Efficient unimolecular deprotonation of aniline radical cations

Gary W. Dombrowski, Joseph P. Dinnocenzo, Paul A. Zielinski, Samir Farid, Zofia M. Wosinska, Ian Gould

Research output: Contribution to journalArticlepeer-review

37 Scopus citations

Abstract

Deprotonation of the radical cations of aromatic amines, such as anilines, generally occurs much more slowly than other fragmentation reactions. Here we report a stereoelectronic effect involving twisting of the anilino group out of the plane of the benzene ring that results in a significantly increased rate of reactivity toward deprotonation. Quantitative studies of the rate constants for deprotonation as a function of aniline radical cation pKa (Brønsted plots) demonstrate that the effect is not simply due to a change in the reaction thermodynamics. By combining this stereoelectronic effect with covalent attachment of carboxylate as a base, aniline radical cations that undergo unimolecular deprotonation with rate constants as high as 10 8 s-1, even in unfavorable protic media, are described.

Original languageEnglish (US)
Pages (from-to)3791-3800
Number of pages10
JournalJournal of Organic Chemistry
Volume70
Issue number10
DOIs
StatePublished - May 13 2005

ASJC Scopus subject areas

  • Organic Chemistry

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