【结 构 式】 |
【分子编号】59083 【品名】methyl (3R)-3-hydroxydecanoate 【CA登记号】 |
【 分 子 式 】C11H22O3 【 分 子 量 】202.29388 【元素组成】C 65.31% H 10.96% O 23.73% |
合成路线1
该中间体在本合成路线中的序号:(XV)Reformatskii condensation of the organozinc reagent derived from methyl bromoacetate (XIII) with n-heptyl cyanide (XII) gave rise to the keto ester adduct (XIV). Catalytic hydrogenation of (XIV) in the presence of the chiral catalyst generated from dichloro(cycloocta-1,5-diene)ruthenium and (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl furnished the (R)-hydroxyester (XV) in high enantiomeric excess. Ester group reduction in (XV) by means of LiAlH4 afforded diol (XVI), which was further converted to the primary tosylate (XVII) with p-toluenesulfonyl chloride in pyridine. Then, alkylation of the intermediate alcohol (XI) with tosylate (XVII) under Williamson's ether synthesis conditions provided the common precursor (XVIII).
【1】 Christ, W.J.; Kawata, T.; Hawkins, L.D.; Kobayashi, S.; Asano, O.; Rossignol, D.P. (Eisai Co., Ltd.); Anti-endotoxin cpds.. EP 0536969; JP 1993194470; US 5530113 . |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(XI) | 59080 | (4aR,6S,7R,8R,8aS)-7-azido-6-{[tert-butyl(dimethyl)silyl]oxy}-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-8-ol | C15H29N3O5Si | 详情 | 详情 | |
(XII) | 59081 | octanenitrile | 124-12-9 | C8H15N | 详情 | 详情 |
(XIII) | 12309 | methyl 2-bromoacetate; methyl bromoacetate | 96-32-2 | C3H5BrO2 | 详情 | 详情 |
(XIV) | 59082 | methyl 3-oxodecanoate | C11H20O3 | 详情 | 详情 | |
(XV) | 59083 | methyl (3R)-3-hydroxydecanoate | C11H22O3 | 详情 | 详情 | |
(XVI) | 59084 | (3R)-1,3-decanediol | C10H22O2 | 详情 | 详情 | |
(XVII) | 49121 | (3R)-3-hydroxydecyl 4-methylbenzenesulfonate | C17H28O4S | 详情 | 详情 | |
(XVIII) | 59085 | (3R)-1-[((4aR,6S,7R,8R,8aS)-7-azido-6-{[tert-butyl(dimethyl)silyl]oxy}-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-8-yl)oxy]-3-decanol | C25H49N3O6Si | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号:(I)Saponification of (R)-methyl 3-hydroxydecanoate (I) gave hydroxy acid (II), which was reduced to diol (III) using LiAlH4. Selective sulfonylation of the primary hydroxyl group of (III) provided tosylate (IV). The secondary hydroxyl group of (IV) was subsequently alkylated with iodomethane in the presence of NaH to furnish the methyl ether (V).
【1】 Kobayashi, S.; Kawata, T.; Christ, W.J.; Rossignol, D.P. (Eisai Co., Ltd.); Substd. liposaccharides useful in the treatment and prevention of endotoxemia. US 5750664; WO 9639411 . |
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) | 59083 | methyl (3R)-3-hydroxydecanoate | C11H22O3 | 详情 | 详情 | |
(II) | 64140 | (3R)-3-hydroxydecanoic acid | C10H20O3 | 详情 | 详情 | |
(III) | 59084 | (3R)-1,3-decanediol | C10H22O2 | 详情 | 详情 | |
(IV) | 49121 | (3R)-3-hydroxydecyl 4-methylbenzenesulfonate | C17H28O4S | 详情 | 详情 | |
(V) | 64141 | (3R)-3-methoxydecyl 4-methylbenzenesulfonate | C18H30O4S | 详情 | 详情 |