2,3-dioxabicyclo[2.2.2]oct-7-en-5-one: Synthesis and reactions of the keto endoperoxide of phenol

Adam W., Balci M., Kilic H.

JOURNAL OF ORGANIC CHEMISTRY, vol.65, no.19, pp.5926-5931, 2000 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 65 Issue: 19
  • Publication Date: 2000
  • Doi Number: 10.1021/jo000120p
  • Journal Name: JOURNAL OF ORGANIC CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.5926-5931
  • Middle East Technical University Affiliated: No

Abstract

The photooxygenation of 1,4-cyclohexadiene (3) affords the diastereomeric hydroperoxy endoperoxides exo-4 and endo-4 and the diastereomeric hydroperoxides trans-5 and cis-5 in a ratio of 87: 9:3.5:0.5. Selective reduction of hydroperoxide group in the endoperoxides exo-4 and endo-4 in the presence of titanium tetraisopropoxide-diethyl sulfide gave the corresponding hydroxy endoperoxides exo-7 and endo-7, which on PCC oxidation leads to the phenol-derived keto endoperoxide 2. The triphenylphosphine deoxygenation of the keto endoperoxide 2 produces a 9:1 mixture of 1,2- and 1,4-dihydroxybenzenes 10 and 11, while the CoTPP-catalyzed rearrangement affords the bisepoxide 12, malealdehyde (13), and beta-lactone 14. The mechanisms of these transformations are presented.