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Letters in Organic Chemistry

Editor-in-Chief

ISSN (Print): 1570-1786
ISSN (Online): 1875-6255

Brown Selectivity Disobedience of Hyperdeaminative Friedel-Crafts Benzylation: Electrophilic Aromatic Substitutions via Hyperdeaminatively Generated Benzyl Carbocations

Author(s): R. W. Darbeau, L. M. Siso, G. A. Trahan and R. S. Nolan

Volume 2, Issue 2, 2005

Page: [139 - 144] Pages: 6

DOI: 10.2174/1570178053202928

Price: $65

Abstract

Hyperdeamination generates multiple spacer-molecule separated ion-pairs containing high-energy, relatively long-lived carbocations showing near specificity for arenes over their nascent counterions. They exhibit low intermolecular selectivity but surprisingly high intramolecular selectivity. Unlike analogous deaminative benzylations, hyperdeaminative benzylations disobey the Brown Selectivity Relationship. A model for EAS reactions with hyperactive electrophiles is proposed.

Keywords: hyperdeamination, deamination, brown selectivity relationship, friedel-crafts, benzylation


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