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【结 构 式】 
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【分子编号】59890 【品名】2-((3R,4S,5R)-5-{[tert-butyl(dimethyl)silyl]oxy}-3,4-dihydroxy-2-methylenecyclohexylidene)ethyl pivalate 【CA登记号】 |
【 分 子 式 】C20H36O5Si 【 分 子 量 】384.58834 【元素组成】C 62.46% H 9.43% O 20.8% Si 7.3% |
合成路线1
该中间体在本合成路线中的序号：(LII)The title compound was also prepared using solid-phase methodology within a parallel synthesis protocol for the construction of a combinatorial library of vitamin D3 analogues. The A-ring synthon (LVIII) was synthesized as follows. Esterification of the previously reported alcohol intermediate (L) with pivaloyl chloride gave pivalate ester (LI). Acetonide hydrolysis in (LI) and then selective mono-silylation of the resultant diol (LII) yielded (LIII). Michael addition of ethyl acrylate (LIV) to the free hydroxyl group of (LIII) furnished ester (LV). Subsequently reduction of methyl ester (LV), with simultaneous reductive cleavage of the pivaloyl group in the presence of LiAlH4 led to diol (LVI). Chlorination of the allylic alcohol of (LVI) by means of N-chlorosuccinimide and dimethylsulfide, followed by silylation of the remaining hydroxyl group gave (LVII). Conversion of chloride (LVII) into the phosphine oxide (LVIII) was then performed using a similar procedure as that for intermediate (XXXII)
| 【1】 Hijikuro, I.; Doi, T.; Takahashi, T.; Parallel synthesis of a vitamin D3 library in the solid-phase. J Am Chem Soc 2001, 123, 16, 3716. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (L) | 59888 | 2-[(3aR,7R,7aS)-7-{[tert-butyl(dimethyl)silyl]oxy}-2,2-dimethyl-4-methylenetetrahydro-1,3-benzodioxol-5(4H)-ylidene]-1-ethanol | C18H32O4Si | 详情 | 详情 | |
| (LI) | 59889 | 2-[(3aR,7R,7aS)-7-{[tert-butyl(dimethyl)silyl]oxy}-2,2-dimethyl-4-methylenetetrahydro-1,3-benzodioxol-5(4H)-ylidene]ethyl pivalate | C23H40O5Si | 详情 | 详情 | |
| (LII) | 59890 | 2-((3R,4S,5R)-5-{[tert-butyl(dimethyl)silyl]oxy}-3,4-dihydroxy-2-methylenecyclohexylidene)ethyl pivalate | C20H36O5Si | 详情 | 详情 | |
| (LIII) | 59891 | 2-((3R,4R,5R)-3,5-bis{[tert-butyl(dimethyl)silyl]oxy}-4-hydroxy-2-methylenecyclohexylidene)ethyl pivalate | C26H50O5Si2 | 详情 | 详情 | |
| (LIV) | 14156 | methyl acrylate | 96-33-3 | C4H6O2 | 详情 | 详情 |
| (LV) | 59892 | 2-[(3R,4R,5R)-3,5-bis{[tert-butyl(dimethyl)silyl]oxy}-4-(3-methoxy-3-oxopropoxy)-2-methylenecyclohexylidene]ethyl pivalate | C30H56O7Si2 | 详情 | 详情 | |
| (LVI) | 59893 | 3-({(1R,2R,6R)-2,6-bis{[tert-butyl(dimethyl)silyl]oxy}-4-[(Z)-2-hydroxyethylidene]-3-methylenecyclohexyl}oxy)-1-propanol | C24H48O5Si2 | 详情 | 详情 | |
| (LVII) | 59894 | tert-butyl({(1R,2R,3R)-3-{[tert-butyl(dimethyl)silyl]oxy}-2-(3-{[tert-butyl(dimethyl)silyl]oxy}propoxy)-5-[(Z)-2-chloroethylidene]-4-methylenecyclohexyl}oxy)dimethylsilane; (1R,2R,6R)-2,6-bis{[tert-butyl(dimethyl)silyl]oxy}-4-[(Z)-2-chloroethylidene]-3-methylenecyclohexyl 3-{[tert-butyl(dimethyl)silyl]oxy}propyl ether | C30H61ClO4Si3 | 详情 | 详情 | |
| (LVIII) | 59895 | 2-[(3R,4R,5R)-3,5-bis{[tert-butyl(dimethyl)silyl]oxy}-4-(3-{[tert-butyl(dimethyl)silyl]oxy}propoxy)-2-methylenecyclohexylidene]ethyl(diphenyl)phosphine oxide; {2-[(3R,4R,5R)-3,5-bis{[tert-butyl(dimethyl)silyl]oxy}-4-(3-{[tert-butyl(dimethyl)silyl]oxy}propoxy)-2-methylenecyclohexylidene]ethyl}(oxo)diphenylphosphorane | C42H71O5PSi3 | 详情 | 详情 |