(-)-(2Z,5S,6E)-5-{[叔-丁基(二甲基)硅烷基]氧基}-2,6-二甲基-7-(2-甲基-1,3-噻唑-4-基)庚-2,6-二烯-1-醇合成路线 （共 8 条）
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 View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Tetrahedron Letters, 1998 , vol. 39, # 47 p. 8633 - 8636
→
193146-53-1(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-1-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七-12,16-二烯-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 7.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C 8.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Tetrahedron Letters, 1998 , vol. 39, # 47 p. 8633 - 8636
反应条件
1.1: Et3N / CH2Cl2 / 0.17 h / 0 °C 2.1: 84 percent / LiBr / acetone; CH2Cl2 / 1.8 h / 20 °C 3.1: CuI; Et3N / diethyl ether; dimethylformamide / 20 °C 3.2: 60 percent / diethyl ether; dimethylformamide / 18 h / 20 °C 4.1: 68 percent / H2; Pb(OAc)2 / Pd/CaCO3 / hexane / 28 h / 20 °C 5.1: 66 percent / aq. NaOH / propan-2-ol / 16 h / 45 °C 6.1: 89 percent / TBAF / tetrahydrofuran / 16 h / 0 - 25 °C 7.1: 1,3,5-Cl3C6H2COCl; Et3N / tetrahydrofuran / 0.75 h / 0 °C 7.2: 63 percent / DMAP / toluene; tetrahydrofuran / 4.5 h / 75 °C 8.1: 83 percent / TFA / CH2Cl2 / 4.5 h / 0 °C 9.1: 52 percent / KO2CN=NCO2K; AcOH / CH2Cl2 / 25 h / Heating 10.1: 78 percent / dimethyldioxirane / CH2Cl2 / -50 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
反应条件
1.1: Et3N / CH2Cl2 / 0.17 h / 0 °C 2.1: 84 percent / LiBr / acetone; CH2Cl2 / 1.8 h / 20 °C 3.1: CuI; Et3N / diethyl ether; dimethylformamide / 20 °C 3.2: 60 percent / diethyl ether; dimethylformamide / 18 h / 20 °C 4.1: 68 percent / H2; Pb(OAc)2 / Pd/CaCO3 / hexane / 28 h / 20 °C 5.1: 66 percent / aq. NaOH / propan-2-ol / 16 h / 45 °C 6.1: 89 percent / TBAF / tetrahydrofuran / 16 h / 0 - 25 °C 7.1: 1,3,5-Cl3C6H2COCl; Et3N / tetrahydrofuran / 0.75 h / 0 °C 7.2: 63 percent / DMAP / toluene; tetrahydrofuran / 4.5 h / 75 °C 8.1: 83 percent / TFA / CH2Cl2 / 4.5 h / 0 °C 9.1: 52 percent / KO2CN=NCO2K; AcOH / CH2Cl2 / 25 h / Heating View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
→
193146-51-9(3S,6R,7S,8S,12Z,15S,16E)-1,3,7,15-四-{[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)十七-12,16-二烯-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
7.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Tetrahedron Letters, 1998 , vol. 39, # 47 p. 8633 - 8636
→
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: 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
7.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
8.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C
9.1: Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 20 °C
10.1: 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
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
1.1: 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
Tetrahedron Letters, 1998 , vol. 39, # 47 p. 8633 - 8636
反应条件
Multi-step reaction with 3 steps 1.1: oxalyl chloride; DMSO; DIPEA / CH2Cl2 / -78 - 20 °C2.1: KHMDS; 18-crown-6 / tetrahydrofuran / 0.25 h2.2: 5.45 g / tetrahydrofuran / 0.5 h / -78 °C3.1: 98 percent / DIBALH / tetrahydrofuran; heptane / 2.5 h / 0 °C
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
