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Electrochemical 1,2‐Diarylation of Alkenes Enabled by Direct Dual C–H Functionalizations of Electron‐Rich Aromatic Hydrocarbons

Jing‐Hao Qin, Mu‐Jia Luo, Delie An, Jin‐Heng Li

2020Angewandte Chemie International Edition95 citationsDOIOpen Access PDF

Abstract

Abstract A cobalt‐promoted electrochemical 1,2‐diarylation of alkenes with electron‐rich aromatic hydrocarbons via direct dual C−H functionalizations is described, which employs a radical relay strategy to produce polyaryl‐functionalized alkanes. Simply by using graphite rod cathode instead of platinum plate cathode, chemoselectivity of this radical relay strategy is shifted to the dehydrogenative [2+2+2] cycloaddition via 1,2‐diarylation, annulation, and dehydrogenation cascades leading to complex 11,12‐dihydroindolo[2,3‐ a ]carbazoles. Mechanistical studies indicate that a key step for the radical relay processes is transformations of the aromatic hydrocarbons to the aryl sp 2 ‐hybridized carbon‐centered radicals via deprotonation of the corresponding aryl radical cation intermediates with bases.

Topics & Concepts

ChemistryDehydrogenationDeprotonationElectrochemistryRadicalPhotochemistryAryl radicalChemoselectivityAromaticityCombinatorial chemistryArylBoronAnnulationOrganic chemistryCatalysisAlkylElectrodeMoleculeIonPhysical chemistryCatalytic C–H Functionalization MethodsRadical Photochemical ReactionsFluorine in Organic Chemistry
Electrochemical 1,2‐Diarylation of Alkenes Enabled by Direct Dual C–H Functionalizations of Electron‐Rich Aromatic Hydrocarbons | Litcius