(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: lithium tri-tert-butoxyaluminohydride / tetrahydrofuran / 1) -78 deg C, 5 min, 2) 0 deg C, 15 min
2: 1.26 g / Et3N, 4-DMAP / CH2Cl2 / 1) 0 deg C, 2 h, 2) 25 deg C, 10 h
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: 98 percent / Pb(OAc)4 / ethyl acetate / 0.25 h / 0 °C
2: 95 percent / benzene / 3 h / Heating
3: 98 percent / DIBAL / tetrahydrofuran; CH2Cl2 / 3 h / -78 °C
4: 83 percent / Ph3P, CCl4 / 24 h / 100 °C
5: 99 percent / LiEt3BH / tetrahydrofuran / 1 h / 0 °C
6: 91 percent / 9-BBN / tetrahydrofuran / 2 h / 0 °C
7: 92 percent / I2, imidazole, Ph3P / diethyl ether; acetonitrile / 0.5 h / 0 °C
8: 1) LDA / 1) THF, 0 deg C, 8 h, 2) THF, -100 deg C -> -20 deg C, 10 h
9: 80 percent / monoperoxyphthalic acid magnesium salt / methanol / 1 h / 0 °C
10: 82 percent / DIBAL / toluene / 1 h / -78 °C
11: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
12: 96 percent / 2,6-lutidine / CH2Cl2 / 2 h / 0 °C
13: 85 percent / camphorsulfonic acid / CH2Cl2; methanol / 0.5 h / 0 - 25 °C
14: 1) (COCl)2, DMSO, 2) Et3N / 1) CH2Cl2, -78 deg C, 30 min, 2) CH2Cl2, -78 deg C -> 0 deg C, 30 min
15: 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: 1.26 g / Et3N, 4-DMAP / CH2Cl2 / 1) 0 deg C, 2 h, 2) 25 deg C, 10 h
2: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
3: 96 percent / 2,6-lutidine / CH2Cl2 / 2 h / 0 °C
4: 85 percent / camphorsulfonic acid / CH2Cl2; methanol / 0.5 h / 0 - 25 °C
5: 1) (COCl)2, DMSO, 2) Et3N / 1) CH2Cl2, -78 deg C, 30 min, 2) CH2Cl2, -78 deg C -> 0 deg C, 30 min
6: 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: 91 percent / 9-BBN / tetrahydrofuran / 2 h / 0 °C
2: 92 percent / I2, imidazole, Ph3P / diethyl ether; acetonitrile / 0.5 h / 0 °C
3: 1) LDA / 1) THF, 0 deg C, 8 h, 2) THF, -100 deg C -> -20 deg C, 10 h
4: 80 percent / monoperoxyphthalic acid magnesium salt / methanol / 1 h / 0 °C
5: 82 percent / DIBAL / toluene / 1 h / -78 °C
6: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
7: 96 percent / 2,6-lutidine / CH2Cl2 / 2 h / 0 °C
8: 85 percent / camphorsulfonic acid / CH2Cl2; methanol / 0.5 h / 0 - 25 °C
9: 1) (COCl)2, DMSO, 2) Et3N / 1) CH2Cl2, -78 deg C, 30 min, 2) CH2Cl2, -78 deg C -> 0 deg C, 30 min
10: 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: 92 percent / I2, imidazole, Ph3P / diethyl ether; acetonitrile / 0.5 h / 0 °C
2: 1) LDA / 1) THF, 0 deg C, 8 h, 2) THF, -100 deg C -> -20 deg C, 10 h
3: 80 percent / monoperoxyphthalic acid magnesium salt / methanol / 1 h / 0 °C
4: 82 percent / DIBAL / toluene / 1 h / -78 °C
5: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
6: 96 percent / 2,6-lutidine / CH2Cl2 / 2 h / 0 °C
7: 85 percent / camphorsulfonic acid / CH2Cl2; methanol / 0.5 h / 0 - 25 °C
8: 1) (COCl)2, DMSO, 2) Et3N / 1) CH2Cl2, -78 deg C, 30 min, 2) CH2Cl2, -78 deg C -> 0 deg C, 30 min
9: 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) LDA / 1) THF, 0 deg C, 8 h, 2) THF, -100 deg C -> -20 deg C, 10 h
2: 80 percent / monoperoxyphthalic acid magnesium salt / methanol / 1 h / 0 °C
3: 82 percent / DIBAL / toluene / 1 h / -78 °C
