Selective monodeoxygenation of quinoxaline-amino acid and ester dioxides

Abstract

Trimethyl phosphite selectively removes the N-1-oxygen in N-(3-methyl-2-quinoxaloyl) L-α-amino ester-1,4-dioxides, whereas it removes the N-4-oxygen in the corresponding series of dioxides lacking the C 3-Me. This selectivity reversal reflects the relative strength of the intrahydrogen-bridging to the N-1-oxygen. The monoxides having the favourable N-oxygen are not reduced to the quinoxalines, implying that the reagent requires doubling of the N-oxide function for deoxygenation. However, alkaline sodium dithionite removes the N-1-oxygen in both series of the amino acid-dioxides, as well as in the parent quinoxaline-2-carboxylic acid-dioxides, a result that contradicts the report stating removal of the N-4-oxygen. The N-oxygenated quinoxalinium ion ( m e 145 or 159) prevails in the MS of the 4-oxides, but it is not observed (<1%) for the isomeric 1-oxides. 1H NMR, 13C NMR and UV spectral data also offer diagnostic criteria for differentiation between the isomeric 1- and 4-oxides. Aryl-heteryl “interaction” (as revealed by 1H NMR, though not by 13C NMR in the aromatic amino ester dioxides) is not manifested in the corresponding monoxides.