Gold vs Light: Chemodivergent Reactivity of Diazoesters toward 2<i>H</i>-Azirine-2-carboxylic Acids
Gleb D. Titov, Grigory I. Antonychev, Михаил С. Новиков, Alexander F. Khlebnikov, Elizaveta Rogacheva, Л. А. Краева, Николай В. Ростовский
Abstract
An orthogonal reactivity of diazo compounds toward azirine-2-carboxylic acids, switching with the reaction conditions, is demonstrated. A gold-catalyzed reaction is N-selective and produces 1,3-oxazin-6-ones, whereas a blue light activation leads to O-H insertion products, azirine-2-carboxylic esters. The observed chemodivergence is explained by the metal-bound and metal-free carbenes exhibiting different electronic properties in these reactions. In addition, a high antibacterial potential of the 1,3-oxazin-6-ones synthesized is shown.
Topics & Concepts
ChemistryAzirineReactivity (psychology)DiazoMetalCatalysisCombinatorial chemistryMedicinal chemistryOrganic chemistryMedicineAlternative medicinePathologyRing (chemistry)Cyclopropane Reaction MechanismsCatalytic C–H Functionalization MethodsSynthesis and Catalytic Reactions