Ishikawa Teruhiko, Shimizu Yoshihiro, Kudoh Takayuki, Saito Seiki
Department of Bioscience and Biotechnology, School of Engineering and School of Education, Okayama University, Tsushima, Okayama, Japan 700-8530.
Org Lett. 2003 Oct 16;5(21):3879-82. doi: 10.1021/ol035424n.
[reaction: see text] A diastereoisomeric mixture of 1-nitro-6-heptene-2,3,4,5-tetraol derivative (A) was prepared by Henry reaction between d-glucose-based aldehyde and nitromethane. Only the (2S)-isomer of A led to cyclitol (B) via nitronate-olefin cycloaddition on treatment with TMS-Cl and Et(3)N in the presence of catalytic DMAP followed by acid treatment. (+)-Cyclophellitol (1) was synthesized from B in eight steps.
[反应：见正文] 通过基于d-葡萄糖的醛与硝基甲烷之间的亨利反应制备了1-硝基-6-庚烯-2,3,4,5-四醇衍生物（A）的非对映异构体混合物。在用TMS-Cl和Et(3)N在催化量的DMAP存在下处理然后进行酸处理时，只有A的(2S)-异构体通过硝酮-烯烃环加成反应生成环多元醇（B）。(+)-环落叶松醇（1）由B经八步合成得到。
