Synlett
DOI: 10.1055/s-0036-1590882
letter
© Georg Thieme Verlag Stuttgart · New York

Unexpected Rearrangement of 2-Bromoaniline under Biphasic Alkylation Conditions

Scott J. Barraza, Scott E. Denmark*
  • Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, IL 61801, USA   Email: sdenmark@illinois.edu
This work is generously supported by Janssen Research and Development LLC, San Diego.
Further Information

Publication History

Received: 21 June 2017

Accepted after revision: 28 July 2017

Publication Date:
21 August 2017 (eFirst)

Dedicated to big brother Vic on the festive occasion of his entry into the ninth decade

Abstract

Alkylation of 2-bromoaniline with benzyl bromide under ostensibly basic N-alkylation conditions resulted in migration of bromine from the 2- to the 4-aryl position. Herein we report our studies to elucidate the mechanism of this rearrangement with the objective of suppressing this unexpected outcome. We find that careful choice of reagents is critical, and that this behavior may be extrapolated to alkylation reactions of electron-rich bromo- and iodoanilines in general.

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