Ring Expansion of Bicyclic Methyleneaziridines via Concerted, Near-Barrierless [2,3]-Stevens Rearrangements of Aziridinium Ylides.

ABSTRACT: The synthesis of densely functionalized azetidinesin a highly stereocontrolled manner is challenging, but interest in the bioactivities of these small heterocycles has stimulated methods for their preparation. We recently reported a one-carbon ring expansion of bicyclic methylene aziridines under dirhodium catalysis capable of delivering enantioenriched azetidines. This work explores this ring expansion using computational and experimental studies. DFT computations indicate that the reaction proceeds through formation of an aziridinium ylide, which is precisely poised for concerted, asynchronous ring-opening/closing to deliver the azetidines in a [2,3]-Stevens-type rearrangement. The concerted nature of this rearrangement is responsible for the stereospecificity of the reaction, where axia

SUBMITTER: Schmid SC 

PROVIDER: S-EPMC6173328 | biostudies-literature | 2018 Sep

REPOSITORIES: biostudies-literature