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We present a novel deoxygenation method for heterocyclic Noxides utilizing iodide as a catalyst. Iodide acts as a reducing catalyst that is regenerated by formic acid, which also serves as a Brønsted activator and solvent. The method demonstrates high efficiency and excellent selectivity in the reduction of a variety of heterocyclic N-oxides and tertiary amines. Our computational DFT investigation revealed that the reduction mechanism entails a direct interaction between iodide and the oxygen of the N-oxide within a Mg2+/formic acid framework, resulting in the formation of the N-heterocycle and the release of a hypoiodite unit. Additionally, a molecular mechanism for the regeneration of iodide from hypoiodite, facilitated by formic acid, is suggested. This method provides an environmentally friendly approach for the deoxygenation of N-oxides and related species. [ABSTRACT FROM AUTHOR]

Ethyl cyanoformate and methyl cyanoformate (Mander's reagent) are both routinely used to perform C-selective ketone alkoxycarbonylations. Interestingly, both reagents were found to yield oxoalkenenitriles through an unprecedented deoxycyanation of 1,3-dicarbonyl compounds (e.g., 2-methylcyclohexane-1,3-dione). Although this method is not general, this is the first time that both Mander's reagent and ethyl cyanoformate have been used for the deoxycyanation of 1,3-dicarbonyl compounds for the preparation of synthetically useful oxoalkenenitriles. Limitations on the substrate scope of the present method are discussed. [ABSTRACT FROM AUTHOR]