【结 构 式】 |
【分子编号】60336 【品名】5-iodo-2,4-dimethyl-3-{[tris(1-methylethyl)silyl]oxy}-4-penten-1-ol 【CA登记号】 |
【 分 子 式 】C16H33IO2Si 【 分 子 量 】412.42679 【元素组成】C 46.6% H 8.06% I 30.77% O 7.76% Si 6.81% |
合成路线1
该中间体在本合成路线中的序号:(V)Synthesis of intermediates: Iodinated pivalate (X): The condensation of 3-iodo-2-methyl-2-propenal (I) with the silylated enol ether (II) by means of Zr(O-tBu)4 and 3,3'-I2-BINOL in toluene gives the iodopentenoic acid (III), which is treated with Tips-Cl and imidazole to yield the silyl ether (IV). The reduction of (IV) by means of DIBAL in dichloromethane affords the 5-iodopenten-1-ol (V), which is oxidized by means of (COCl)2 in DMSO/dichloromethane to provide the aldehyde (VI). The Wittig condensation of (VI) with phosphorane (VII) in refluxing THF leads to the heptadienoic ester (VIII), which is reduced with DIBAL in dichloromethane giving the primary alcohol (IX). Finally this alcohol is esterified pivaloyl chloride and pyridine to affords the target iodinated pivalate (X).
【1】 Kobayashi, S.; Mori, K.; Wakabayashi, T.; Yasuda, S.; Hanada, K.; Convergent total synthesis of khafrefungin and its inhibitory activity of fungal sphigolipid syntheses. J Org Chem 2001, 66, 16, 5580. |
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) | 37952 | (E)-3-iodo-2-methyl-2-propenal | C4H5IO | 详情 | 详情 | |
(II) | 60333 | phenyl 1-[(trimethylsilyl)oxy]-1-propenyl ether; trimethyl{[1-(phenyloxy)-1-propenyl]oxy}silane | C12H18O2Si | 详情 | 详情 | |
(III) | 60334 | phenyl 3-hydroxy-5-iodo-2,4-dimethyl-4-pentenoate | C13H15IO3 | 详情 | 详情 | |
(IV) | 60335 | phenyl 5-iodo-2,4-dimethyl-3-{[tris(1-methylethyl)silyl]oxy}-4-pentenoate | C22H35IO3Si | 详情 | 详情 | |
(V) | 60336 | 5-iodo-2,4-dimethyl-3-{[tris(1-methylethyl)silyl]oxy}-4-penten-1-ol | C16H33IO2Si | 详情 | 详情 | |
(VI) | 60337 | 5-iodo-2,4-dimethyl-3-{[tris(1-methylethyl)silyl]oxy}-4-pentenal | C16H31IO2Si | 详情 | 详情 | |
(VII) | 47172 | propyl 2-(triphenylphosphoranylidene)propanoate | C24H25O2P | 详情 | 详情 | |
(VIII) | 60338 | propyl 7-iodo-2,4,6-trimethyl-5-{[tris(1-methylethyl)silyl]oxy}-2,6-heptadienoate | C22H41IO3Si | 详情 | 详情 | |
(IX) | 60339 | 7-iodo-2,4,6-trimethyl-5-{[tris(1-methylethyl)silyl]oxy}-2,6-heptadien-1-ol | C19H37IO2Si | 详情 | 详情 | |
(X) | 60340 | 7-iodo-2,4,6-trimethyl-5-{[tris(1-methylethyl)silyl]oxy}-2,6-heptadienyl 2,2-dimethylpropanoate | C24H45IO3Si | 详情 | 详情 |