(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
1.1: 87 percent / SOCl2 / diethyl ether; pentane / 6.5 h / -78 - 0 °C
2.1: 88 percent / LiEt3BH / tetrahydrofuran / 2 h / -78 - 20 °C
3.1: 80 percent / PCC
4.1: LDA
5.1: 88 percent / CSA / methanol
6.1: PCC
6.2: 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: 88 percent / LiEt3BH / tetrahydrofuran / 2 h / -78 - 20 °C
2.1: 80 percent / PCC
3.1: LDA
4.1: 88 percent / CSA / methanol
5.1: PCC
5.2: 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: 4.96 g / tetrahydrofuran; diethyl ether / 1.5 h / -78 °C
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
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: oxalyl chloride; DMSO; DIPEA / CH2Cl2 / -78 - 20 °C
2.1: KHMDS; 18-crown-6 / tetrahydrofuran / 0.25 h
2.2: 5.45 g / tetrahydrofuran / 0.5 h / -78 °C
3.1: 98 percent / DIBALH / tetrahydrofuran; heptane / 2.5 h / 0 °C
4.1: Ph3P; imidazole; I2 / acetonitrile; diethyl ether / 1 h / 20 °C
5.1: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C
5.2: 93 percent / tetrahydrofuran / 1 h / -78 °C
6.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C
7.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C
8.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C
9.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C
9.2: tetrahydrofuran / 1.5 h / -95 - -80 °C
10.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
11.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C
12.1: Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 20 °C
13.1: 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: 10.95 g / LiHMDS / tetrahydrofuran / 0.67 h / 55 °C
2.1: oxalyl chloride; DMSO; DIPEA / CH2Cl2 / -78 - 20 °C
3.1: KHMDS; 18-crown-6 / tetrahydrofuran / 0.25 h
3.2: 5.45 g / tetrahydrofuran / 0.5 h / -78 °C
4.1: 98 percent / DIBALH / tetrahydrofuran; heptane / 2.5 h / 0 °C
5.1: Ph3P; imidazole; I2 / acetonitrile; diethyl ether / 1 h / 20 °C
6.1: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C
6.2: 93 percent / tetrahydrofuran / 1 h / -78 °C
7.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C
8.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C
9.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C
10.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C
10.2: tetrahydrofuran / 1.5 h / -95 - -80 °C
11.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
12.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C
13.1: Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 20 °C
14.1: 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: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C
2.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °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: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C
1.2: 93 percent / tetrahydrofuran / 1 h / -78 °C
2.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C
3.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C
4.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C
5.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C
5.2: tetrahydrofuran / 1.5 h / -95 - -80 °C
6.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
7.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C
8.1: Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 20 °C
9.1: 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: LDA / tetrahydrofuran; hexane / 0.5 h / -78 °C
1.2: 85 percent / tetrahydrofuran / 1.5 h / -78 - 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
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: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C
1.2: 93 percent / tetrahydrofuran / 1 h / -78 °C
2.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C
3.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C
4.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C
5.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C
5.2: tetrahydrofuran / 1.5 h / -95 - -80 °C
6.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C
7.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C
8.1: Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 20 °C
9.1: 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: 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
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
