(-)-(3S,4E)-3-{[叔-丁基(二甲基)硅烷基]氧基}-4-甲基-5-(2-甲基-1,3-噻唑-4-基)戊-4-烯-1-醇 合成路线 （共 12 条）
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 View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
→
反应条件
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: 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 View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
反应条件
1.1: Dess-Martin periodinane / CH2Cl2 / 0.25 h / 20 °C 2.1: tetrahydrofuran / 0.33 h / -78 - 20 °C 3.1: aqueous HF / acetonitrile / 16 h 4.1: 95 percent / DMAP; Et3N / CH2Cl2 / 2 h / 0 °C 5.1: 9-BBN / tetrahydrofuran / 4 h / 20 °C 5.2: 60 percent / Cs2CO3; AsPh3 / PdCl2(dppf) / H2O; tetrahydrofuran / 1.5 h 6.1: 93 percent / HF*pyridine / tetrahydrofuran / 36 h / 20 °C 7.1: 92 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C 8.1: 87 percent / TiCl4 / CH2Cl2 / 0.25 h / -78 °C 9.1: 89 percent / tetrabutylammonium fluoride / tetrahydrofuran / 0.17 h / 0 °C 10.1: 91 percent / imidazole / dimethylformamide / 36 h / 20 °C 11.1: 95 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 20 °C 12.1: 62 percent / 2 N NaOH / H2O / 1.5 h / Heating 13.1: Et3N; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 0.08 h / 0 °C 13.2: 73 percent / DMAP / toluene; tetrahydrofuran / 0.5 h / 20 °C 14.1: 82 percent / 2,3-dichloro-5,6-dicyano-1,4-benzoquinone / CH2Cl2; H2O / 2.5 h 15.1: 90 percent / trifluoroacetic acid / CH2Cl2 / 2.5 h / 20 °C 16.1: 30 percent aq. H2O2; KHCO3 / methanol; acetonitrile / 24 h / 20 °C View Scheme
参考文献
Schinzer, Dieter; Limberg, Anja; Bauer, Armin; Boehm, Oliver M.; Cordes, Martin
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 14.1: 55 percent / TBAF / tetrahydrofuran / 10 h / 20 °C 15.1: 69 percent / N-ethyl-N'-(3-(dimethylamino)propyl)carbodiimide *HCl; DMAP; DMAP*HCl / CHCl3 / 17 h / Heating 16.1: 96 percent / HF*Py; Py / tetrahydrofuran / 36 h / 0 - 20 °C 17.1: m-CPBA / CHCl3 / 5 h / -18 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
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 14.1: 55 percent / TBAF / tetrahydrofuran / 10 h / 20 °C 15.1: 69 percent / N-ethyl-N'-(3-(dimethylamino)propyl)carbodiimide *HCl; DMAP; DMAP*HCl / CHCl3 / 17 h / Heating 16.1: 96 percent / HF*Py; Py / tetrahydrofuran / 36 h / 0 - 20 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
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反应条件
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: 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
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: 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
→
反应条件
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: 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
View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
反应条件
1.1: Dess-Martin periodinane / CH2Cl2 / 0.25 h / 20 °C
2.1: tetrahydrofuran / 0.33 h / -78 - 20 °C
3.1: aqueous HF / acetonitrile / 16 h
4.1: 95 percent / DMAP; Et3N / CH2Cl2 / 2 h / 0 °C
5.1: 9-BBN / tetrahydrofuran / 4 h / 20 °C
5.2: 60 percent / Cs2CO3; AsPh3 / PdCl2(dppf) / H2O; tetrahydrofuran / 1.5 h
6.1: 93 percent / HF*pyridine / tetrahydrofuran / 36 h / 20 °C
7.1: 92 percent / Dess-Martin periodinane / CH2Cl2 / 1 h / 20 °C
8.1: 87 percent / TiCl4 / CH2Cl2 / 0.25 h / -78 °C
9.1: 89 percent / tetrabutylammonium fluoride / tetrahydrofuran / 0.17 h / 0 °C
10.1: 91 percent / imidazole / dimethylformamide / 36 h / 20 °C
11.1: 95 percent / Dess-Martin periodinane / CH2Cl2 / 2 h / 20 °C
12.1: 62 percent / 2 N NaOH / H2O / 1.5 h / Heating
13.1: Et3N; 2,4,6-trichlorobenzoyl chloride / tetrahydrofuran / 0.08 h / 0 °C
13.2: 73 percent / DMAP / toluene; tetrahydrofuran / 0.5 h / 20 °C
14.1: 82 percent / 2,3-dichloro-5,6-dicyano-1,4-benzoquinone / CH2Cl2; H2O / 2.5 h
15.1: 90 percent / trifluoroacetic acid / CH2Cl2 / 2.5 h / 20 °C
View Scheme
参考文献
Zhu, Bin; Panek, James S.
反应条件
1.1: 84 percent / Dess-Martin periodinane / CH2Cl2 / 0.5 h / 20 °C
2.1: NaNH2 / tetrahydrofuran / 0.5 h / 20 °C
2.2: 85 percent / tetrahydrofuran / 0.25 h / 20 °C
3.1: 99 percent / TBAF; 4 Angstroem molecular sieves / tetrahydrofuran / 1.33 h / 0 °C
View Scheme
参考文献
Schinzer, Dieter; Limberg, Anja; Bauer, Armin; Boehm, Oliver M.; Cordes, Martin
