[(1S,3S,4aR,7S,8S,8aR)-8-[2-[(2R,4R)-4-羟基-6-氧代四氢吡喃-2-基]乙基]-3,7-二甲基-1,2,3,4,4a,7,8,8a-八氢萘-1-基] (2S)-2-甲基丁酸酯合成路线 （共 63 条）
→
77517-29-4[(1S,3S,4aR,7S,8S,8aR)-8-[2-[(2R,4R)-4-羟基-6-氧代四氢吡喃-2-基]乙基]-3,7-二甲基-1,2,3,4,4a,7,8,8a-八氢萘-1-基] (2S)-2-甲基丁酸酯
反应条件
1: 570 mg / H2 / platinum oxide / ethyl acetate / 1 h / 760 Torr / Ambient temperature
2: 75.4 percent / toluene / 0.5 h / Heating
3: 63 percent / triethyl phosphite / 140 h / Heating
4: 4.0 mg / 2.5 N aqueous HCl / acetic acid; H2O; tetrahydrofuran / 9 h / Ambient temperature
View Scheme
参考文献
Kuo, C. H.; Patchett, A. A.; Wendler, N. L.
Journal of Organic Chemistry, 1983 , vol. 48, # 12 p. 1991 - 1998
→
77517-29-4[(1S,3S,4aR,7S,8S,8aR)-8-[2-[(2R,4R)-4-羟基-6-氧代四氢吡喃-2-基]乙基]-3,7-二甲基-1,2,3,4,4a,7,8,8a-八氢萘-1-基] (2S)-2-甲基丁酸酯
反应条件
1: 2.) NaOMe / 1.) diethylether, 0 deg C, 30 min. 2.) MeOH, 40 deg C, 24 h
2: TsOH / benzene / 72 h / 80 °C
3: LiAlH4 / tetrahydrofuran / 2 h
4: Me3SiCl, NaI / acetonitrile / 0.5 h
5: benzene / 5 h / 80 °C
6: BF3*Et2O / CH2Cl2 / 15 h
8: DCC, DMAP / CH2Cl2 / 72 h
9: 10percent HCl / tetrahydrofuran / 4 h / 50 °C
10: PCC-Al2O3 / CH2Cl2 / 8 h
11: 48percent HF / acetonitrile / 6 h / 50 °C
View Scheme
参考文献
Falck; Yang
Tetrahedron Letters, 1984 , vol. 25, # 33 p. 3563 - 3566
→
77517-29-4[(1S,3S,4aR,7S,8S,8aR)-8-[2-[(2R,4R)-4-羟基-6-氧代四氢吡喃-2-基]乙基]-3,7-二甲基-1,2,3,4,4a,7,8,8a-八氢萘-1-基] (2S)-2-甲基丁酸酯
反应条件
1: TsOH / benzene / 72 h / 80 °C
2: LiAlH4 / tetrahydrofuran / 2 h
3: Me3SiCl, NaI / acetonitrile / 0.5 h
4: benzene / 5 h / 80 °C
5: BF3*Et2O / CH2Cl2 / 15 h
7: DCC, DMAP / CH2Cl2 / 72 h
8: 10percent HCl / tetrahydrofuran / 4 h / 50 °C
9: PCC-Al2O3 / CH2Cl2 / 8 h
10: 48percent HF / acetonitrile / 6 h / 50 °C
View Scheme
参考文献
Falck; Yang
Tetrahedron Letters, 1984 , vol. 25, # 33 p. 3563 - 3566
→
77517-29-4[(1S,3S,4aR,7S,8S,8aR)-8-[2-[(2R,4R)-4-羟基-6-氧代四氢吡喃-2-基]乙基]-3,7-二甲基-1,2,3,4,4a,7,8,8a-八氢萘-1-基] (2S)-2-甲基丁酸酯
反应条件
1: LiN(SiMe3)2 / tetrahydrofuran / 1.) -78 deg C, 5 d 2.) -40 deg C, 8 h
3: P(OMe)3 / CCl4 / 5 h / 55 °C
4: 2.) NaOMe / 1.) diethylether, 0 deg C, 30 min. 2.) MeOH, 40 deg C, 24 h
5: TsOH / benzene / 72 h / 80 °C
6: LiAlH4 / tetrahydrofuran / 2 h
7: Me3SiCl, NaI / acetonitrile / 0.5 h
8: benzene / 5 h / 80 °C
9: BF3*Et2O / CH2Cl2 / 15 h
11: DCC, DMAP / CH2Cl2 / 72 h
12: 10percent HCl / tetrahydrofuran / 4 h / 50 °C
13: PCC-Al2O3 / CH2Cl2 / 8 h
14: 48percent HF / acetonitrile / 6 h / 50 °C
View Scheme
参考文献
Falck; Yang
