(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）
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反应条件
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: 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
8.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
9.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C
10.1: Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 20 °C
11.1: 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
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反应条件
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: 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
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
→
反应条件
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: 97 percent / benzene / 8 h / Heating
2.1: 10.95 g / LiHMDS / tetrahydrofuran / 0.67 h / 55 °C
3.1: oxalyl chloride; DMSO; DIPEA / CH2Cl2 / -78 - 20 °C
4.1: KHMDS; 18-crown-6 / tetrahydrofuran / 0.25 h
4.2: 5.45 g / tetrahydrofuran / 0.5 h / -78 °C
5.1: 98 percent / DIBALH / tetrahydrofuran; heptane / 2.5 h / 0 °C
6.1: Ph3P; imidazole; I2 / acetonitrile; diethyl ether / 1 h / 20 °C
7.1: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C
7.2: 93 percent / tetrahydrofuran / 1 h / -78 °C
8.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C
9.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C
10.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C
11.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C
11.2: tetrahydrofuran / 1.5 h / -95 - -80 °C
12.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
13.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C
14.1: Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 20 °C
15.1: 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
→
反应条件
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: 99 percent / imidazole / dimethylformamide / 3 h / 0 - 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
→
反应条件
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: 99 percent / Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 0 °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
→
反应条件
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: 88 percent / TBAF / tetrahydrofuran / 10 h / 20 °C
2.1: 99 percent / imidazole / dimethylformamide / 3 h / 0 - 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
8.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
9.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C
10.1: Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 20 °C
11.1: 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
→
反应条件
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: N-Tos-D-valine, BH3*THF / CH2Cl2 / 4 h / -78 °C
2: 99 percent / 2,6-lutidine / CH2Cl2 / 2 h / 0 °C
3: 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
4: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C
5: Dess-Martin periodinane / CH2Cl2 / 2 h / 0 °C
6: NaClO2, Na2HPO4, 2,3-dimethylbut-2-ene / 2-methyl-propan-2-ol; H2O / 0.67 h
View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
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反应条件
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: n-butyllithium; diisopropylamine / tetrahydrofuran / 1.75 h / -78 - 40 °C
1.2: 0.08 h / -78 °C
2.1: formic acid / diethyl ether / 10 h / 5 - 20 °C
3.1: [bis(acetoxy)iodo]benzene; water / tetrahydrofuran / 0.67 h / 20 °C
4.1: 2,6-dimethylpyridine / dichloromethane / 4 h / 0 - 5 °C
4.2: 3 h / 5 °C
View Scheme
参考文献
Hurski; Kulinkovich
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反应条件
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: pyridinium p-toluenesulfonate; dimethyl sulfoxide / 4 h / 65 °C
2.1: oxalyl dichloride; dimethyl sulfoxide / dichloromethane / -78 °C
2.2: -78 - 0 °C
3.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 1.75 h / -78 - 40 °C
3.2: 0.08 h / -78 °C
4.1: formic acid / diethyl ether / 10 h / 5 - 20 °C
5.1: [bis(acetoxy)iodo]benzene; water / tetrahydrofuran / 0.67 h / 20 °C
6.1: 2,6-dimethylpyridine / dichloromethane / 4 h / 0 - 5 °C
6.2: 3 h / 5 °C
View Scheme
参考文献
Hurski; Kulinkovich
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反应条件
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: formic acid / diethyl ether / 10 h / 5 - 20 °C
2.1: [bis(acetoxy)iodo]benzene; water / tetrahydrofuran / 0.67 h / 20 °C
3.1: 2,6-dimethylpyridine / dichloromethane / 4 h / 0 - 5 °C
3.2: 3 h / 5 °C
View Scheme
参考文献
Hurski; Kulinkovich
