(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)-5-氧代-十七-12,16-二烯酸合成路线 （共 69 条）
→
193146-63-3(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)-5-氧代-十七-12,16-二烯酸
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
4: 96 percent / 2,6-lutidine / CH2Cl2 / 2 h / 0 °C
5: 85 percent / camphorsulfonic acid / CH2Cl2; methanol / 0.5 h / 0 - 25 °C
6: 1) (COCl)2, DMSO, 2) Et3N / 1) CH2Cl2, -78 deg C, 30 min, 2) CH2Cl2, -78 deg C -> 0 deg C, 30 min
7: 90 percent / NaClO2, isobutylene, NaH2PO4 / 2-methyl-propan-2-ol; H2O; tetrahydrofuran / 1 h / Ambient temperature
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
→
193146-63-3(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)-5-氧代-十七-12,16-二烯酸
反应条件
1.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C
2.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C
2.2: tetrahydrofuran / 1.5 h / -95 - -80 °C
3.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
4.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C
5.1: Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 20 °C
6.1: 380 mg / NaClO2; NaH2PO4 / 2-methyl-propan-2-ol; various solvent(s); H2O / 3 h
View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
→
193146-63-3(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)-5-氧代-十七-12,16-二烯酸
反应条件
1.1: pentane / 4 h / 0 °C
1.2: 97 percent / MeOH / 1 h / 20 °C
2.1: LDA / tetrahydrofuran; hexane / 0.5 h / -78 °C
2.2: 85 percent / tetrahydrofuran / 1.5 h / -78 - 0 °C
3.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C
3.2: tetrahydrofuran / 1.5 h / -95 - -80 °C
4.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
5.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C
6.1: Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 20 °C
7.1: 380 mg / NaClO2; NaH2PO4 / 2-methyl-propan-2-ol; various solvent(s); H2O / 3 h
View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
→
193146-63-3(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)-5-氧代-十七-12,16-二烯酸
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
5.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
6.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C
7.1: Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 20 °C
8.1: 380 mg / NaClO2; NaH2PO4 / 2-methyl-propan-2-ol; various solvent(s); H2O / 3 h
View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
→
193146-63-3(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)-5-氧代-十七-12,16-二烯酸
反应条件
1.1: TiCl4; iPr2NEt / CH2Cl2 / 1 h / -78 °C
1.2: 85 percent / CH2Cl2 / -78 - 0 °C
2.1: 72 percent / 2,6-lutidine / CH2Cl2 / 3.5 h / 0 °C
3.1: 30 percent / LiOH; H2O2 / tetrahydrofuran; H2O / 84 h / 20 °C
View Scheme
参考文献
Koch, Guido; Loiseleur, Olivier; Fuentes, Daniel; Jantsch, Andrea; Altmann, Karl-Heinz
Organic Letters, 2002 , vol. 4, # 22 p. 3811 - 3814
→
193146-63-3(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)-5-氧代-十七-12,16-二烯酸
反应条件
1: 72 percent / 2,6-lutidine / CH2Cl2 / 3.5 h / 0 °C
2: 30 percent / LiOH; H2O2 / tetrahydrofuran; H2O / 84 h / 20 °C
View Scheme
参考文献
Koch, Guido; Loiseleur, Olivier; Fuentes, Daniel; Jantsch, Andrea; Altmann, Karl-Heinz
Organic Letters, 2002 , vol. 4, # 22 p. 3811 - 3814
→
193146-63-3(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)-5-氧代-十七-12,16-二烯酸
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
7.1: 88 percent / CSA / methanol
8.1: PCC
8.2: 90 percent / NaClO2
View Scheme
参考文献
Taylor, Richard E.; Chen, Yue
Organic Letters, 2001 , vol. 3, # 14 p. 2221 - 2223
→
193146-63-3(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)-5-氧代-十七-12,16-二烯酸
反应条件
1.1: 77 percent / Et3N
2.1: LDA
3.1: 88 percent / CSA / methanol
4.1: PCC
4.2: 90 percent / NaClO2
View Scheme
参考文献
Taylor, Richard E.; Chen, Yue
Organic Letters, 2001 , vol. 3, # 14 p. 2221 - 2223
→
193146-63-3(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)-5-氧代-十七-12,16-二烯酸
反应条件
1.1: 93 percent / NiCl2; CrCl2 / dimethylformamide / 0.67 h / 20 °C
2.1: 87 percent / SOCl2 / diethyl ether; pentane / 6.5 h / -78 - 0 °C
3.1: 88 percent / LiEt3BH / tetrahydrofuran / 2 h / -78 - 20 °C
4.1: 80 percent / PCC
5.1: LDA
6.1: 88 percent / CSA / methanol
7.1: PCC
7.2: 90 percent / NaClO2
View Scheme
参考文献
Taylor, Richard E.; Chen, Yue
Organic Letters, 2001 , vol. 3, # 14 p. 2221 - 2223
→
193146-63-3(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)-5-氧代-十七-12,16-二烯酸
反应条件
1.1: 77 percent / Et3N
2.1: LDA
3.1: 88 percent / CSA / methanol
4.1: PCC
4.2: 90 percent / NaClO2
View Scheme
参考文献
Taylor, Richard E.; Chen, Yue
Organic Letters, 2001 , vol. 3, # 14 p. 2221 - 2223
