Visible Light-Driven Radical-Mediated C-C Bond Cleavage/Functionalization in Organic Synthesis
作者:
Yu, Xiao-Ye;Chen, Jia-Rong* ;Xiao, Wen-Jing*
期刊:
Chemical Reviews ,2021年121(1):506-561 ISSN:0009-2665
通讯作者:
Chen, Jia-Rong;Xiao, Wen-Jing
作者机构:
[Chen, Jia-Rong; Xiao, WJ; Xiao, Wen-Jing; Yu, Xiao-Ye] Cent China Normal Univ, Coll Chem, CCNU uOttawa Joint Res Ctr, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
通讯机构:
[Chen, JR; Xiao, WJ] C;Cent China Normal Univ, Coll Chem, CCNU uOttawa Joint Res Ctr, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
摘要:
Thermal C-C bond cleavage reactions allow the construction of structurally diverse molecular skeletons via predictable and efficient bond reorganizations. Visible light photoredox-catalyzed radical-mediated C-C bond cleavage reactions have recently emerged as a powerful alternative method for overcoming the thermodynamic and kinetic barrier of C-C bond cleavage in diverse molecular scaffolds. In recent years, a plethora of elegant and useful reactions have been invented, and the products are sometimes otherwise inaccessible by classic thermal reactions. Considering the great influence and synthetic potential of these reactions, we provide a summary of the state of art visible light-driven radical-mediated C-C bond cleavage/functionalization strategies with a specific emphasis on the working models. We hoped that this review will be useful for medicinal and synthetic organic chemists and will inspire further reaction development in this interesting area. © 2021 American Chemical Society. All rights reserved.
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英文
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When Nanozymes Meet Single-Atom Catalysis
作者:
Jiao, Lei;Yan, Hongye;Wu, Yu;Gu, Wenling;Zhu, Chengzhou* ;...
期刊:
Angewandte Chemie - International Edition ,2020年59(7):2565-2576 ISSN:1433-7851
通讯作者:
Zhu, Chengzhou;Lin, Yuehe
作者机构:
[Zhu, Chengzhou; Yan, Hongye; Wu, Yu; Jiao, Lei; Gu, Wenling] Cent China Normal Univ Wuhan, Key Lab Pesticide & Chem Biol, Int Joint Res Ctr Intelligent Biosensing Technol, Minist Educ,Coll Chem, Wuhan 430079, Peoples R China.;[Du, Dan; Lin, Yuehe] Washington State Univ, Sch Mech & Mat Engn, Pullman, WA 99164 USA.
通讯机构:
[Zhu, Chengzhou] C;[Lin, Yuehe] W;Cent China Normal Univ Wuhan, Key Lab Pesticide & Chem Biol, Int Joint Res Ctr Intelligent Biosensing Technol, Minist Educ,Coll Chem, Wuhan 430079, Peoples R China.;Washington State Univ, Sch Mech & Mat Engn, Pullman, WA 99164 USA.
