aza-Patternå–Büchi反应是亚胺和烯烃之间制备氮杂环丁烷，即四元含氮杂环的[2+2]-环加成反应。目前，成功的例子主要依赖于分子内变体或环状亚胺当量。为了释放aza-Patternå–Büchi反应的全部合成潜力，必须将反应扩展到无环亚胺当量。
该文中，研究人员报道了烯烃的前沿分子轨道能量与无环肟的前沿分子轨能量的匹配，通过三重态能量转移催化实现了可见光介导的aza-Parternå–Büchi反应。该反应的实用性在epi-penaresin B的合成中得到了进一步展示。
密度泛函理论计算表明，所需[2+2]-环加成和烯烃二聚之间的竞争决定了反应的成功。反应组分之间的前沿轨道能量匹配降低了过渡态能量（ΔG）值，并最终促进了反应性。
附：英文原文
Title: Visible light–mediated aza Paternò–Büchi reaction of acyclic oximes and alkenes to azetidines
Author: Emily R. Wearing, Yu-Cheng Yeh, Gianmarco G. Terrones, Seren G. Parikh, Ilia Kevlishvili, Heather J. Kulik, Corinna S. Schindler
Issue&Volume: 2024-06-28
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 epi-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 (ΔG) values and ultimately promotes reactivity.
DOI: adj6771