Tetrahedron Letters, 1984 , vol. 25, # 33 p. 3563 - 3566
→
77517-29-4[(1S,3S,4aR,7S,8S,8aR)-8-[2-[(2R,4R)-4-羟基-6-氧代四氢吡喃-2-基]乙基]-3,7-二甲基-1,2,3,4,4a,7,8,8a-八氢萘-1-基] (2S)-2-甲基丁酸酯
反应条件
1: 94 percent / LAH / tetrahydrofuran / 0.5 h / 0 °C
2: 91 percent / pyridine / Ambient temperature
3: 85 percent / triethylamine / CH2Cl2 / 0.5 h / Ambient temperature
4: 90 percent / LAH / tetrahydrofuran / 0.67 h / 0 °C
5: 1.) oxalyl chloride, dimethylsulfoxide 2.) triethylamine / 1.) CH2Cl2, -10 deg C, 20 min 2.) -10 deg C, 5 min
6: 53 percent / K2CO3 / methanol / 19 h / 100 °C
7: 73 percent / sodium methoxide / methanol / 2 h / Ambient temperature
8: 85 percent / methanesulfonyl chloride, triethylamine / CH2Cl2 / 1 h / 0 °C
9: 90 percent / NaBH4 / propan-2-ol; CHCl3 / 0.67 h / Ambient temperature
10: 93 percent / aq.HF / acetonitrile / 24 h / Ambient temperature
11: 70 percent / DMAP / 0.33 h / 40 °C
12: 70 percent / Amberlyst A-21 / diethyl ether / 2 h / Ambient temperature
13: 55 percent / n-Bu3SnH, AIBN / toluene / 0.5 h / Heating
14: 0.034 g / sodium borohydride / propan-2-ol; tetrahydrofuran / -78 deg C to rt, overnight
15: 80 percent / n-tetrabutylammonium iodide, NaH / tetrahydrofuran / 18 h / Ambient temperature
16: 85 percent / 48percent aq. HF / acetonitrile / 1.5 h / Ambient temperature
17: 1.) oxalyl chloride, DMSO 2.) triethylamine / 1.) CH2Cl2, -60 deg C, 15 min 2.) -60 deg C, 15 min
18: 78 percent / BF3.Et2O, bis(trimethylsilyl)peroxide / CH2Cl2 / 1.5 h / Ambient temperature; 2
19: 42 percent / boron trichloride / CH2Cl2; hexane / 4 h / -78 °C
View Scheme
参考文献
Hanessian; Roy; Petrini; Hodges; Di Fabio; Carganico
Journal of Organic Chemistry, 1990 , vol. 55, # 22 p. 5766 - 5777
→
77517-29-4[(1S,3S,4aR,7S,8S,8aR)-8-[2-[(2R,4R)-4-羟基-6-氧代四氢吡喃-2-基]乙基]-3,7-二甲基-1,2,3,4,4a,7,8,8a-八氢萘-1-基] (2S)-2-甲基丁酸酯
反应条件
1: 75 percent / pyridine / CH2Cl2 / -5 °C
2: 87 percent / sodium methoxide / CH2Cl2; methanol / 0.67 h / 0 °C
4: 65 percent / 2,6-di-tert-butyl-4-methylphenol / o-xylene / 144 h / Heating
5: 95 percent / 6 M HCl / tetrahydrofuran / 19 h / 40 °C
7: 68 percent / n-Bu3SnH, AIBN / toluene / 0.58 h / Heating
8: 94 percent / LAH / tetrahydrofuran / 0.5 h / 0 °C
9: 91 percent / pyridine / Ambient temperature
10: 85 percent / triethylamine / CH2Cl2 / 0.5 h / Ambient temperature
11: 90 percent / LAH / tetrahydrofuran / 0.67 h / 0 °C
12: 1.) oxalyl chloride, dimethylsulfoxide 2.) triethylamine / 1.) CH2Cl2, -10 deg C, 20 min 2.) -10 deg C, 5 min
