Expedient Access to Structural Complexity via Radical β-Fragmentation of N-O Bonds

Structures containing N-O bonds are well-established precursors of nitrogen- and/or oxygen-centered radicals under visible-light conditions in modern organic synthesis. Whereas both heterolytic and homolytic scissions of N-O bonds have been extensively documented, intrinsic limitations related to substrate structure somewhat restrict their broader application. This paper highlights a novel strategy that synergistically combines a radical-generation process that is independent of the substrate's redox potential with a radical-induced β-fragmentation of the N-O bond. Subsequent manipulation of the generated nitrogen- or oxygen-centered radicals leads to the successful development of group-transfer carboamination of alkenes, ring-opening functionalization of heterocycles, and efficient trifunctionalization of nonactivated alkenes. 1 Introduction 2 Carboamination of Nonactivated Alkenes 3 Radical-Addition-Induced Ring-Opening Functionalization of 4-Isoxazolines 4 Multisite Functionalization of Alkenes by Merging Cycloaddition and Ring-Opening Functionalization 5 Conclusion.