicolaou; Ninkovic; Sarabia; Vourloumis; He; Vallberg; Finlay; Yang
Journal of the American Chemical Society, 1997 , vol. 119, # 34 p. 7974 - 7991
→
193146-49-5(3S,6R,7S,8S,12Z,15S,16E)-1,3,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-7-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七烷基-12,16-二烯-5-酮
反应条件
lithium diisopropyl amide in tetrahydrofuran
T=-95°C; 2 h; Yield given;
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Tetrahedron Letters, 1998 , vol. 39, # 47 p. 8633 - 8636
→
193146-49-5(3S,6R,7S,8S,12Z,15S,16E)-1,3,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-7-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七烷基-12,16-二烯-5-酮
反应条件
1: 71 percent / Kiyooka's chiral boron reagent
2: 77 percent / Et3N
3: LDA
View Scheme
参考文献
Taylor, Richard E.; Chen, Yue
Organic Letters, 2001 , vol. 3, # 14 p. 2221 - 2223
→
193146-49-5(3S,6R,7S,8S,12Z,15S,16E)-1,3,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-7-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七烷基-12,16-二烯-5-酮
反应条件
1.1: OsO4
1.2: 80 percent / NaIO4
2.1: 93 percent / NiCl2; CrCl2 / dimethylformamide / 0.67 h / 20 °C
3.1: 87 percent / SOCl2 / diethyl ether; pentane / 6.5 h / -78 - 0 °C
4.1: 88 percent / LiEt3BH / tetrahydrofuran / 2 h / -78 - 20 °C
5.1: 80 percent / PCC
6.1: LDA
View Scheme
参考文献
Taylor, Richard E.; Chen, Yue
Organic Letters, 2001 , vol. 3, # 14 p. 2221 - 2223
