Oxime-Derived Iminyl Radicals in Selective Processes of Hydrogen Atom Transfer and Addition to Carbon-Carbon π-Bonds

Oximes represent one of the fundamental organic compound classes with a wide range of synthetic applications. In the last decade O-substituted oximes were recognized as the synthetically available and versatile precursors of iminyl radicals via one-electron oxidation or one-electron reduction employing visible light photoredox catalysts, salts of abundant metals (such as Cu or Fe), or other convenient reagents. Iminyl radicals are powerful synthons for various processes of cyclization, ring-opening, CH-functionalization, and coupling. The present review is focused on the synthetic methods based on oxime-derived iminyl radicals developed in the last few years excluding ring opening reactions of cyclic iminyl radicals that were summarized in recent publications. The review consists of two main parts: (1) reactions of iminyl radicals involving 1,n-hydrogen atom transfer (n=5 in most cases) and (2) reactions involving the addition of iminyl radical to the carbon-carbon pi-bond.

Automated summary

This review focuses on synthetic methods based on oxime-derived iminyl radicals developed in the last few years, excluding ring opening reactions of cyclic iminyl radicals summarized in recent publications. It highlights reactions involving 1,n-hydrogen atom transfer and addition of iminyl radicals to the carbon-carbon pi-bond, showcasing the versatility and utility of these methods in organic synthesis.