(1,4/2)-环己-5-烯三醇的一种新颖且简短的合成方法及其向(±)-原栎醇的转化。

A novel and short synthesis of (1,4/2)-cyclohex-5-ene-triol and its conversion to (+/-)-proto-quercitol.

作者信息

Gültekin M Serdar, Salamci Emine, Balci Metin

机构信息

Department of Chemistry, Faculty of Arts and Sciences, Atatürk University, 25240 Erzurum, Turkey.

出版信息

Carbohydr Res. 2003 Jul 29;338(16):1615-9. doi: 10.1016/s0008-6215(03)00256-8.

DOI:10.1016/s0008-6215(03)00256-8

PMID:12873418

Abstract

(1,4/2)-cyclohex-5-ene-triol was synthesized starting from cyclohexa-1,4-diene with two different approaches. Photooxygenation of cyclohexa-1,4-diene and epoxy-cyclohexene afforded anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxide and anti-7-oxabicyclo[4.1.0]hept-4-en-3-yl hydroperoxide, respectively. Hydroperoxy endoperoxide was reduced with aqueous sodium bisulfite; hydroperoxy-epoxide with dimethylsulfide-titanium tetraisopropoxide to give 7-oxabicyclo[4.1.0]hept-4-en-3-ol. Acidic hydrolysis of the epoxy-alcohol gave the (1,4/2)-cyclohex-3-ene-triol. Oxidation of the double bond with KMnO4 resulted in the formation of (+/-)-proto-quercitol.

摘要

(1,4/2)-环己-5-烯三醇由环己-1,4-二烯通过两种不同方法合成。环己-1,4-二烯和环氧环己烯的光氧化分别得到反式-2,3-二氧杂双环[2.2.2]辛-7-烯-5-基氢过氧化物和反式-7-氧杂双环[4.1.0]庚-4-烯-3-基氢过氧化物。氢过氧内过氧化物用亚硫酸氢钠水溶液还原；氢过氧环氧化物用二甲基硫醚-四异丙醇钛还原得到7-氧杂双环[4.1.0]庚-4-烯-3-醇。环氧醇的酸水解得到(1,4/2)-环己-3-烯三醇。用高锰酸钾氧化双键得到(±)-原栎醇。