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

Date

2000-09-22

Author

Adam, W
Balcı, Metin
Kilic, H

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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.

Subject Keywords

Singlet oxygen, Bicyclic endoperoxides, Oxidation

URI

https://hdl.handle.net/11511/57841

Journal

JOURNAL OF ORGANIC CHEMISTRY

DOI

https://doi.org/10.1021/jo000120p

Collections

Graduate School of Natural and Applied Sciences, Article

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Citation Formats

W. Adam, M. Balcı, and H. Kilic, “2,3-dioxabicyclo[2.2.2]oct-7-en-5-one: Synthesis and reactions of the keto endoperoxide of phenol,” JOURNAL OF ORGANIC CHEMISTRY, pp. 5926–5931, 2000, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/57841.