13: 53 percent / K2CO3 / methanol / 19 h / 100 °C
14: 73 percent / sodium methoxide / methanol / 2 h / Ambient temperature
15: 85 percent / methanesulfonyl chloride, triethylamine / CH2Cl2 / 1 h / 0 °C
16: 90 percent / NaBH4 / propan-2-ol; CHCl3 / 0.67 h / Ambient temperature
17: 93 percent / aq.HF / acetonitrile / 24 h / Ambient temperature
18: 70 percent / DMAP / 0.33 h / 40 °C
19: 70 percent / Amberlyst A-21 / diethyl ether / 2 h / Ambient temperature
20: 55 percent / n-Bu3SnH, AIBN / toluene / 0.5 h / Heating
21: 0.034 g / sodium borohydride / propan-2-ol; tetrahydrofuran / -78 deg C to rt, overnight
22: 80 percent / n-tetrabutylammonium iodide, NaH / tetrahydrofuran / 18 h / Ambient temperature
23: 85 percent / 48percent aq. HF / acetonitrile / 1.5 h / Ambient temperature
24: 1.) oxalyl chloride, DMSO 2.) triethylamine / 1.) CH2Cl2, -60 deg C, 15 min 2.) -60 deg C, 15 min
25: 78 percent / BF3.Et2O, bis(trimethylsilyl)peroxide / CH2Cl2 / 1.5 h / Ambient temperature; 2
26: 42 percent / boron trichloride / CH2Cl2; hexane / 4 h / -78 °C
View Scheme
参考文献
Hanessian; Roy; Petrini; Hodges; Di Fabio; Carganico
Journal of Organic Chemistry, 1990 , vol. 55, # 22 p. 5766 - 5777
→
77517-29-4[(1S,3S,4aR,7S,8S,8aR)-8-[2-[(2R,4R)-4-羟基-6-氧代四氢吡喃-2-基]乙基]-3,7-二甲基-1,2,3,4,4a,7,8,8a-八氢萘-1-基] (2S)-2-甲基丁酸酯
反应条件
2: 65 percent / 2,6-di-tert-butyl-4-methylphenol / o-xylene / 144 h / Heating
3: 95 percent / 6 M HCl / tetrahydrofuran / 19 h / 40 °C
5: 68 percent / n-Bu3SnH, AIBN / toluene / 0.58 h / Heating
6: 94 percent / LAH / tetrahydrofuran / 0.5 h / 0 °C
7: 91 percent / pyridine / Ambient temperature
8: 85 percent / triethylamine / CH2Cl2 / 0.5 h / Ambient temperature
9: 90 percent / LAH / tetrahydrofuran / 0.67 h / 0 °C
10: 1.) oxalyl chloride, dimethylsulfoxide 2.) triethylamine / 1.) CH2Cl2, -10 deg C, 20 min 2.) -10 deg C, 5 min
11: 53 percent / K2CO3 / methanol / 19 h / 100 °C
12: 73 percent / sodium methoxide / methanol / 2 h / Ambient temperature
13: 85 percent / methanesulfonyl chloride, triethylamine / CH2Cl2 / 1 h / 0 °C
14: 90 percent / NaBH4 / propan-2-ol; CHCl3 / 0.67 h / Ambient temperature
15: 93 percent / aq.HF / acetonitrile / 24 h / Ambient temperature
16: 70 percent / DMAP / 0.33 h / 40 °C
17: 70 percent / Amberlyst A-21 / diethyl ether / 2 h / Ambient temperature
18: 55 percent / n-Bu3SnH, AIBN / toluene / 0.5 h / Heating
