Visible-Light Photoredox Catalysis Xuan, Jun; Xiao, Wen-Jing
Angewandte Chemie (International ed.),
July 9, 2012, Volume:
51, Issue:
28
Journal Article
Peer reviewed
In the last few years, visible‐light initiated organic transformations have attracted increasing attention. The development of visible‐light‐promoted photocatalytic reactions, which enable rapid and ...efficient synthesis of fine chemicals, is highly desirable from the viewpoint of cost, safety, availability, and environmental friendliness. In this Minireview, recent advances made in this fast developing area of research are discussed.
In the spotlight: The title catalysis is an area of research that is developing quickly and has become a powerful and efficient tool in synthetic organic chemistry (see picture, S=Substrates, P=Products). There is little doubt that continued exploration of visible light photoredox catalysis will uncover a wide range of fascinating and useful chemical reactions.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
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.
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IJS, KILJ, NUK, PNG, UL, UM
Visible‐light‐induced radical decarboxylative functionalization of carboxylic acids and their derivatives has recently received considerable attention as a novel and efficient method to create CC ...and CX bonds. Generally, this visible‐light‐promoted decarboxylation process can smoothly occur under mild reaction conditions with a broad range of substrates and an excellent functional‐group tolerance. The radical species formed from the decarboxylation step can participate in not only single photocatalytic transformations, but also dual‐catalytic cross‐coupling reactions by combining photoredox catalysis with other catalytic processes. Recent advances in this research area are discussed herein.
Photo op: A novel functionalization reaction using visible‐light‐induced photoredox catalysis has recently been developed (see title). The formed radical species can participate in not only single photocatalytic transformations, but also dual‐catalytic reactions by combining photoredox catalysis with other catalytic methods. Recent advances in this research area are discussed herein.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Due to their inherent ring strain, three-membered carbocyclic- and heterocyclic ring structures are versatile synthetic building blocks. Traditional ring-opening methods of these molecules require ...the use of thermolysis, acid catalysts or transition-metals
via
ionic reaction pathways. Recently, visible light-induced photoredox catalysis has emerged as a powerful platform for initiating new chemical transformations. In this tutorial review, the synthetic and mechanistic aspects of visible light-promoted ring-opening functionalization of three-membered carbo- and heterocycles are highlighted. By using these strategies, a variety of ring-opening functionalization products, including biologically important carbo- and heterocycles, can be efficiently accessed in a high chemo- and regioselective manner.
In this tutorial review, synthetic and mechanistic aspects of visible light-promoted ring-opening functionalization of three-membered carbo- and heterocycles are highlighted.
Visible‐light photocatalysis is a rapidly developing and powerful strategy to initiate organic transformations, as it closely adheres to the tenants of green and sustainable chemistry. Generally, ...most visible‐light‐induced photochemical reactions occur through single‐electron transfer (SET) pathways. Recently, visible‐light‐induced energy‐transfer (EnT) reactions have received considerable attentions from the synthetic community as this strategy provides a distinct reaction pathway, and remarkable achievements have been made in this field. In this Review, we highlight the most recent advances in visible‐light‐induced EnT reactions.
Making light of synthesis: The distinctive reaction pathways provided by visible‐light‐induced energy transfer (EnT) has resulted in it receiving considerable attention. This Review discusses the most recent advances in visible‐light‐induced EnT reactions.
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Hantzsch esters were often previously used as reductants in thermal catalytic hydrogenation reactions. Over the last few decades, Hantzsch esters have proven to be a useful class of electron donors ...and proton sources in photoredox catalyzed processes. Moreover, under photoredox catalytic conditions, alkyl-1,4-dihydropyridines can serve as versatile types of alkylation reagents
via
oxidative fragmentation mechanisms. This minireview highlights the recent advances in the chemistry of Hantzsch esters in photoredox catalyzed organic synthesis, with particular emphasis placed on reaction mechanisms. We hope that this review will inspire further new reaction design and developments with such a class of readily accessible reagents.
This minireview highlights the recent advances in the chemistry of Hantzsch esters in photoredox catalyzed organic synthesis, with particular emphasis placed on reaction mechanisms.
A room‐temperature, visible‐light‐driven N‐centered iminyl radical‐mediated and redox‐neutral C−C single bond cleavage/radical addition cascade reaction of oxime esters and unsaturated systems has ...been accomplished. The strategy tolerates a wide range of O‐acyl oximes and unsaturated systems, such as alkenes, silyl enol ethers, alkynes, and isonitrile, enabling highly selective formation of various chemical bonds. This method thus provides an efficient approach to various diversely substituted cyano‐containing alkenes, ketones, carbocycles, and heterocycles.
A visible‐light‐driven room‐temperature N‐centered iminyl radical‐mediated and redox‐neutral C−C single bond cleavage/radical addition cascade reaction of oxime esters and unsaturated systems has been accomplished. The strategy tolerates a wide range of O‐acyl oximes and alkenes, silyl enol ethers, alkynes, and isonitrile. This method allows access to various cyano‐containing alkenes, ketones, carbocycles, and heterocycles.
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A visible‐light‐driven, copper‐catalyzed three‐component radical cross‐coupling of oxime esters, styrenes, and boronic acids has been developed. Key steps of this protocol involve catalytic ...generation of an iminyl radical from a redox‐active oxime ester and subsequent C−C bond cleavage to generate a cyanoalkyl radical. Upon its addition to styrene, the newly formed benzylic radical undergoes coupling with a boronic‐acid‐derived ArCuII complex to achieve 1,1‐diarylmethane‐containing alkylnitriles.
Key steps of the visible‐light‐driven title reaction involve catalytic generation of an iminyl radical from a redox‐active oxime ester and subsequent C−C bond cleavage to give a cyanoalkyl radical. Upon its addition to styrene, a benzylic radical is formed that undergoes coupling with a boronic‐acid‐derived ArCuII complex to give 1,1‐diarylmethane‐containing alkylnitriles. The method features the use of readily available substrates and high functional‐group tolerance.
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Radicals are an important class of versatile and highly reactive species. Compared with the wide applications of various C-centred radicals, however, the N-radical species including N-centred ...radicals and radical ions remain largely unexplored due to the lack of convenient methods for their generation. In recent years, visible light photoredox catalysis has emerged as a powerful platform for the generation of various N-radical species and methodology development towards the synthesis of diverse N-containing compounds. In this tutorial review, we highlight recent advances in this rapidly developing area with particular emphases put on the working models and new reaction design.
Neutral eosin Y‐derived photoexcited states have been found to serve as photoacids and direct hydrogen atom transfer (HAT) catalysts in the activation of glycals and C−H bonds, respectively. These ...studies pave the way for further use of eosin Y in photochemical synthesis.
New sides of eosin Y: Neutral eosin Y‐derived photoexcited states have been found to serve as photoacids and direct hydrogen atom transfer (HAT) catalysts in the activation of glycals and C−H bonds, respectively. These studies pave the way for further use of eosin Y in photochemical synthesis.
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