Visible light-mediated aza Paternò-Büchi reaction of acyclic oximes and alkenes to azetidines.
basic_science · Level V
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- Record sourced from PubMed, PMID 38935726.
- Also identified by DOI 10.1126/science.adj6771.
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Abstract
The aza Paternò-Büchi reaction is a [2+2]-cycloaddition reaction between imines and alkenes that produces azetidines, four-membered nitrogen-containing heterocycles. Currently, successful examples rely primarily on either intramolecular variants or cyclic imine equivalents. To unlock the full synthetic potential of aza Paternò-Büchi reactions, it is essential to extend the reaction to acyclic imine equivalents. Here, we report that matching of the frontier molecular orbital energies of alkenes with those of acyclic oximes enables visible light-mediated aza Paternò-Büchi reactions through triplet energy transfer catalysis. The utility of this reaction is further showcased in the synthesis of <i>epi-</i>penaresidin B. Density functional theory computations reveal that a competition between the desired [2+2]-cycloaddition and alkene dimerization determines the success of the reaction. Frontier orbital energy matching between the reactive components lowers transition-state energy (Δ<i>G</i><sup>ǂ</sup>) values and ultimately promotes reactivity.