4: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
5: 96 percent / 2,6-lutidine / CH2Cl2 / 2 h / 0 °C
6: 85 percent / camphorsulfonic acid / CH2Cl2; methanol / 0.5 h / 0 - 25 °C
7: 1) (COCl)2, DMSO, 2) Et3N / 1) CH2Cl2, -78 deg C, 30 min, 2) CH2Cl2, -78 deg C -> 0 deg C, 30 min
8: 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: 83 percent / Ph3P, CCl4 / 24 h / 100 °C
2: 99 percent / LiEt3BH / tetrahydrofuran / 1 h / 0 °C
3: 91 percent / 9-BBN / tetrahydrofuran / 2 h / 0 °C
4: 92 percent / I2, imidazole, Ph3P / diethyl ether; acetonitrile / 0.5 h / 0 °C
5: 1) LDA / 1) THF, 0 deg C, 8 h, 2) THF, -100 deg C -> -20 deg C, 10 h
6: 80 percent / monoperoxyphthalic acid magnesium salt / methanol / 1 h / 0 °C
7: 82 percent / DIBAL / toluene / 1 h / -78 °C
8: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
9: 96 percent / 2,6-lutidine / CH2Cl2 / 2 h / 0 °C
10: 85 percent / camphorsulfonic acid / CH2Cl2; methanol / 0.5 h / 0 - 25 °C
11: 1) (COCl)2, DMSO, 2) Et3N / 1) CH2Cl2, -78 deg C, 30 min, 2) CH2Cl2, -78 deg C -> 0 deg C, 30 min
12: 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: 99 percent / LiEt3BH / tetrahydrofuran / 1 h / 0 °C
2: 91 percent / 9-BBN / tetrahydrofuran / 2 h / 0 °C
3: 92 percent / I2, imidazole, Ph3P / diethyl ether; acetonitrile / 0.5 h / 0 °C
4: 1) LDA / 1) THF, 0 deg C, 8 h, 2) THF, -100 deg C -> -20 deg C, 10 h
5: 80 percent / monoperoxyphthalic acid magnesium salt / methanol / 1 h / 0 °C
6: 82 percent / DIBAL / toluene / 1 h / -78 °C
7: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
8: 96 percent / 2,6-lutidine / CH2Cl2 / 2 h / 0 °C
9: 85 percent / camphorsulfonic acid / CH2Cl2; methanol / 0.5 h / 0 - 25 °C
10: 1) (COCl)2, DMSO, 2) Et3N / 1) CH2Cl2, -78 deg C, 30 min, 2) CH2Cl2, -78 deg C -> 0 deg C, 30 min
11: 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: 98 percent / DIBAL / tetrahydrofuran; CH2Cl2 / 3 h / -78 °C
2: 83 percent / Ph3P, CCl4 / 24 h / 100 °C
3: 99 percent / LiEt3BH / tetrahydrofuran / 1 h / 0 °C
4: 91 percent / 9-BBN / tetrahydrofuran / 2 h / 0 °C
5: 92 percent / I2, imidazole, Ph3P / diethyl ether; acetonitrile / 0.5 h / 0 °C
6: 1) LDA / 1) THF, 0 deg C, 8 h, 2) THF, -100 deg C -> -20 deg C, 10 h
7: 80 percent / monoperoxyphthalic acid magnesium salt / methanol / 1 h / 0 °C
8: 82 percent / DIBAL / toluene / 1 h / -78 °C
9: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
10: 96 percent / 2,6-lutidine / CH2Cl2 / 2 h / 0 °C
11: 85 percent / camphorsulfonic acid / CH2Cl2; methanol / 0.5 h / 0 - 25 °C
12: 1) (COCl)2, DMSO, 2) Et3N / 1) CH2Cl2, -78 deg C, 30 min, 2) CH2Cl2, -78 deg C -> 0 deg C, 30 min
13: 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: 82 percent / DIBAL / toluene / 1 h / -78 °C
2: 1) LDA / 1) THF, -78 deg C, 15 min; -78 deg C -> -40 deg C, 1 h, 2) THF, -78 deg C, 15 min
3: 96 percent / 2,6-lutidine / CH2Cl2 / 2 h / 0 °C
4: 85 percent / camphorsulfonic acid / CH2Cl2; methanol / 0.5 h / 0 - 25 °C
5: 1) (COCl)2, DMSO, 2) Et3N / 1) CH2Cl2, -78 deg C, 30 min, 2) CH2Cl2, -78 deg C -> 0 deg C, 30 min
6: 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
