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Updated: Sep 19, 2025

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Monocyclic Azetidines via a Visible-Light-Mediated Aza Paternò-Büchi Reaction of Ketone-Derived Sulfonylimines
Cody H Ng1,2, Emily R Wearing1, Dominique E Blackmun1,2
1Department of Chemistry, University of Michigan, 930 N University Ave, Ann Arbor, Michigan 48109, United States.
Abstract:
The recent rise in popularity of azetidines in pharmaceutical chemistry has inspired the development of visible-light-mediated aza Paternò-Büchi reactions as direct transformations to form these desirable products. Despite these advancements, successful reports of accessing monocyclic azetidines from acyclic imines remain scarce. Here, we report a visible-light-mediated aza Paternò-Büchi reaction of acyclic ketone-derived sulfonylimines, which are previously unexplored substrates in this transformation, with activated alkenes (i.e., styrenes and dienes) to form 2,2-disubstituted monocyclic azetidines that can be further modified to reveal free N-H azetidines. Computational and experimental mechanistic studies reveal that in contrast to aldehyde-derived oximes, the use of ketone-derived sulfonylimines enables tuning of the reaction mechanism to favor initial formation of the C-N rather than C-C bond, thus enabling access to 2,2-disubstituted monocyclic azetidine scaffolds.
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