Asymmetric Coupling of Carbon‐Centered Radicals Adjacent to Nitrogen: Copper‐Catalyzed Cyanation and Etherification of Enamides
Guoyu Zhang, Song Zhou, Liang Fu, Pinhong Chen, Yibiao Li, Jian‐Ping Zou, Guosheng Liu
Abstract
The first copper-catalyzed asymmetric cyanation and etherification reactions of enamides have been established, where a carbon-centered radical adjacent to a nitrogen atom (CRAN) is enantioselectively trapped by a chiral copper(II) species. Moreover, the asymmetric cyanation of vinyl esters was disclosed as well. These reactions feature very mild reaction conditions and high functional group tolerance, and give a series of chiral α-cyano amides, α-cyano esters and α-hemiaminals in good yields with excellent enantioselectivity. The chiral α-cyano amides can be easily converted into enantioenriched 1,2-diamines and amino acids.
Topics & Concepts
CyanationChemistryCopperCatalysisAsymmetric carbonRadicalNitrogen atomCarbon fibersEnantioselective synthesisNitrogenCarbon atomOrganic chemistryCombinatorial chemistryGroup (periodic table)Optically activeComposite numberAlkylMaterials scienceComposite materialCatalytic C–H Functionalization MethodsRadical Photochemical ReactionsSulfur-Based Synthesis Techniques