Mander’s Reagent for the Deoxycyanation of β-Diketones: A Direct Synthesis of Oxoalkenenitriles

Abstract

Ethyl and methyl cyanoformate (Mander’s reagent) are reagents to routinely perform C-selective ketone alcoxycarbonylations. Interestingly, both reagents were found to yield oxoalkenenitriles through an unprecedented deoxycyanation on 1,3-dicarbonyl compounds (e. g. 2-methyl-1,3-cyclohexanedione). Although this method was not general, this is the first time both Mander’s reagent and ethyl cyanoformate were used for the deoxycyanation of 1,3-dicarbonyl compounds for the preparation of synthetically useful oxoalkenenitriles. Limitations on the substrate scope for the present methodology are discussed.