Photoredox-Catalyzed Decarboxylation of Oxetane-2-Carboxylic Acids and Unique Mechanistic Insights

Oxetanes are valuable motifs in medicinal chemistry applications, with demonstrated potential to serve as bioisosteres for an array of functional groups. Through the visible-light-mediated photoredox hydrodecarboxylation of 2-aryl oxetane 2-carboxylic acids this work enables access to the products of a [2+2]-photocycloaddition between alkenes and aryl aldehydes without the challenges associated with a traditional UV-light-mediated Paternò-Büchi reaction. Investigation into the hydrodecarboxylation mechanism reveals substrate-dependent modes of initiation under the conditions reported herein. Divergence in diastereomeric outcome is observed, with mechanistic probes elucidating key hydrogen-bonding and steric interactions.