Visible Light-Driven Radical-Mediated C–C Bond Cleavage/Functionalization in Organic Synthesis

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(1), P. 506 - 561

Published: May 29, 2020

Thermal C–C bond cleavage reactions allow the construction of structurally diverse molecular skeletons via predictable and efficient reorganizations. Visible light photoredox-catalyzed radical-mediated have recently emerged as a powerful alternative method for overcoming thermodynamic kinetic barrier in scaffolds. In recent years, plethora elegant useful been invented, products are sometimes otherwise inaccessible by classic thermal reactions. Considering great influence synthetic potential these reactions, we provide summary state art visible light-driven cleavage/functionalization strategies with specific emphasis on working models. We hoped that this review will be medicinal organic chemists inspire further reaction development interesting area.

Language: Английский

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Mechanistic Studies in Photocatalysis

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(12), P. 3730 - 3747

Published: Oct. 19, 2018

Abstract The fast‐moving fields of photoredox and photocatalysis have recently provided fresh opportunities to expand the potential synthetic organic chemistry. Advances in light‐mediated processes mainly been guided so far by empirical findings quest for reaction invention. general perception, however, is that entering a more mature phase where combination experimental mechanistic studies will play dominant role sustaining further innovation. This Review outlines key consider when developing photochemical process, best techniques available acquiring relevant information. discussion use selected case highlight how investigations can be instrumental guiding invention development synthetically useful photocatalytic transformations.

Language: Английский

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Intermolecular radical carboamination of alkenes

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(6), P. 1790 - 1811

Published: Jan. 1, 2020

Vicinal alkene carboamination is a highly efficient and practical synthetic strategy for the straightforward preparation of diverse valuable amine derivatives starting from simple compounds. During last decade that approach has found continuous research interests various methods have been developed using transition-metal catalysis. Driven by renaissance radical chemistry, intermolecular comprising C-C bond C-N forming step intensively investigated recently culminating in novel strategies improved protocols which complement existing methodologies. Radical can be achieved via three different reaction modes. Such cascades proceed through N-radical addition to an with subsequent formation leading 2,1-carboamination products. Alternatively, installed prior initial C-radical β-amination resulting 1,2-carboamination. The third mode comprises single electron oxidation corresponding cation gets trapped N-nucleophile cascade terminated formation. In this review, conceptual approaches will discussed examples recent literature presented. Further, reader get insights into mechanism transformations.

Language: Английский

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Photoinduced Remote Functionalisations by Iminyl Radical Promoted C−C and C−H Bond Cleavage Cascades

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 57(3), P. 744 - 748

Published: Nov. 8, 2017

Abstract A photoinduced cascade strategy leading to a variety of differentially functionalised nitriles and ketones has been developed. These reactions rely on the oxidative generation iminyl radicals from simple oximes. Radical transposition by C(sp 3 )−(sp ) )−H bond cleavage gives access distal carbon that undergo S H 2 functionalisations. mild, visible‐light‐mediated procedures can be used for remote fluorination, chlorination, azidation, were applied modification bioactive structurally complex molecules.

Language: Английский

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Organic thermally activated delayed fluorescence (TADF) compounds used in photocatalysis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(13), P. 7587 - 7680

Published: Jan. 1, 2021

Organic compounds that show Thermally Activated Delayed Fluorescence (TADF) have become wildly popular as next generation emitters in organic light-emitting diodes (OLEDs), but since 2016, received significant and increasing attention photocatalysts.

Language: Английский

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Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(2), P. 766 - 897

Published: Dec. 22, 2020

Recent developments and future prospects of visible-light photocatalysis in the late-stage functionalization pharmaceuticals natural bioactive compounds.

Language: Английский

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A Visible‐Light‐Driven Iminyl Radical‐Mediated C−C Single Bond Cleavage/Radical Addition Cascade of Oxime Esters

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 57(3), P. 738 - 743

Published: Dec. 7, 2017

Abstract 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 unsaturated systems has been accomplished. The strategy tolerates a wide range O‐acyl oximes systems, such as alkenes, silyl enol ethers, alkynes, isonitrile, enabling highly selective formation various chemical bonds. This method thus provides an efficient approach to diversely substituted cyano‐containing ketones, carbocycles, heterocycles.

Language: Английский

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Hydroxylamine Derivatives as Nitrogen‐Radical Precursors in Visible‐Light Photochemistry

Chemistry - A European Journal, Journal Year: 2018, Volume and Issue: 24(47), P. 12154 - 12163

Published: May 22, 2018

In recent years, hydroxylamines derivatives have been exploited as nitrogen-radical precursors in visible-light photochemistry. Their ability to serve electrophores redox chemistry has propelled the development of many novel transformations. Fundamental mechanistic aspects well importance preparation nitrogen-containing molecules will be highlighted.

Language: Английский

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Strategies to Generate Nitrogen-centered Radicals That May Rely on Photoredox Catalysis: Development in Reaction Methodology and Applications in Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2353 - 2428

Published: Oct. 8, 2021

For more than 70 years, nitrogen-centered radicals have been recognized as potent synthetic intermediates. This review is a survey designed for use by chemists engaged in target-oriented synthesis. summarizes the recent paradigm shift access to and application of N-centered enabled visible-light photocatalysis. broadens streamlines approaches many small molecules because photocatalysis conditions are mild. Explicit attention paid innovative advances N–X bonds radical precursors, where X = Cl, N, S, O, H. clarity, key mechanistic data noted, available. Synthetic applications limitations summarized illuminate tremendous utility photocatalytically generated radicals.

Language: Английский

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Photoinduced Remote Functionalization of Amides and Amines Using Electrophilic Nitrogen Radicals

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(39), P. 12945 - 12949

Published: Aug. 7, 2018

Abstract The selective functionalization of C(sp 3 )−H bonds at distal positions to functional groups is a challenging task in synthetic chemistry. Reported here photoinduced radical cascade strategy for the divergent amides and protected amines. process based on oxidative generation electrophilic amidyl radicals their subsequent transposition by 1,5‐H‐atom transfer, resulting remote fluorination, chlorination and, first time, thioetherification, cyanation, alkynylation. tolerant most common delivers useful building blocks that can be further elaborated. utility this demonstrated through late‐stage amino acids dipeptide.

Language: Английский

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