A novel and short synthesis of (1,4/2)-cyclohex-5-ene-triol and its conversion to (+/-)-proto-quercitol.
(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.
Gültekin
M Serdar
MS
Department of Chemistry, Faculty of Arts and Sciences, Atatürk University, 25240 Erzurum, Turkey.
Salamci
Emine
E
Balci
Metin
M
D003510:Cyclohexanes / Q000138:chemical synthesis* / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D007294:Inositol / Q000031:analogs & derivatives / Q000138:chemical synthesis* / Q000737:chemistry*; D007536:Isomerism; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D011522:Protons; D013447:Sulfites / Q000737:chemistry
C483224:(1,4,2)-cyclohex-5-ene-triol; D003510:Cyclohexanes; D004852:Epoxy Compounds; D011522:Protons; D013447:Sulfites; C483225:proto-quercitol; D007294:Inositol; C009279:sodium bisulfite