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      Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

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          Abstract

          We present here a review of the photochemical and electrochemical applications of multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms in which both an electron and a proton are exchanged together, often in a concerted elementary step. As such, MS-PCET can function as a non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from a wide variety of common organic functional groups. We present an introduction to MS-PCET and a practitioner’s guide to reaction design, with an emphasis on the unique energetic and selectivity features that are characteristic of this reaction class. We then present chapters on oxidative N–H, O–H, S–H, and C–H bond homolysis methods, for the generation of the corresponding neutral radical species. Then, chapters for reductive PCET activations involving carbonyl, imine, other X=Y π-systems, and heteroarenes, where neutral ketyl, α-amino, and heteroarene-derived radicals can be generated. Finally, we present chapters on the applications of MS-PCET in asymmetric catalysis and in materials and device applications. Within each chapter, we subdivide by the functional group undergoing homolysis, and thereafter by the type of transformation being promoted. Methods published prior to the end of December 2020 are presented.

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          Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis.

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            Organic Photoredox Catalysis.

            In this review, we highlight the use of organic photoredox catalysts in a myriad of synthetic transformations with a range of applications. This overview is arranged by catalyst class where the photophysics and electrochemical characteristics of each is discussed to underscore the differences and advantages to each type of single electron redox agent. We highlight both net reductive and oxidative as well as redox neutral transformations that can be accomplished using purely organic photoredox-active catalysts. An overview of the basic photophysics and electron transfer theory is presented in order to provide a comprehensive guide for employing this class of catalysts in photoredox manifolds.
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              Analysis of the structural diversity, substitution patterns, and frequency of nitrogen heterocycles among U.S. FDA approved pharmaceuticals.

              Nitrogen heterocycles are among the most significant structural components of pharmaceuticals. Analysis of our database of U.S. FDA approved drugs reveals that 59% of unique small-molecule drugs contain a nitrogen heterocycle. In this review we report on the top 25 most commonly utilized nitrogen heterocycles found in pharmaceuticals. The main part of our analysis is divided into seven sections: (1) three- and four-membered heterocycles, (2) five-, (3) six-, and (4) seven- and eight-membered heterocycles, as well as (5) fused, (6) bridged bicyclic, and (7) macrocyclic nitrogen heterocycles. Each section reveals the top nitrogen heterocyclic structures and their relative impact for that ring type. For the most commonly used nitrogen heterocycles, we report detailed substitution patterns, highlight common architectural cores, and discuss unusual or rare structures.
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                Author and article information

                Journal
                Chem Rev
                Chem Rev
                cr
                chreay
                Chemical Reviews
                American Chemical Society
                0009-2665
                1520-6890
                23 November 2021
                26 January 2022
                : 122
                : 2 , Photochemical Catalytic Processes
                : 2017-2291
                Affiliations
                Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States
                Author notes
                Author information
                https://orcid.org/0000-0001-7873-5232
                https://orcid.org/0000-0002-1631-3031
                https://orcid.org/0000-0003-0469-1008
                https://orcid.org/0000-0002-2734-5848
                https://orcid.org/0000-0003-1481-266X
                https://orcid.org/0000-0002-5745-9096
                https://orcid.org/0000-0002-3146-9579
                https://orcid.org/0000-0001-7705-2886
                https://orcid.org/0000-0002-5872-4824
                https://orcid.org/0000-0003-3132-502X
                https://orcid.org/0000-0002-9892-7837
                https://orcid.org/0000-0003-3818-3896
                https://orcid.org/0000-0003-1044-4900
                Article
                10.1021/acs.chemrev.1c00374
                8796287
                34813277
                14f6be7f-6296-49e9-8df2-ae2f8f07ef56
                © 2021 The Authors. Published by American Chemical Society

                Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works ( https://creativecommons.org/licenses/by-nc-nd/4.0/).

                History
                : 01 May 2021
                Funding
                Funded by: National Institute of General Medical Sciences, doi 10.13039/100000057;
                Award ID: F32GM142190
                Funded by: H2020 Marie SkÃ…?odowska-Curie Actions, doi 10.13039/100010665;
                Award ID: 886224
                Funded by: Division of Graduate Education, doi 10.13039/100000082;
                Award ID: DGE-2039656
                Funded by: National Institute of General Medical Sciences, doi 10.13039/100000057;
                Award ID: R35 GM134893
                Categories
                Review
                Custom metadata
                cr1c00374
                cr1c00374

                Chemistry
                Chemistry

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