Gold vs Light: Chemodivergent Reactivity of Diazoesters toward 2 H -Azirine-2-carboxylic Acids.
Gleb D TitovGrigory I AntonychevMikhail S NovikovAlexander F KhlebnikovElizaveta V RogachevaLiudmila A KraevaNikolai V RostovskiiPublished in: Organic letters (2023)
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.