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Accelerated Electrophotocatalytic C(sp3)−H Heteroarylation Enabled by an Efficient Continuous-Flow Reactor**
Authors:Dimitris I Ioannou  Prof Dr Luca Capaldo  Jiri Sanramat  Prof Dr Joost N H Reek  Prof Dr Timothy Noël
Institution:1. Flow Chemistry Group, van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands

Supramolecular and Homogeneous Catalysis Group, van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands;2. Flow Chemistry Group, van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands

SynCat Lab, Department of Chemistry, Life Sciences and Environmental Sustainability, University of Parma, 43124 Parma, Italy;3. Flow Chemistry Group, van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands;4. Supramolecular and Homogeneous Catalysis Group, van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands

Abstract:Electrophotocatalytic transformations are garnering attention in organic synthesis, particularly for accessing reactive intermediates under mild conditions. Moving these methodologies to continuous-flow systems, or flow ElectroPhotoCatalysis (f-EPC), showcases potential for scalable processes due to enhanced irradiation, increased electrode surface, and improved mixing of the reaction mixture. Traditional methods sequentially link photochemical and electrochemical reactions, using flow reactors connected in series, yet struggle to accommodate reactive transient species. In this study, we introduce a new flow reactor concept for electrophotocatalysis (EPC) that simultaneously utilizes photons and electrons. The reactor is designed with a transparent electrode and employs cost-effective materials. We used this technology to develop an efficient process for electrophotocatalytic heteroarylation of C(sp3)−H bonds. Importantly, the same setup can also facilitate purely electrochemical and photochemical transformations. This reactor represents a significant advancement in electrophotocatalysis, providing a framework for its application in flow for complex synthetic transformations.
Keywords:Electrophotocatalysis  Flow Chemistry  Heteroarylation  Hydrogen Atom Transfer  Microreactor
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