Oxidation Reactions of Benzvalene: Ozonolysis, cis-Hydroxylation, Epoxidation, and Singlet Oxygen Addition

✍ Scribed by Dipl.-Chem. Hartmut Leininger; Prof. Dr. Manfred Christl

• Publisher: John Wiley and Sons
• Year: 1980
• Tongue: English
• Weight: 252 KB
• Volume: 19
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/anie.198004581

✦ Synopsis

chain reaction already accepted in the case of other bicy-cl~[l.l.O]butanes[~~.

Why does the phenylthio radical attack benzvalene (1) at the double bond but homobenzvalene (8) at the bicy-clot1 .I .O]butane system? Since thio radicals have electrophilic characterf7I, the interaction with the HOMO of the substrate may play the decisive role in the transition state of the addition. As shown by the ionization potentials determined by photoelectron spectroscopy and assigned on the basis of MIND0/3 caIculations['l, the HOMO in (1) is located in the double bond, in @), however, in the central bond of the bicyclo[l.l.O]butane system (Fig. ).