(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: Ph3P; imidazole; I2 / acetonitrile; diethyl ether / 1 h / 20 °C
2.1: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C
2.2: 93 percent / tetrahydrofuran / 1 h / -78 °C
3.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C
4.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C
5.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C
6.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C
6.2: tetrahydrofuran / 1.5 h / -95 - -80 °C
View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
→
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: 98 percent / DIBALH / tetrahydrofuran; heptane / 2.5 h / 0 °C
2.1: Ph3P; imidazole; I2 / acetonitrile; diethyl ether / 1 h / 20 °C
3.1: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C
3.2: 93 percent / tetrahydrofuran / 1 h / -78 °C
4.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C
5.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C
6.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C
7.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C
7.2: tetrahydrofuran / 1.5 h / -95 - -80 °C
View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
→
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: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C
2.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C
3.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C
4.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C
4.2: tetrahydrofuran / 1.5 h / -95 - -80 °C
View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
→
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: 96 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
2.1: pentane / 4 h / 0 °C
2.2: 97 percent / MeOH / 1 h / 20 °C
3.1: LDA / tetrahydrofuran; hexane / 0.5 h / -78 °C
3.2: 85 percent / tetrahydrofuran / 1.5 h / -78 - 0 °C
4.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C
4.2: tetrahydrofuran / 1.5 h / -95 - -80 °C
View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
→
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: 2 h / 100 °C
2: KHMDS / tetrahydrofuran / 1.) 0 deg C, 30 min, 2.) -78 deg C, 3 h
3: benzene / 18 h / Heating
4: DIBAL-H / tetrahydrofuran / 3 h / -78 °C
5: 80 percent / CCl4, PPh3 / 18 h / Heating
6: 92 percent / LiEt3BH / tetrahydrofuran / 1 h / -78 °C
7: 95 percent / CSA / methanol / 1 h / 25 °C
8: SO3*Py, DMSO, Et3N / tetrahydrofuran / 1 h / 0 °C
9: LDA / tetrahydrofuran / 1.) -78 to -40 deg C, 1 h, 2.) -78 deg C, 2 min
View Scheme
参考文献
Nicolaou; Hepworth, David; Finlay, M. Ray V.; King, N. Paul; Werschkun, Barbara; Bigot, Antony
Chemical Communications, 1999 , # 6 p. 519 - 520
→
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: NaBH4 / ethanol / 0.5 h / 0 °C
2: 100 percent / I2, PPh3 / acetonitrile; diethyl ether / 1 h / 0 - 25 °C
3: 2 h / 100 °C
4: KHMDS / tetrahydrofuran / 1.) 0 deg C, 30 min, 2.) -78 deg C, 3 h
5: benzene / 18 h / Heating
6: DIBAL-H / tetrahydrofuran / 3 h / -78 °C
7: 80 percent / CCl4, PPh3 / 18 h / Heating
8: 92 percent / LiEt3BH / tetrahydrofuran / 1 h / -78 °C
9: 95 percent / CSA / methanol / 1 h / 25 °C
10: SO3*Py, DMSO, Et3N / tetrahydrofuran / 1 h / 0 °C
11: LDA / tetrahydrofuran / 1.) -78 to -40 deg C, 1 h, 2.) -78 deg C, 2 min
View Scheme
参考文献
Nicolaou; Hepworth, David; Finlay, M. Ray V.; King, N. Paul; Werschkun, Barbara; Bigot, Antony
Chemical Communications, 1999 , # 6 p. 519 - 520
→
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.) O3, 2.) PPh3 / 1.) CH2Cl2, -78 deg C, 2.) CH2Cl2
2: NaBH4 / ethanol / 0.5 h / 0 °C
3: 100 percent / I2, PPh3 / acetonitrile; diethyl ether / 1 h / 0 - 25 °C
4: 2 h / 100 °C
5: KHMDS / tetrahydrofuran / 1.) 0 deg C, 30 min, 2.) -78 deg C, 3 h
6: benzene / 18 h / Heating
7: DIBAL-H / tetrahydrofuran / 3 h / -78 °C
8: 80 percent / CCl4, PPh3 / 18 h / Heating
9: 92 percent / LiEt3BH / tetrahydrofuran / 1 h / -78 °C
10: 95 percent / CSA / methanol / 1 h / 25 °C
11: SO3*Py, DMSO, Et3N / tetrahydrofuran / 1 h / 0 °C
12: LDA / tetrahydrofuran / 1.) -78 to -40 deg C, 1 h, 2.) -78 deg C, 2 min
View Scheme
参考文献
Nicolaou; Hepworth, David; Finlay, M. Ray V.; King, N. Paul; Werschkun, Barbara; Bigot, Antony
Chemical Communications, 1999 , # 6 p. 519 - 520
→
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: benzene / 18 h / Heating
2: DIBAL-H / tetrahydrofuran / 3 h / -78 °C
3: 80 percent / CCl4, PPh3 / 18 h / Heating
4: 92 percent / LiEt3BH / tetrahydrofuran / 1 h / -78 °C
5: 95 percent / CSA / methanol / 1 h / 25 °C
6: SO3*Py, DMSO, Et3N / tetrahydrofuran / 1 h / 0 °C
7: LDA / tetrahydrofuran / 1.) -78 to -40 deg C, 1 h, 2.) -78 deg C, 2 min
View Scheme
参考文献
Nicolaou; Hepworth, David; Finlay, M. Ray V.; King, N. Paul; Werschkun, Barbara; Bigot, Antony
Chemical Communications, 1999 , # 6 p. 519 - 520
→
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: 92 percent / LiEt3BH / tetrahydrofuran / 1 h / -78 °C
2: 95 percent / CSA / methanol / 1 h / 25 °C
3: SO3*Py, DMSO, Et3N / tetrahydrofuran / 1 h / 0 °C
4: LDA / tetrahydrofuran / 1.) -78 to -40 deg C, 1 h, 2.) -78 deg C, 2 min
View Scheme
参考文献
Nicolaou; Hepworth, David; Finlay, M. Ray V.; King, N. Paul; Werschkun, Barbara; Bigot, Antony
Chemical Communications, 1999 , # 6 p. 519 - 520
→
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 / CCl4, PPh3 / 18 h / Heating
2: 92 percent / LiEt3BH / tetrahydrofuran / 1 h / -78 °C
3: 95 percent / CSA / methanol / 1 h / 25 °C
4: SO3*Py, DMSO, Et3N / tetrahydrofuran / 1 h / 0 °C
5: LDA / tetrahydrofuran / 1.) -78 to -40 deg C, 1 h, 2.) -78 deg C, 2 min
View Scheme
参考文献
Nicolaou; Hepworth, David; Finlay, M. Ray V.; King, N. Paul; Werschkun, Barbara; Bigot, Antony
Chemical Communications, 1999 , # 6 p. 519 - 520