19: 0.034 g / sodium borohydride / propan-2-ol; tetrahydrofuran / -78 deg C to rt, overnight
20: 80 percent / n-tetrabutylammonium iodide, NaH / tetrahydrofuran / 18 h / Ambient temperature
21: 85 percent / 48percent aq. HF / acetonitrile / 1.5 h / Ambient temperature
22: 1.) oxalyl chloride, DMSO 2.) triethylamine / 1.) CH2Cl2, -60 deg C, 15 min 2.) -60 deg C, 15 min
23: 78 percent / BF3.Et2O, bis(trimethylsilyl)peroxide / CH2Cl2 / 1.5 h / Ambient temperature; 2
24: 42 percent / boron trichloride / CH2Cl2; hexane / 4 h / -78 °C
View Scheme
参考文献
Hanessian; Roy; Petrini; Hodges; Di Fabio; Carganico
Journal of Organic Chemistry, 1990 , vol. 55, # 22 p. 5766 - 5777
→
77517-29-4[(1S,3S,4aR,7S,8S,8aR)-8-[2-[(2R,4R)-4-羟基-6-氧代四氢吡喃-2-基]乙基]-3,7-二甲基-1,2,3,4,4a,7,8,8a-八氢萘-1-基] (2S)-2-甲基丁酸酯
反应条件
2: 68 percent / n-Bu3SnH, AIBN / toluene / 0.58 h / Heating
3: 94 percent / LAH / tetrahydrofuran / 0.5 h / 0 °C
4: 91 percent / pyridine / Ambient temperature
5: 85 percent / triethylamine / CH2Cl2 / 0.5 h / Ambient temperature
6: 90 percent / LAH / tetrahydrofuran / 0.67 h / 0 °C
7: 1.) oxalyl chloride, dimethylsulfoxide 2.) triethylamine / 1.) CH2Cl2, -10 deg C, 20 min 2.) -10 deg C, 5 min
8: 53 percent / K2CO3 / methanol / 19 h / 100 °C
9: 73 percent / sodium methoxide / methanol / 2 h / Ambient temperature
10: 85 percent / methanesulfonyl chloride, triethylamine / CH2Cl2 / 1 h / 0 °C
11: 90 percent / NaBH4 / propan-2-ol; CHCl3 / 0.67 h / Ambient temperature
12: 93 percent / aq.HF / acetonitrile / 24 h / Ambient temperature
13: 70 percent / DMAP / 0.33 h / 40 °C
14: 70 percent / Amberlyst A-21 / diethyl ether / 2 h / Ambient temperature
15: 55 percent / n-Bu3SnH, AIBN / toluene / 0.5 h / Heating
16: 0.034 g / sodium borohydride / propan-2-ol; tetrahydrofuran / -78 deg C to rt, overnight
17: 80 percent / n-tetrabutylammonium iodide, NaH / tetrahydrofuran / 18 h / Ambient temperature
18: 85 percent / 48percent aq. HF / acetonitrile / 1.5 h / Ambient temperature
19: 1.) oxalyl chloride, DMSO 2.) triethylamine / 1.) CH2Cl2, -60 deg C, 15 min 2.) -60 deg C, 15 min
20: 78 percent / BF3.Et2O, bis(trimethylsilyl)peroxide / CH2Cl2 / 1.5 h / Ambient temperature; 2
21: 42 percent / boron trichloride / CH2Cl2; hexane / 4 h / -78 °C
View Scheme
参考文献
Hanessian; Roy; Petrini; Hodges; Di Fabio; Carganico
Journal of Organic Chemistry, 1990 , vol. 55, # 22 p. 5766 - 5777
→
77517-29-4[(1S,3S,4aR,7S,8S,8aR)-8-[2-[(2R,4R)-4-羟基-6-氧代四氢吡喃-2-基]乙基]-3,7-二甲基-1,2,3,4,4a,7,8,8a-八氢萘-1-基] (2S)-2-甲基丁酸酯
