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Nitrogenation and Oxygenation of an Unstrained C–C Bond Enabled by the Merger of Visible-Light and Cu-Catalysis

Yu Wang, Huan Meng, Sifan Li, Wei Shu

2024ACS Catalysis11 citationsDOI

Abstract

Unstrained carbon–carbon bonds are among the most prevalent and inert chemical bonds. Thus, developing synthetic transformations directly from unstrained carbon–carbon bonds under mild conditions is ideal yet challenging due to the inertness and steric hindrance. Here, a visible-light and copper-catalyzed azidation and etherification of a remote and unstrained C–C bond of amines via 1,4-aryl migration have been reported. This redox-neutral protocol shows exquisite site-selectivity, broad scope, and good functional group tolerance, directly transforming unstrained C–C bonds to C–N and C–O bonds at room temperature. Facile derivatizations of benzyl azide products into free amines, triazoles, and phosphamides highlight the potential utility of this method for target molecule synthesis and medicinal chemistry.

Topics & Concepts

ChemistrySteric effectsCatalysisPhotochemistryMoleculeArylCombinatorial chemistryOrganometallic chemistryCarbon fibersFunctional groupAzideOrganic chemistryMaterials sciencePolymerComposite numberAlkylComposite materialCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling ReactionsSulfur-Based Synthesis Techniques
Nitrogenation and Oxygenation of an Unstrained C–C Bond Enabled by the Merger of Visible-Light and Cu-Catalysis | Litcius