A New Algorithm for the Reactivity Umpolung of Aliphatic Nitro Compounds

Abstract

A new four-stage algorithm for the reactivity umpolung of aliphatic nitro compounds has been proposed and experimentally confirmed. Bis(trialkylsilyloxy)iminium cations, which are key intermediates in the new scheme, have been qualitatively and quantitatively determined by the method of double nuclear magnetic resonance. Their thermodynamic parameters have been determined. The kinetics of coupling of these cations with π-nucleophiles has been measured experimentally, and the stereodynamics of the interaction of these cations has been discussed using a general model involving anomeric assistance. The utility and novelty of the proposed approach for the development of modern methodology of organic synthesis using available aliphatic nitro compounds as initial reagents have been demonstarted.