Unexpected Rearrangement of 2-Bromoaniline under Biphasic Alkylation ConditionsThis work is generously supported by Janssen Research and Development LLC, San Diego.
Received: 21 June 2017
Accepted after revision: 28 July 2017
21 August 2017 (eFirst)
Dedicated to big brother Vic on the festive occasion of his entry into the ninth decade
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.