反应条件
1: 85 percent / triethylamine / CH2Cl2 / 0.5 h / Ambient temperature
2: 90 percent / LAH / tetrahydrofuran / 0.67 h / 0 °C
3: 1.) oxalyl chloride, dimethylsulfoxide 2.) triethylamine / 1.) CH2Cl2, -10 deg C, 20 min 2.) -10 deg C, 5 min
4: 53 percent / K2CO3 / methanol / 19 h / 100 °C
5: 73 percent / sodium methoxide / methanol / 2 h / Ambient temperature
6: 85 percent / methanesulfonyl chloride, triethylamine / CH2Cl2 / 1 h / 0 °C
7: 90 percent / NaBH4 / propan-2-ol; CHCl3 / 0.67 h / Ambient temperature
8: 93 percent / aq.HF / acetonitrile / 24 h / Ambient temperature
9: 70 percent / DMAP / 0.33 h / 40 °C
10: 70 percent / Amberlyst A-21 / diethyl ether / 2 h / Ambient temperature
11: 55 percent / n-Bu3SnH, AIBN / toluene / 0.5 h / Heating
12: 0.034 g / sodium borohydride / propan-2-ol; tetrahydrofuran / -78 deg C to rt, overnight
13: 80 percent / n-tetrabutylammonium iodide, NaH / tetrahydrofuran / 18 h / Ambient temperature
14: 85 percent / 48percent aq. HF / acetonitrile / 1.5 h / Ambient temperature
15: 1.) oxalyl chloride, DMSO 2.) triethylamine / 1.) CH2Cl2, -60 deg C, 15 min 2.) -60 deg C, 15 min
16: 78 percent / BF3.Et2O, bis(trimethylsilyl)peroxide / CH2Cl2 / 1.5 h / Ambient temperature; 2
17: 42 percent / boron trichloride / CH2Cl2; hexane / 4 h / -78 °C
View Scheme
参考文献
Hanessian; Roy; Petrini; Hodges; Di Fabio; Carganico
Journal of Organic Chemistry, 1990 , vol. 55, # 22 p. 5766 - 5777
→
77517-29-4[(1S,3S,4aR,7S,8S,8aR)-8-[2-[(2R,4R)-4-羟基-6-氧代四氢吡喃-2-基]乙基]-3,7-二甲基-1,2,3,4,4a,7,8,8a-八氢萘-1-基] (2S)-2-甲基丁酸酯
反应条件
1: 70 percent / DMAP / 0.33 h / 40 °C
2: 70 percent / Amberlyst A-21 / diethyl ether / 2 h / Ambient temperature
3: 55 percent / n-Bu3SnH, AIBN / toluene / 0.5 h / Heating
4: 0.034 g / sodium borohydride / propan-2-ol; tetrahydrofuran / -78 deg C to rt, overnight
5: 80 percent / n-tetrabutylammonium iodide, NaH / tetrahydrofuran / 18 h / Ambient temperature
6: 85 percent / 48percent aq. HF / acetonitrile / 1.5 h / Ambient temperature
7: 1.) oxalyl chloride, DMSO 2.) triethylamine / 1.) CH2Cl2, -60 deg C, 15 min 2.) -60 deg C, 15 min
8: 78 percent / BF3.Et2O, bis(trimethylsilyl)peroxide / CH2Cl2 / 1.5 h / Ambient temperature; 2
9: 42 percent / boron trichloride / CH2Cl2; hexane / 4 h / -78 °C
View Scheme
参考文献
Hanessian; Roy; Petrini; Hodges; Di Fabio; Carganico
Journal of Organic Chemistry, 1990 , vol. 55, # 22 p. 5766 - 5777
