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【结 构 式】 
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【分子编号】42634 【品名】(2S,4S,5S)-1-(benzyloxy)-5-hydroxy-2,4-dimethyl-3-hexanone 【CA登记号】 |
【 分 子 式 】C15H22O3 【 分 子 量 】250.33788 【元素组成】C 71.97% H 8.86% O 19.17% |
合成路线1
该中间体在本合成路线中的序号：(XXIV)The intermediate (XXX) has been obtained as follows: The condensation of benzylated hydroxypentanone (XXII) with acetaldehyde (XXIII) by means of DCHBCl gives the hydroxyhexanone (XXIV), which is reduced with LiBH4, yielding the diol (XXV). The silylation of (XXV) with Tbdms-OTf affords the disilyl ether (XXVI), which is regioselectively monodesilylated with CSA, providing the alcohol (XXVII). The hydrogenolysis of (XXVII) with H2 over Pd/C gives the primary alcohol (XXVIII), which is treated with (COCl)2 and NaClO2 in order to oxidize the primary alcohol to carboxylic acid and the secondary alcohol to ketone to furnish the ketoacid (XXIX). Finally, this compound is esterified with diazomethane to afford the desired ester intermediate (XXX).
| 【1】 Paterson, I.; Florence, G.J.; Synthesis of (+)-discodermolide and analogues by control of asymmetric induction in aldol reactions of gamma-chiral (Z)-enals. Tetrahedron Lett 2000, 41, 35, 6935. |
| 【2】 Paterson, I.; et al.; Total synthesis of the antimicrotubule agent (+)-discodermolide using boron-mediated aldol reactions of chiral ketones. Angew Chem. Int Ed Engl 2000, 39, 2, 377. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXII) | 42633 | (2S)-1-(benzyloxy)-2-methyl-3-pentanone | C13H18O2 | 详情 | 详情 | |
| (XXIII) | 11974 | Acetaldehyde | 75-07-0 | C2H4O | 详情 | 详情 |
| (XXIV) | 42634 | (2S,4S,5S)-1-(benzyloxy)-5-hydroxy-2,4-dimethyl-3-hexanone | C15H22O3 | 详情 | 详情 | |
| (XXV) | 42635 | (2S,3S,4R,5S)-6-(benzyloxy)-3,5-dimethyl-2,4-hexanediol | C15H24O3 | 详情 | 详情 | |
| (XXVI) | 42636 | benzyl (2S,3R,4S,5S)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2,4-dimethylhexyl ether; (5R,6S,7S)-5-[(1S)-2-(benzyloxy)-1-methylethyl]-2,2,3,3,6,7,9,9,10,10-decamethyl-4,8-dioxa-3,9-disilaundecane | n/a | C27H52O3Si2 | 详情 | 详情 |
| (XXVII) | 42637 | (2S,3S,4R,5S)-6-(benzyloxy)-4-[[tert-butyl(dimethyl)silyl]oxy]-3,5-dimethyl-2-hexanol | n/a | C21H38O3Si | 详情 | 详情 |
| (XXVIII) | 42638 | (2S,3R,4S,5S)-3-[[tert-butyl(dimethyl)silyl]oxy]-2,4-dimethyl-1,5-hexanediol | C14H32O3Si | 详情 | 详情 | |
| (XXIX) | 42639 | (2R,3S,4R)-3-[[tert-butyl(dimethyl)silyl]oxy]-2,4-dimethyl-5-oxohexanoic acid | C14H28O4Si | 详情 | 详情 | |
| (XXX) | 42640 | methyl (2R,3S,4R)-3-[[tert-butyl(dimethyl)silyl]oxy]-2,4-dimethyl-5-oxohexanoate | C15H30O4Si | 详情 | 详情 |