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【结 构 式】 
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【分子编号】25611 【品名】3',6'-Dimethoxy-p-terphenyl-2',3,4,4''-tetrol 2'-O,3-O,4''-O-tris methanesulfonate 【CA登记号】 |
【 分 子 式 】C23H24O12S3 【 分 子 量 】588.63436 【元素组成】C 46.93% H 4.11% O 32.62% S 16.34% |
合成路线1
该中间体在本合成路线中的序号：(X)1. The Suzuki coupling of arylboronic acid (I) with 3-bromo-2,5-dimethoxybenzaldehyde (II) with concomitant desilylation provided biphenyl aldehyde (III). After protection of the phenolic hydroxyl as the mesylate (IV), selective bromination of (IV) in the presence of NaOAc in AcOH provided bromoaldehyde (V). A Baeyer-Villiger oxidation of the aldehyde group of (V) with m-chloroperbenzoic acid, followed by acid hydrolysis of the intermediate formate ester, produced phenol (VI). which was coupled with protected boronic acid (VII) in the presence of Pd(PPh3)4 to yield terphenyl (VIII). Mesylation of the hydroxyl groups of (VIII) and further hydrogenolytic cleavage of the benzyl ether gave phenol (X). Then, alkylationof (X) with prenyl bromide (XI) provided prenyl ether (XII). The mesylate groups of (XII) were finally removed by hydrolysis with KOH to furnish 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 |
|---|---|---|---|---|---|---|
| (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 | |
| (III) | 25604 | 4'-hydroxy-2,5-dimethoxy[1,1'-biphenyl]-3-carbaldehyde | C15H14O4 | 详情 | 详情 | |
| (IV) | 25605 | 3'-formyl-2',5'-dimethoxy[1,1'-biphenyl]-4-yl methanesulfonate | C16H16O6S | 详情 | 详情 | |
| (V) | 25606 | 4'-bromo-3'-formyl-2',5'-dimethoxy[1,1'-biphenyl]-4-yl methanesulfonate | C16H15BrO6S | 详情 | 详情 | |
| (VI) | 25607 | 4'-bromo-3'-hydroxy-2',5'-dimethoxy[1,1'-biphenyl]-4-yl methanesulfonate | C15H15BrO6S | 详情 | 详情 | |
| (VII) | 25608 | 4-(benzyloxy)-3-[[tert-butyl(dimethyl)silyl]oxy]phenylboronic acid | C19H27BO4Si | 详情 | 详情 | |
| (VIII) | 25609 | Methanesulfonic acid 4''-benzyloxy-3',3''-dihydroxy-2',5'-dimethoxy-p-terphenyl-4-yl ester | C28H26O8S | 详情 | 详情 | |
| (IX) | 25610 | 4-Benzyloxy-3',6'-dimethoxy-p-terphenyl-3,2',4''-triol tris methanesuolfonyl ester | C30H30O12S3 | 详情 | 详情 | |
| (X) | 25611 | 3',6'-Dimethoxy-p-terphenyl-2',3,4,4''-tetrol 2'-O,3-O,4''-O-tris methanesulfonate | C23H24O12S3 | 详情 | 详情 | |
| (XII) | 25612 | 3',6'-Dimethoxy-4-(3-methyl-2-butenyloxy)-p-terphenyl-2',3,4''-triol tris methanesulfonate | C28H32O12S3 | 详情 | 详情 |