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RESEARCH ARTICLE
Contents Vol 67(3)

Intermediates in the Formation and Thermolysis of Peroxides from Oxidations with Singlet Oxygen

Werner Fudickar A and Torsten Linker A B
+ Author Affiliations
- Author Affiliations

A Department of Chemistry, University of Potsdam, Karl-Liebknecht-Str. 24–25, 14476 Potsdam, Germany.

B Corresponding author. Email: linker@uni-potsdam.de

Australian Journal of Chemistry 67(3) 320-327 https://doi.org/10.1071/CH13423
Submitted: 15 August 2013  Accepted: 3 October 2013   Published: 30 October 2013

Abstract

Herein we describe the recent mechanistic understandings of the singlet oxygen ene reaction to give hydroperoxides and the [4+2] cycloaddition affording endoperoxides. Both experimental findings and theoretical work conclude in the formation of intermediates structurally similar to perepoxides during the ene reaction. Such intermediates mainly control the regio- and stereoselectivities of this reaction class. For the [4+2] cycloaddition, both a synchronous concerted reaction (benzene, naphthalenes) and a stepwise reaction with a non-symmetric zwitterionic intermediate (larger acenes) have been found. The thermolysis of endoperoxides derived from acenes proceeds stepwise for anthracenes, but in a concerted manner for less stable adducts such as naphthalene.


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