Electrophilic Addition of Arylsulfenyl Chlorides to Tricyclo[4.2.2.02,5]deca-3,7-diene and -3,7,9-triene Systems. Novel Skeletal Rearrangements and Serendipitous Products

Nikolai S. Zefirov, Anatoly S. Koz'min, Valery N. Kirin, Viktor V. Zhdankin, Ronald Caple

Research output: Contribution to journalArticle

41 Scopus citations

Abstract

The addition of 2-nitro- and 2,4-dinitrobenzenesulfenyl chlorides in AcOH and under “doping conditions” (AcOH + LiClO4) to the olefins 8-10 has been investigated, and novel types of Wagner-Meerwein rearrangement have been found. The product distributions as well as the different configurations of rearranged chlorides (e.g., 18c) and acetates (e.g., 18d) were explained in terms of an ion-pair mechanism. Doping addition leads in part to the formation of covalent perchlorates (e.g., 12d,e), which have been isolated and identified. The general mechanistic features and stereochemical sequence for the ion-pair mechanism of ArSCl addition to a carbon-carbon double bond are discussed.

Original languageEnglish (US)
Pages (from-to)5264-5275
Number of pages12
JournalJournal of Organic Chemistry
Volume46
Issue number26
DOIs
StatePublished - Dec 1981

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