文献类型：期刊文献

英文题名：Stereoselective synthesis of (+)-valienamine starting from the naturally abundant (-)-shildmic acid

作者：Ding, Wei[1];Yu, Jiang-Ping[1];Shi, Xiao-Xin[1];Nie, Liang-Deng[1];Quan, Na[1];Li, Feng-Lei[1]

机构：[1]E China Univ Sci & Technol, Sch Pharm, Dept Pharmaceut Engn, Shanghai 200237, Peoples R China

年份：2015

卷号：26

期号：18-19

起止页码：1037

外文期刊名：TETRAHEDRON-ASYMMETRY

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000363077100002)，CCR-EXPANDED(收录号:WOS:000363077100002)】；

基金：We are grateful to the National Natural Science Foundation of China (No. 20972048) for the financial support of this work.

语种：英文

摘要：A stereoselective synthesis of the pharmaceutically useful pseudo-aminosugar (+)-valienamine 1 is described. Epoxide 2 was first prepared via four steps in 79.7% overall yield starting from the naturally abundant (-)-shikimic acid. Epoxide 2 was then converted into the vicinal dihydroxyl compound 3 in 96% yield via a highly regio- and stereoselective water-mediated epoxide opening. Compound 3 was transformed into compound 4 in 86% yield over two steps via ester-reduction and benzylation of the three hydroxyl groups. Compound 4 was converted into azido compound 5 in 90% yield via an S(N)2-type nucleophilic substitution of the OMs leaving group with sodium azide. Ruthenium-catalyzed stereoselective dihydroxylation of compound 5 afforded dihydroxyl compound 6 in 91% yield. Compound 6 was transformed into compound 7 in 92% yield via selective mono-acetylation of the less-hindered hydroxyl group. Dehydration of tertiary alcohol 7 via an acid-mediated elimination furnished olefinic compound 8 in 85% yield. Finally, compound 8 was converted into the title compound 1 in 91% yield over two steps via deprotection and Lindlar-catalyst-promoted highly selective hydrogenation of the azido group (N-3) in the presence of a double bond. (+)-Valienamine 1 was thus synthesized starting from the naturally abundant (-)-shikimic acid via 13 steps in 38.3% total yield. (C) 2015 Elsevier Ltd. All rights reserved.