Visible light-mediated aza Paterno-Buchi reaction of acyclic oximes and alkenes to azetidines

• 成果类型: Article
• 署名作者: Wearing, Emily R.; Yeh, Yu-Cheng; Terrones, Gianmarco G.; Parikh, Seren G.; Kevlishvili, Ilia; Kulik, Heather J.; Schindler, Corinna S.
• 署名单位: University of Michigan System; University of Michigan; Massachusetts Institute of Technology (MIT); Massachusetts Institute of Technology (MIT); University of British Columbia; University of British Columbia; British Columbia Cancer Agency
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-10187
• DOI: 10.1126/science.adj6771
• 发表日期: 2024-06-28
• 页码: 1468-1476
• 关键词: stereoselective-synthesis; penaresidin-b; enantioselective synthesis; asymmetric-synthesis; c(sp(3))-h; amination; potent; bonds; aryl; photochemistry

摘要

The aza Paterno-Buchi 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 Paterno-Buchi 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 Paterno-Buchi 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 (Delta G(double dagger)) values and ultimately promotes reactivity.