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Catalytic Desaturation of Aliphatic Amides and Imides Enabled by Excited-State Base-Metal Catalysis

Chenyang Wang, Luis Miguel Azofra, Phong Dam, Michael Šebek, Norbert Steinfeldt, Jabor Rabeah, Osama El‐Sepelgy

2022ACS Catalysis41 citationsDOI

Abstract

Herein, we report a photoexcited base-metal-catalyzed selective desaturation of aliphatic amides and imides. The reaction is catalyzed by a base-metal cobalt complex under visible-light irradiation. This transformation can be efficiently processed at room temperature and enables the synthesis of valuable cyclic and acyclic enamides and enimides from abundant chemicals. Density functional theory (DFT) analysis, electron paramagnetic resonance (EPR), and UV–vis studies rationalized the discovered reactivity of the cobalt catalyst for the photochemical C(sp3)–H activation reaction. Finally, we demonstrated the potential of our process by scaling-up experiments using a continuous flow photoreactor.

Topics & Concepts

CatalysisChemistryCobaltElectron paramagnetic resonanceReactivity (psychology)PhotochemistryMetalDensity functional theoryBase (topology)Combinatorial chemistryOrganic chemistryComputational chemistryMathematical analysisMedicinePathologyPhysicsAlternative medicineNuclear magnetic resonanceMathematicsCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling ReactionsAsymmetric Hydrogenation and Catalysis