Authors: Lutz Ackermann | Song Lin
Source: European Journal of Organic Chemistry (article, 2023-03-30)
Field: Chemistry — Organic Chemistry

Special Collection on Organic Electrocatalysis The past several years has witnessed an exciting renaissance of the field of organic electrosynthesis and electrocatalysis. As an unconventional reaction tool with many unique features, electrochemistry has enabled synthetic chemists to invent novel transformations, advance new synthetic strategies, and improve the sustainability of organic synthesis. In this Guest Editorial, Song Lin and Lutz Ackermann introduce the special collection on organic electrocatalysis. Electrochemistry represents an attractive approach to discovering new reactions and overcoming current challenges in organic synthesis.1 In particular, electrocatalysis—a process that integrates electrochemistry and homogenous or heterogeneous catalysis—has the potential to substantially improve the scope of synthetic electrochemistry and provide a wide range of useful transformations.2 Innovative research in the past several years has demonstrated that electrochemistry and electrocatalysis offer unique opportunities for increasing the efficiencies and sustainability of chemical synthesis and for granting access to new molecules that are not readily accessible by conventional methods. In this Special Collection, the European Journal of Organic Chemistry highlights the latest progress in this field. Articles enclosed in this Special Collection cover a broad range of research topics within the scope of organic electrosynthesis and electrocatalysis. In the realm of transition-metal-catalyzed electrosynthesis, Fu and co-workers achieve the radical-based difunctionalization of alkenes by means of Fe/Mn dual catalysis; Jones and co-workers employ a catalytic dyad encompassing a benzoquinone and an iron complex to effect the dehydrogenation of alcohols; and Wang, Wang, and co-workers establish a Ni-catalyzed strategy for the C−S cross-coupling to transform aryl iodides to sulfides and sulfones. Moving beyond methodology development, Frankowski and co-workers apply a late-stage anodic cyclization reaction to achieve a concise total synthesis of natural product (±)-physovenine. Finally, Zeng, Xu, and co-workers review electrocatalytic methods for the generation of acyl radicals and their applications in organic synthesis. In addition to method development, this Special Collection highlights a number of mechanistic studies of electrosynthetic transformations. Okada and co-workers contribute two reports in this regard to elucidate the mechanism of radical cation-mediated vinylcyclopropane rearrangement and [4+2] cycloaddition. Sigman, Minteer, and co-workers employ a combination of electroanalytical and data science tools to examine halogen-atom abstraction kinetics for a series of first-row transition metal complexes, thus laying the mechanistic basis for the development of electrocatalytic functionalization of alkyl halides. In recent years, the development of technology has further driven innovations in electrosynthesis and electrocatalysis. In this Special Collection, contributions by Ye and co-workers as well as Xu and co-workers each demonstrate the use of continuous flow to facilitate the electrochemical synthesis of heterocyclic compounds such as thiophenes and spirooxindoles. Moreover, Atobe, Shida and co-workers report the design of three electrochemical flow microreactors to promote a series of electrochemical and electrophotochemical reactions in both divided and undivided cell settings. Molecular electrosynthesis has been recognized as an increasingly powerful platform for organic synthesis. Hence, organic electrosynthesis has emerged as a uniquely effective toolbox, enabling innovative reactions through the identification of new mechanistic insights.3 This Special Collection nicely mirrors the potential and emerging trends of organic electrosynthesis. Given the transformative power of molecular electrosynthesis summarized herein, we feel that exciting future developments are expected in this rapidly evolving research area. For instance, innovative electrode materials are expected to have a major impact in the field by allowing chemists to understand and improve the efficacy of proton-coupled electron transfer (PCET) to control overpotentials.4, 5 Likewise, the synergistic use of both half-cell reactions within paired electrolysis will set the stage for improved resource economy.6 On a different note, electrophotocatalysis allows for reactions at extreme redox potentials to enable entirely novel chemical transformations.7 Enantioselective electrocatalysis remains underexplored, yet bears great potential for asymmetric transformations under exceedingly mild conditions.8 The integration of biocatalysis with electrochemistry will unlock new ways to achieve enantioselective redox transformations.9 Finally, the adoption of modern data analysis techniques and artificial intelligence, guided by mechanistic insights, promises to unveil novel reaction manifolds.10 The success of these challenging objectives will strongly rely on interdisciplinary approaches between molecular synthesis, catalysis, material sciences, physics, and computation. The opinions expressed in this publication are the view of the authors and do not necessarily reflect the opinions or views of the European Journal of Organic Chemistry, the Publisher, Chemistry Europe, or the affiliated editors. The authors acknowledge Andrew Ressler (Cornell) for proofreading the manuscript. Lutz Ackermann studied Chemistry at the University Kiel, and performed his PhD with Prof. A. Fürstner at the MPI für Kohlenforschung (2001). After a postdoctoral stay at UC Berkeley with Prof. Robert G. Bergman, he initiated his independent research career in 2003 at the LMU München. In 2007, he became Full Professor at the Georg-August-University Göttingen. His recent distinctions include an AstraZeneca Excellence in Chemistry Award (2011), an ERC Consolidator (2012) and Advanced Grant (2021), and a Gottfried-Wilhelm-Leibniz-Preis (2017). The development and application of novel concepts for sustainable catalysis constitutes his major current research interests, with a topical focus on organic electrocatalysis and C-H activation. Song Lin grew up in Tianjin, China. He obtained B.S. from Peking University (2008) and Ph.D. at Harvard University (2013) working with Eric Jacobsen. He then carried out postdoctoral studies with Chris Chang at UC Berkeley. In 2016, he started his independent career at Cornell University, where he is currently a Tisch University Professor. He has received several early career awards including the Sloan Fellowship, National Fresenius Award, and EPA Green Chemistry Challenge. He is currently an Associate Editor at Organic Letters and serves on the Advisory Board of Synlett and Chemistry – A European Journal. His research focuses on using fundamental principles of electrochemistry and radical chemistry to discover new organic transformations and uncover new reaction mechanisms. Electrocatalyst ; Electrosynthesis ; Chemistry ; Organic synthesis ; Nanotechnology ; Electrochemistry ; Catalysis ; Organic chemistry ; Materials science Radical Photochemical Reactions ; Sulfur-Based Synthesis Techniques ; Oxidative Organic Chemistry Reactions