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Photochemical transformations. 36. Intramolecular electron transfer from photoexcited benzene rings to carbon-mercury bonds. Stereochemical fate of zwitterionic biradicals leading to Wagner-Meerwein rearranged products.

Authors
Journal
Tetrahedron Letters
0040-4039
Publisher
Elsevier
Publication Date
Volume
24
Issue
52
Identifiers
DOI: 10.1016/s0040-4039(00)94215-1

Abstract

Abstract Irradiation of cis -8-X-mercuri-2,3;5,6-dibenzobicyclo[2.2.2]-octa-2,5-diene-7-ol acetate (X = Cl and OAc) ( 3 ) and the trans -diastereoisomer ( 4 ) (X = Cl) in glacial acetic acid, in acetonitrile, or in a mixture of glacial acetic acid and acetonitrile with 254-nm and 285-nm light gives metallic mercury and Wagner-Meerwein rearranged photosolvolysis or ion-pair return products. The reactions are stereoconvergent. A mechanistic path involving intramolecular electron transfer and an excited-state πp cation biradical is suggested to rationalize the results.

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