Alkynolate anions via a new rearrangement: the carbon analog of the Hofmann reaction

CJ Kowalski, KW Fields

Index: Kowalski, Conrad J.; Fields, Kevin W. Journal of the American Chemical Society, 1982 , vol. 104, # 1 p. 321 - 323

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Citation Number: 50

Abstract

Herein we report the first examples of a previously unknown reaction, the carbon analogue of the Hofmann rearrangement. The classical Hofmann reaction* involves deprotonation of an N-bromoamide (1-2) followed by migration of a group to nitrogen with loss of bromide to form an isocyanate (2-3). The new reaction described herein is formally isoelectronic with that process; ie, an a-bromoketone enolate is deprotonated (4-5) and rearranges with loss ...