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【结 构 式】 
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【分子编号】25616 【品名】7-bromo-2,3-dihydro-1,4-benzodioxin-2-yl methyl ether 【CA登记号】 |
【 分 子 式 】C9H9BrO3 【 分 子 量 】245.07266 【元素组成】C 44.11% H 3.7% Br 32.6% O 19.59% |
合成路线1
该中间体在本合成路线中的序号：(XVII)2. In an alternative synthesis, 5-bromosalicylaldehyde (XIII) was alkylated with bromoacetaldehyde dimethyl acetal (XIV) to afford ether (XV). Further Baeyer-Villiger reaction with (XV) produced phenol (XVI), which was cyclized to the benzodioxine (XVII) with p-TsOH. Lithiation of (XVII), followed by reaction with triisopropyl borate and hydrolytic work-up, gave boronic acid (XVIII). Aldehyde (II) was treated with MCPBA yielding phenol (XIII), which was iodinated in the presence of tert-butylamine to give the bromo iodo derivative (XIV). Sequential Suzuki coupling of bromo iodo compound (XIV) with boronic acid (XVIII) yielding (XIX), and then with boronic acid (I) provided terphenyl (XX). Hydrolysis of the methyl acetal of (XX) using p-TsOH gave cyclic hemiacetal (XXI). Finally, Wittig reaction of (XXI) with the phosphorane prepared from isopropyl triphenylphosphonium iodide and n-BuLi provided the title compound.
| 【1】 Yonezawa, S.; et al.; Total synthesis of terprenin, a novel immunosuppressive p-terphenyl derivative. J Org Chem 1998, 63, 17, 5831. |
| 【2】 Nagashima, K.; Kamigauchi, T.; Sakazaki, R.; et al.; Terprenins, novel immunosuppressants produced by Aspergillus candidus. J Antibiot 1998, 51, 4, 445. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XIIIa) | 25618 | 3-bromo-2,5-dimethoxyphenol | C8H9BrO3 | 详情 | 详情 | |
| (XIVb) | 25619 | 3-bromo-6-iodo-2,5-dimethoxyphenol | C8H8BrIO3 | 详情 | 详情 | |
| (I) | 25602 | 4-[[tert-butyl(dimethyl)silyl]oxy]phenylboronic acid | C12H21BO3Si | 详情 | 详情 | |
| (II) | 25603 | 3-bromo-2,5-dimethoxybenzaldehyde | C9H9BrO3 | 详情 | 详情 | |
| (XIII) | 25613 | 5-bromo-2-hydroxybenzaldehyde; 5-Bromosalicylaldehyde | 1761-61-1 | C7H5BrO2 | 详情 | 详情 |
| (XIV) | 13183 | 2-Bromo-1,1-dimethoxyethane; 2-Bromo-1-methoxyethyl methyl ether; Bromoacetaldehyde dimethyl acetal | 7252-83-7 | C4H9BrO2 | 详情 | 详情 |
| (XV) | 25614 | 5-bromo-2-(2,2-dimethoxyethoxy)benzaldehyde | C11H13BrO4 | 详情 | 详情 | |
| (XVI) | 25615 | 5-bromo-2-(2,2-dimethoxyethoxy)phenol | C10H13BrO4 | 详情 | 详情 | |
| (XVII) | 25616 | 7-bromo-2,3-dihydro-1,4-benzodioxin-2-yl methyl ether | C9H9BrO3 | 详情 | 详情 | |
| (XVIII) | 25617 | 3-methoxy-2,3-dihydro-1,4-benzodioxin-6-ylboronic acid | C9H11BO5 | 详情 | 详情 | |
| (XIX) | 25620 | 3-bromo-2,5-dimethoxy-6-(3-methoxy-2,3-dihydro-1,4-benzodioxin-6-yl)phenol | C17H17BrO6 | 详情 | 详情 | |
| (XX) | 25621 | 2,5-dimethoxy-4-(3-methoxy-2,3-dihydro-1,4-benzodioxin-6-yl)[1,1'-biphenyl]-3,4'-diol | C23H22O7 | 详情 | 详情 | |
| (XXI) | 25622 | 4-(3-hydroxy-2,3-dihydro-1,4-benzodioxin-6-yl)-2,5-dimethoxy[1,1'-biphenyl]-3,4'-diol | C22H20O7 | 详情 | 详情 |