关键词:
biosensors;nanozymes;organic pollutant degradation;SAzymes;therapeutic drugs
摘要:
Nanomaterials with enzyme-like activities, coined nanozymes, have been researched widely as they offer unparalleled advantages in terms of low cost, superior activity, and high stability. The complex structure and composition of nanozymes has led to extensive investigation of their catalytic sites at an atomic scale, and to an in-depth understanding of the biocatalysis occurring. Single-atom catalysts (SACs), characterized by atomically dispersed active sites, have provided opportunities for mimicking metalloprotease and for bridging the gap between natural enzymes and nanozymes. In this Minireview, we illustrate the unique properties of nanozymes and we discuss recent advances in the synthesis, characterization, and applications of SACs. Subsequently, we outline the impressive progress made in single-atom nanozymes and we discuss their applications in sensing, degradation of organic pollutants, and in therapeutic roles. Finally, we present the major challenges and opportunities remaining for a successful marriage of nanozymes and SACs. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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英文
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When Light Meets Nitrogen-Centered Radicals: From Reagents to Catalysts
作者:
Yu, Xiao-Ye;Zhao, Quan-Qing;Chen, Jun;Xiao, Wen-Jing;Chen, Jia-Rong*
期刊:
Accounts of Chemical Research ,2020年53(5):1066-1083 ISSN:0001-4842
通讯作者:
Chen, Jia-Rong
作者机构:
[Zhao, Quan-Qing; Xiao, Wen-Jing; Chen, Jun; Chen, Jia-Rong; Yu, Xiao-Ye] Cent China Normal Univ, Coll Chem, CCNU uOttawa Joint Res Ctr, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
通讯机构:
[Chen, Jia-Rong] C;Cent China Normal Univ, Coll Chem, CCNU uOttawa Joint Res Ctr, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
摘要:
ConspectusNitrogen-centered radicals (NCRs) are a versatile class of highly reactive species that have a longer history than the classical carbon-based radicals in synthetic chemistry. Depending on the N-hybridization and substitution patterns, NCRs can serve as electrophiles or nucleophiles to undergo various radical transformations. Despite their power, progress in nitrogen-radical chemistry is still slow compared with the popularity of carbon radicals, and their considerable synthetic potential has been largely underexplored, which is, as concluded by Zard, mainly hampered by "a dearth of convenient access to these species and a lack of awareness pertaining to their reactivity".Over the past decade, visible-light photoredox catalysis has been established as a powerful toolbox that synthetic chemists can use to generate a diverse range of radical intermediates from native organic functional groups via a single electron transfer process or energy transfer under mild reaction conditions. This catalytic strategy typically obviates the need for external stoichiometric activation reagents or toxic initiators and often enables traditionally inaccessible ionic chemical reactions. On the basis of our long-standing interest in nitrogen chemistry and catalysis, we have emphasized the use of visible-light photoredox catalysis as a tactic to discover and develop novel methods for generating NCRs in a controlled fashion and synthetic applications. In this Account, we describe our recent advances in the development of visible-light-driven photoredox-catalyzed generation of NCRs and their synthetic applications.Inspired by the natural biological proton-coupled electron transfer (PCET) process, we first developed a strategy of visible-light-driven photoredox-catalyzed oxidative deprotonation electron transfer to activate the N-H bonds of hydrazones, benzamides, and sulfonamides to give the corresponding NCRs under mild reaction conditions. With these reactive species, we then achieved a range of 5-exo and 6-endo radical cyclizations as well as cascade reactions in a highly regioselective manner, providing access to a variety of potentially useful nitrogen heterocycles. To further expand the repertoire of possible reactions of NCRs, we also revealed that iminyl radicals, derived from O-acyl cycloalkanone oxime esters, can undergo facile ring-opening C-C bond cleavage to give cyanoalkyl radicals. These newly formed radical species can further undergo a variety of C-C bond-forming reactions to allow the synthesis of diverse distally functionalized alkyl nitriles. Stimulated by these studies, we further developed a wide variety of visible-light-driven copper-catalyzed radical cross-coupling reactions of cyanoalkyl radicals. Because of their inherent highly reactive and transient properties, the strategy of heteroatom-centered radical catalysis is still largely underexplored in organic synthesis. Building on our understanding of the fundamental chemistry of NCRs, we also developed for the first time the concept of NCR covalent catalysis, which involves the use of in situ-photogenerated NCRs to activate allyl sulfones, vinylcyclopropanes, and N-tosyl vinylaziridines. This catalytic strategy has thus enabled efficient difunctionalization of various alkenes and late-stage modification of complex biologically active molecules.In this Account, we describe a panoramic picture of our recent contributions since 2014 to the development and application of the visible-light-driven photoredox systems in the field of NCR chemistry. These studies provide not only efficient methods for the synthesis of functionally rich molecules but also some insight into the exploration of new reactivity or reaction modes of NCRs. © 2020 American Chemical Society.
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