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(2+4)‐Cycloaddition with Singlet Oxygen. 17 O‐lnvestigation of the Reactivity of Furfuryl Alcohol Endoperoxide¶

1999; Wiley; Volume: 70; Issue: 6 Linguagem: Inglês

10.1111/j.1751-1097.1999.tb08295.x

1751-1097

André M. Braun, H. Dahn, Ernst Gassmann, Ioannis P. Gerothanassis, Laurent Jakob, J. Kateva, Claudia G. Martı́nez, Esther Oliveros,

Radical Photochemical Reactions

Abstract In earlier work, the use of furfuryl alcohol as a specific singlet oxygen acceptor was proposed because of the high ratio between the rate constants of chemical reaction and physical quenching. In contrast to furfuryl aldehyde, a number of products are formed by this type II photo‐oxidation of furfuryl alcohol. These products may be derived from the endoperoxide of furfuryl alcohol as a common intermediate. The present work focuses on the reactivity of this endoperoxide that was marked specifically by the use of 17 O 2 as a source for singlet oxygen. The analyses of the stable products, their yields and their labeling distribution reveal a strong solvent effect on the primary reaction pathways, and nucleophilic substitution reactions leading to hydroperoxide intermediates are dominant.