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【结 构 式】 
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【分子编号】38553 【品名】1-bromo-2-(chloromethyl)-4-methoxybenzene; 4-bromo-3-(chloromethyl)phenyl methyl ether 【CA登记号】 |
【 分 子 式 】C8H8BrClO 【 分 子 量 】235.50762 【元素组成】C 40.8% H 3.42% Br 33.93% Cl 15.05% O 6.79% |
合成路线1
该中间体在本合成路线中的序号：(IX)The intermediate 3-(2-bromo-5-methoxyphenyl)-2(S)-methyl-1-propanol tert-butyldimethylsilyl ether (XIV) has been obtained as follows: the reduction of 2-bromo-5-methoxybenzoic acid (VII) with NaBH4/BF3 gives the expected benzyl alcohol (VIII), which by treatment with SOCl2 is converted into the benzyl chloride (IX). The condensation of (IX) with the chiral auxiliary (X) by means of LIHMDS provides the 2(S)-methylpropionic acid derivative (XI). Elimination of the chiral auxiliary with sulfuric acid gives 3-(2-bromo-5-methoxyphenyl)-2(S)-methylpropionic acid (XII), which is reduced with NaBH4/BF3 to the corresponding alcohol (XIII). Finally, this compound is silylated to afford the intermediate (XIV) with TBDMS-Cl and imidazole.
| 【1】 Song, Z.J.; et al.; Practical asymetric synthesis of an endothelin receptor antagonist. J Org Chem 1999, 64, 26, 9658. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (VII) | 17819 | 2-bromo-5-methoxybenzoic acid | 22921-68-2 | C8H7BrO3 | 详情 | 详情 |
| (VIII) | 27551 | (2-bromo-5-methoxyphenyl)methanol | C8H9BrO2 | 详情 | 详情 | |
| (IX) | 38553 | 1-bromo-2-(chloromethyl)-4-methoxybenzene; 4-bromo-3-(chloromethyl)phenyl methyl ether | C8H8BrClO | 详情 | 详情 | |
| (X) | 27554 | 1-[(3aR,8aS)-2,2-dimethyl-8,8a-dihydro-2H-indeno[1,2-d][1,3]oxazol-3(3aH)-yl]-1-propanone | C15H19NO2 | 详情 | 详情 | |
| (XI) | 27555 | (2S)-1-[(3aR,8aS)-2,2-dimethyl-8,8a-dihydro-2H-indeno[1,2-d][1,3]oxazol-3(3aH)-yl]-3-(2-bromo-5-methoxyphenyl)-2-methyl-1-propanone | C23H26BrNO3 | 详情 | 详情 | |
| (XII) | 27556 | (2S)-3-(2-bromo-5-methoxyphenyl)-2-methylpropionic acid | C11H13BrO3 | 详情 | 详情 | |
| (XIII) | 27558 | (2S)-3-(2-bromo-5-methoxyphenyl)-2-methyl-1-propanol | C11H15BrO2 | 详情 | 详情 | |
| (XIV) | 27567 | 4-bromo-3-((2S)-3-[[tert-butyl(dimethyl)silyl]oxy]-2-methylpropyl)phenyl methyl ether | C17H29BrO2Si | 详情 | 详情 |