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【结 构 式】 
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【分子编号】65665 【品名】4-Bromo-2-methyl-1-butene; 1-Bromo-3-methyl-3-butene; 2-Methyl-4-bromo-1-butene; 3-Methyl-3-butenyl bromide 【CA登记号】20038-12-4 |
【 分 子 式 】C5H9Br 【 分 子 量 】149.03046 【元素组成】C 40.3% H 6.09% Br 53.62% |
合成路线1
该中间体在本合成路线中的序号：(XXVI)The preparation of the C7-C12 building block (II) (segment B) is performed as follows. Protection of methyl 3-hydroxy-2(R)-methylpropionate by means of dihydropyran and p-toluenesulfonic acid in CH2Cl2 gives the tetrahydropyranyl ether (XXII), which is then reduced with LiAlH4 in Et2O to yield alcohol (XXIII) and derivatized to tosylate (XXIV) under the usual conditions. Reaction of 3-methyl-3-buten-1-ol (XXV) with N-bromosuccinimide and triphenylphosphine in CH2Cl2 affords the butenyl bromide (XXVI) which, after conversion to the corresponding Grignard reagent, is coupled with tosylate (XXIV) in the presence of catalytic Li2CuCl4 leading to adduct (XXVII). Then, dihydroxylation of olefin (XXVII) and subsequent oxidative cleavage employing OsO4 and NaIO4 gives the desired ketone (II) (2). Scheme 3.
| 【2】 Klar, U., Buchmann, B., Schwede, W., Skuballa, W., Hoffmann, J., Lichtner, R.B. Total synthesis and antitumor activity of ZK-EPO: The first fully synthetic epothilone in clinical development. Angew Chem Int Ed Engl 2006, 45(47): 7942-8. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (II) | 65645 | C13H25O3 | 详情 | 详情 | ||
| (XXI) | 14965 | methyl 3-hydroxy-2-methylpropanoate; METHYL (S)-(+)-3-HYDROXY-2-METHYLPROPIONATE | 80657-57-4 | C5H10O3 | 详情 | 详情 |
| (XXII) | 65662 | C10H19O4 | 详情 | 详情 | ||
| (XXIII) | 65663 | C9H18O3 | 详情 | 详情 | ||
| (XXIV) | 65664 | C10H20O5S | 详情 | 详情 | ||
| (XXV) | 47474 | 3-methyl-3-buten-1-ol | 763-32-6 | C5H10O | 详情 | 详情 |
| (XXVI) | 65665 | 4-Bromo-2-methyl-1-butene; 1-Bromo-3-methyl-3-butene; 2-Methyl-4-bromo-1-butene; 3-Methyl-3-butenyl bromide | 20038-12-4 | C5H9Br | 详情 | 详情 |
| (XXVII) | 65666 | C14H26O2 | 详情 | 详情 |