【结 构 式】 |
【分子编号】46667 【品名】(E)-4-ethyl-4-[(triethylsilyl)oxy]-2-hexen-1-ol 【CA登记号】 |
【 分 子 式 】C14H30O2Si 【 分 子 量 】258.4765 【元素组成】C 65.06% H 11.7% O 12.38% Si 10.87% |
合成路线1
该中间体在本合成路线中的序号:(IV)The indenone intermediate (XIII) has been obtained as follows: The silylation of 3-methyl-1-pentyn-3-ol (I) with Tes-Cl and DMAP in DMF gives the silyl ether (II), which is condensed with paraformaldehyde and n-BuLi in THF to yield the propargyl alcohol (III). Partial reduction of (III) with Red-Al in THF affords the allyl alcohol (IV), which is treated with Ts-Cl and DMAP in dichloromethane to provide the allyl chloride (V). The condensation of (V) with the unsaturated ester (VI) (obtained by Wittig condensation of perhydroindanone (VII) with triethyl phosphonoacetate (VIII) by means of EtONa) by means of BuLi and dicyclohexylamine in HMPA gives the octenoic ester (IX), which is reduced with LiAlH4, yielding the corresponding primary alcohol (X). The reaction of (X) with TsCl and pyridine affords the tosylate (XI), which is reduced with LiBEt3H in THF with simultaneous opening of the epoxide ring to provide the hexahydroindenol (XII). Finally, this compound is oxidized with pyridinium dichromate (PDC), yielding the target hexahydroindenone intermediate (XIII).
【1】 Radinov, R.N.; Daniewski, A.R. (F. Hoffmann-La Roche AG); Process for preparing anti-osteoporotic agents. EP 1048661; JP 2000336094 . |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(I) | 46664 | 3-ethyl-1-pentyn-3-ol | 6285-06-9 | C7H12O | 详情 | 详情 |
(II) | 46665 | [(1,1-diethyl-2-propynyl)oxy](triethyl)silane; 1,1-diethyl-2-propynyl triethylsilyl ether | C13H26OSi | 详情 | 详情 | |
(III) | 46666 | 4-ethyl-4-[(triethylsilyl)oxy]-2-hexyn-1-ol | C14H28O2Si | 详情 | 详情 | |
(IV) | 46667 | (E)-4-ethyl-4-[(triethylsilyl)oxy]-2-hexen-1-ol | C14H30O2Si | 详情 | 详情 | |
(V) | 46668 | (E)-4-chloro-1,1-diethyl-2-butenyl triethylsilyl ether; [[(E)-4-chloro-1,1-diethyl-2-butenyl]oxy](triethyl)silane | C14H29ClOSi | 详情 | 详情 | |
(VI) | 46669 | ethyl 2-[(1aS,3aS,6aR,6bR)-3a-methyloctahydro-4H-indeno[4,5-b]oxiren-4-ylidene]acetate | C14H20O3 | 详情 | 详情 | |
(VII) | 45538 | (1aS,3aS,6aR,6bR)-3a-methyloctahydro-4H-indeno[4,5-b]oxiren-4-one | C10H14O2 | 详情 | 详情 | |
(VIII) | 10019 | Ethyl 2-(diethoxyphosphoryl)acetate; Triethyl phosphonoacetate | 867-13-0 | C8H17O5P | 详情 | 详情 |
(IX) | 46670 | ethyl (2S,4E)-2-[(1aS,3aS,6aR,6bR)-3a-methyl-2,3,3a,6,6a,6b-hexahydro-1aH-indeno[4,5-b]oxiren-4-yl]-6-ethyl-6-[(triethylsilyl)oxy]-4-octenoate | C28H48O4Si | 详情 | 详情 | |
(X) | 46671 | (3aS,7S,7aR)-3-[(1S,3E)-5-ethyl-1-(hydroxymethyl)-5-[(triethylsilyl)oxy]-3-heptenyl]-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-7-ol | C26H48O3Si | 详情 | 详情 | |
(XI) | 46672 | (2S,4E)-2-[(3aS,7S,7aR)-7-hydroxy-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-3-yl]-6-ethyl-6-[(triethylsilyl)oxy]-4-octenyl 4-methylbenzenesulfonate | C33H54O5SSi | 详情 | 详情 | |
(XII) | 46673 | (3aS,7S,7aR)-3-[(1S,3E)-5-ethyl-1-methyl-5-[(triethylsilyl)oxy]-3-heptenyl]-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-7-ol | C26H48O2Si | 详情 | 详情 | |
(XIII) | 46674 | (3aR,7aS)-1-[(1S,3E)-5-ethyl-1-methyl-5-[(triethylsilyl)oxy]-3-heptenyl]-7a-methyl-3,3a,5,6,7,7a-hexahydro-4H-inden-4-one | C26H46O2Si | 详情 | 详情 |