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      Efficient Aerobic Oxidation of Organic Molecules by Multistep Electron Transfer

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          Abstract

          This Minireview presents recent important homogenous aerobic oxidative reactions which are assisted by electron transfer mediators (ETMs). Compared with direct oxidation by molecular oxygen (O 2), the use of a coupled catalyst system with ETMs leads to a lower overall energy barrier via stepwise electron transfer. This cooperative catalytic process significantly facilitates the transport of electrons from the reduced form of the substrate‐selective redox catalyst (SSRC red) to O 2, thereby increasing the efficiency of the aerobic oxidation. In this Minireview, we have summarized the advances accomplished in recent years in transition‐metal‐catalyzed as well as metal‐free aerobic oxidations of organic molecules in the presence of ETMs. In addition, the recent progress of photochemical and electrochemical oxidative functionalization using ETMs and O 2 as the terminal oxidant is also highlighted. Furthermore, the mechanisms of these transformations are showcased.

          Abstract

          Recent progress in aerobic oxidations using electron transfer mediators (ETMs) via multistep electron relay is highlighted. The coupled catalytic systems significantly facilitate the transport of the electrons from the reduced substrate‐selective redox catalyst (SSRC) to O 2, thereby increasing the efficiency of the aerobic oxidation. This strategy has become powerful and valuable in synthetic organic chemistry.

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          Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

          Electrochemistry represents one of the most intimate ways of interacting with molecules. This review discusses advances in synthetic organic electrochemistry since 2000. Enabling methods and synthetic applications are analyzed alongside innate advantages as well as future challenges of electroorganic chemistry.
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            Redox catalysis in organic electrosynthesis: basic principles and recent developments.

            Electroorganic synthesis has become an established, useful, and environmentally benign alternative to classic organic synthesis for the oxidation or the reduction of organic compounds. In this context, the use of redox mediators to achieve indirect processes is attaining increased significance, since it offers many advantages compared to a direct electrolysis. Kinetic inhibitions that are associated with the electron transfer at the electrode/electrolyte interface, for example, can be eliminated and higher or totally different selectivity can be achieved. In many cases, a mediated electron transfer can occur against a potential gradient, meaning that lower potentials are needed, reducing the probability of undesired side-reactions. In addition, the use of electron transfer mediators can help to avoid electrode passivation resulting from polymer film formation on the electrode surface. Although the principle of indirect electrolysis was established many years ago, new, exciting and useful developments continue to be made. In recent years, several new types of redox mediators have been designed and examined, a process that can be accomplished more efficiently and purposefully using modern computational tools. New protocols including, the development of double mediatory systems in biphasic media, enantioselective mediation and heterogeneous electrocatalysis using immobilized mediators have been established. Furthermore, the understanding of mediated electron transfer reaction mechanisms has advanced. This review describes progress in the field of electroorganic synthesis and summarizes recent advances.
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              Asymmetric Transition Metal-Catalyzed Allylic Alkylations.

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                Author and article information

                Contributors
                jieliu@hnu.edu.cn
                jeb@organ.su.se
                Journal
                Angew Chem Int Ed Engl
                Angew Chem Int Ed Engl
                10.1002/(ISSN)1521-3773
                ANIE
                Angewandte Chemie (International Ed. in English)
                John Wiley and Sons Inc. (Hoboken )
                1433-7851
                1521-3773
                24 March 2021
                12 July 2021
                : 60
                : 29 ( doiID: 10.1002/anie.v60.29 )
                : 15686-15704
                Affiliations
                [ 1 ] State Key Laboratory of Chemo/Biosensing and Chemometrics College of Chemistry and Chemical Engineering Hunan University 410082 Changsha China
                [ 2 ] Department of Organic Chemistry Arrhenius Laboratory Stockholm University SE-10691 Stockholm Sweden
                [ 3 ] Department of Natural Sciences Mid Sweden University Holmgatan 10 SE-85170 Sundsvall Sweden
                Author information
                http://orcid.org/0000-0001-8462-4176
                Article
                ANIE202012707
                10.1002/anie.202012707
                9545650
                33368909
                c40bbebd-d504-43a5-85cb-e8f48da37479
                © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

                This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

                History
                : 18 September 2020
                Page count
                Figures: 39, Tables: 0, References: 227, Pages: 19, Words: 0
                Funding
                Funded by: Vetenskapsrådet , doi 10.13039/501100004359;
                Award ID: 2019-04042
                Categories
                Minireview
                Minireviews
                Aerobic Oxidation
                Custom metadata
                2.0
                July 12, 2021
                Converter:WILEY_ML3GV2_TO_JATSPMC version:6.2.0 mode:remove_FC converted:07.10.2022

                Chemistry
                electron transfer mediator,green oxidation,homogenous catalysis,mechanisms,molecular oxygen

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