Difluorocarbene-induced [1,2]- and [2,3]-Stevens rearrangement of tertiary amines

Abstract

The [1,2]- and [2,3]-Stevens rearrangements are one of the most fascinating chemical bond reorganization strategies in organic chemistry, and they have been demonstrated in a wide range of applications, representing a fundamental reaction tactic for the synthesis of nitrogen compounds in chemical community. However, their applicabilities are limited by the scarcity of efficient, general, and straightforward methods for generating ammonium ylides. Herein, we report a general difluorocarbene-induced tertiary amine-involved [1,2]- and [2,3]-Stevens rearrangements stemmed from in situ generated difluoromethyl ammonium ylides, which allows for the rearrangements of versatile tertiary amines bearing either allyl, benzyl, or propargyl groups, resulting in the corresponding products in one reaction under the same reaction conditions with a general way. Broad substrate scope, simple operation, mild reaction conditions and late-stage modification of natural products highlight the advantages of this strategy, meanwhile, this general rearrangement reaction is believed to bring opportunities for the transformations of nitrogen ylides and the assembly of valuable tertiary amines and amino acids. This will further enrich the reaction repertoire of difluorocarbene species, facilitate the development of reactions involving difluoromethyl ammonium salts, and provide an avenue for the development of this type of rearrangement reactions.