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

Gultekin M., Salamci E., Balci M.

CARBOHYDRATE RESEARCH, vol.338, no.16, pp.1615-1619, 2003 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 338 Issue: 16
  • Publication Date: 2003
  • Doi Number: 10.1016/s0008-6215(03)00256-8
  • Journal Name: CARBOHYDRATE RESEARCH
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.1615-1619
  • Keywords: quercitol, singlet oxygen, ene-reaction, endoperoxide, hydroperoxide, DL-PROTO-QUERCITOL, DIASTEREOSELECTIVE ENE REACTION, SINGLET OXYGEN, CONVENIENT SYNTHESIS, INOSITOL, CONDURITOLS, CONCISE
  • Middle East Technical University Affiliated: No

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-oxabicclo[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. (C) 2003 Elsevier Ltd. All rights reserved.