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【结 构 式】 
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【分子编号】55277 【品名】(1R,2R,6R,10S,11R,13S,15R,17R)-13-benzyl-6-hydroxy-8-(hydroxymethyl)-15-isopropenyl-4,17-dimethyl-12,14,18-trioxapentacyclo[11.4.1.0~1,10~.0~2,6~.0~11,15~]octadeca-3,8-dien-5-one 【CA登记号】 |
【 分 子 式 】C28H32O6 【 分 子 量 】464.55848 【元素组成】C 72.39% H 6.94% O 20.66% |
合成路线1
该中间体在本合成路线中的序号：(XLIII)Bromination at the alpha-position of ketone (XXXIX) to (XLI) was effected via formation of the corresponding silyl enol ether (XL), followed by treatment with N-bromosuccinimide. Dehydrohalogenation of the resultant bromo ketone (XLI) by means of lithium carbonate and lithium bromide in hot DMF afforded enone (XLII). Sequential removal of the O-silyl and benzoate protecting groups of (XLII) provided diol (XLIII). The C20 alcohol of (XLIII) was then esterified with the mixed anhydride (XLIV) to furnish the (4-O-acetyl)homovanillic ester (XLV). Finally, a soultion of pyrrolidine in CH2Cl2 was employed for the cleavage of the O-acetyl protecting group of (XLV).
| 【1】 Boger, D.L.; Searcey, M.; The first synthesis of a daphnane diterpene: The enantiocontrolled total synthesis of (+)-resiniferatoxin. Chemtracts - Org Chem 1998, 11, 9, 647. |
| 【2】 Wender, P.A.; et al.; The first synthesis of a daphnane diterpene: The enantiocontrolled total synthesis of resiniferatoxin. J Am Chem Soc 1997, 119, 52, 12976. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXXIX) | 55273 | {(1R,2S,4S,6R,10S,11R,13S,15R,17R)-13-benzyl-15-isopropenyl-4,17-dimethyl-5-oxo-6-[(trimethylsilyl)oxy]-12,14,18-trioxapentacyclo[11.4.1.0~1,10~.0~2,6~.0~11,15~]octadec-8-en-8-yl}methyl benzoate | C38H46O7Si | 详情 | 详情 | |
| (XL) | 55274 | {(1R,2S,6R,10S,11R,13S,15R,17R)-13-benzyl-15-isopropenyl-4,17-dimethyl-5,6-bis[(trimethylsilyl)oxy]-12,14,18-trioxapentacyclo[11.4.1.0~1,10~.0~2,6~.0~11,15~]octadeca-4,8-dien-8-yl}methyl benzoate | C41H54O7Si2 | 详情 | 详情 | |
| (XLI) | 55275 | {(1R,2S,6R,10S,11R,13S,15R,17R)-13-benzyl-4-bromo-15-isopropenyl-4,17-dimethyl-5-oxo-6-[(trimethylsilyl)oxy]-12,14,18-trioxapentacyclo[11.4.1.0~1,10~.0~2,6~.0~11,15~]octadec-8-en-8-yl}methyl benzoate | C38H45BrO7Si | 详情 | 详情 | |
| (XLII) | 55276 | {(1R,2S,6R,10S,11R,13S,15R,17R)-13-benzyl-15-isopropenyl-4,17-dimethyl-5-oxo-6-[(trimethylsilyl)oxy]-12,14,18-trioxapentacyclo[11.4.1.0~1,10~.0~2,6~.0~11,15~]octadeca-3,8-dien-8-yl}methyl benzoate | C38H44O7Si | 详情 | 详情 | |
| (XLIII) | 55277 | (1R,2R,6R,10S,11R,13S,15R,17R)-13-benzyl-6-hydroxy-8-(hydroxymethyl)-15-isopropenyl-4,17-dimethyl-12,14,18-trioxapentacyclo[11.4.1.0~1,10~.0~2,6~.0~11,15~]octadeca-3,8-dien-5-one | C28H32O6 | 详情 | 详情 | |
| (XLIV) | 55278 | [4-(acetyloxy)-3-methoxyphenyl]acetic 2,4,6-trichloro-1-benzenecarboxylic anhydride | C18H13Cl3O6 | 详情 | 详情 | |
| (XLV) | 55279 | [(1R,2R,6R,10S,11R,13S,15R,17R)-13-benzyl-6-hydroxy-15-isopropenyl-4,17-dimethyl-5-oxo-12,14,18-trioxapentacyclo[11.4.1.0~1,10~.0~2,6~.0~11,15~]octadeca-3,8-dien-8-yl]methyl 2-[4-(acetyloxy)-3-methoxyphenyl]acetate | C39H42O10 | 详情 | 详情 |