Reduction of NN, NN, NO and OO Bonds

Abstract

This chapter covers methods of reduction of nitrogennitrogen multiple bonds and methods for the reductive cleavage of NN, NO and OO bonds. Perhaps the most important use of reactions of these types is that they can allow the introduction of amino and hydroxy groups with considerable control of stereochemistry. Amino groups are often introduced by the use of azide ion and occasionally by hydroxylamines or hydrazines as nucleophiles, followed by reductive cleavage. Hydroxy groups can similarly be introduced by way of peroxides. Activated azo and nitroso compounds and singlet oxygen are excellent dienophiles in the Diels–Alder reaction and the cleavage of the heteroatom to heteroatom bonds permits two functional groups to be introduced in a controlled manner. Alkenes and alkynes can also be functionalized at both termini by the cycloaddition of 1,3-dipoles such as nitrones, nitrile imides and nitrile oxides, followed by reductive cleavage.