Electrochemical Iodine‐Mediated Oxidation of Enamino‐Esters to 2<i>H</i>‐Azirine‐2‐Carboxylates Supported by <i>Design of Experiments</i>
Emre Babaoglu, Gerhard Hilt
Abstract
An electrochemical iodine-mediated transformation of enamino-esters for the synthesis of 2H-azirine-2-carboxylates is presented. In addition, a thermic conversion of azirines to 4-carboxy-oxazoles in quantitative yield without purification was described. Both classes 2H-azirines-2-carboxylates and the 4-carboxy-oxazoles are substructures in natural products and therefore are of considerable interest for synthetic and pharmaceutical chemists. The optimization was not performed in a conventional manner with a one-factor-at-a-time process but with a Design of Experiments (DoE) approach. Beside a broad substrate scope the reaction was also employed to a robustness screen, a sensitivity assessment, and complemented with mechanistic considerations from cyclic voltammetry experiments.