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C(<i>sp</i><sup>3</sup>)−C(<i>sp</i><sup>3</sup>) Cross‐Coupling of Alkyl Bromides and Ethers Mediated by Metal and Visible Light Photoredox Catalysis

Marília S. Santos, Arlene G. Corrêa, Márcio W. Paixão, Burkhard König

2020Advanced Synthesis & Catalysis55 citationsDOIOpen Access PDF

Abstract

Abstract We report a C( sp 3 )−C( sp 3 ) cross‐coupling of alkyl bromides and alkyl chlorides with ethers by dual photoredox‐nickel catalysis. The catalytic system comprises of the organic photocatalyst 1,2,3,5‐tetrakis(carbazol‐9‐yl)‐4,6‐dicyanobenzene (4‐CzIPN) and bench stable nickel (II) acetylacetonate in the presence of visible‐light, providing the coupling products in up to 92% yield. Preliminary mechanistic studies suggest two catalytic cycles, as well as the photogeneration of bromine or chlorine radicals from halide atoms that are present in the structures of the coupling partners. The halide radical mediates the hydrogen atom transfer event, avoiding the need of an additional HAT catalyst. magnified image

Topics & Concepts

ChemistryAlkylCatalysisHalidePhotochemistryNickelPhotocatalysisRadicalYield (engineering)BromineMetalCoupling reactionVisible spectrumMedicinal chemistryInorganic chemistryOrganic chemistryOptoelectronicsMetallurgyMaterials sciencePhysicsRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques