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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Recent advances in visible-light photoredox-catalyzed nitrogen radical cyclization

Green Synthesis and Catalysis, Journal Year: 2020, Volume and Issue: 1(1), P. 42 - 51

Published: June 1, 2020

Visible-light photoredox catalysis is a powerful and attractive strategy for organic molecule activation new reaction design owing to its environmental-friendly characteristics unique catalytic mechanisms, has found wide applications in synthesis. This enables controllable generation of diverse nitrogen-centered radicals (NCRs) under mild conditions, providing access construction nitrogen-containing compounds. In this review, we critically illustrate the recent advances field visible-light photoredox-catalyzed cyclization radicals, based on different radical precursors modes. Wherever possible, particular emphasis also put working models synthetic applications.

Language: Английский

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Strain-Release Photocatalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(38), P. 20716 - 20732

Published: Sept. 15, 2023

The concept of strain in organic compounds is as old modern chemistry and was initially introduced to justify the synthetic setbacks along synthesis small ring systems (pars construens strain). In last decades, chemists have developed an arsenal strain-release reactions destruens strain) which can generate─with significant driving force─rigid aliphatic that act three-dimensional alternatives (hetero)arenes. Photocatalysis added additional dimension processes by leveraging energy photons create chemical complexity under mild conditions. This perspective presents latest advancements photocatalysis─with emphases on mechanisms, catalytic cycles, current limitations─the unique architectures be produced, possible future directions.

Language: Английский

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Cooperative NHC/Photoredox Catalyzed Ring‐Opening of Aryl Cyclopropanes to 1‐Aroyloxylated‐3‐Acylated Alkanes

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(48), P. 25252 - 25257

Published: Sept. 28, 2021

Cyclopropanes are an important class of building blocks in organic synthesis. Herein, a ring-opening/arylcarboxylation/acylation cascade reaction for the 1,3-difunctionalization aryl cyclopropanes enabled by cooperative NHC and organophotoredox catalysis is reported. The works on monosubstituted that contrast to heavily investigated donor-acceptor more challenging be difunctionalized. key step radical/radical cross coupling benzylic radical generated photoredox cycle with ketyl from cycle. transformation features metal-free conditions tolerates diverse range functionalities.

Language: Английский

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Progress in Photoinduced Radical Reactions using Electron Donor‐Acceptor Complexes

Asian Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 10(4), P. 711 - 748

Published: Feb. 11, 2021

Abstract Photocatalyzed organic synthesis transformation is a remarkable green synthetic strategy because of the advantages operational simplicity, high chemoselectivities, cheap, and environmental benignancy, along with extensive applications in fields organic, pharmaceutical functional material chemistry. Generally, photoredox catalysts or photosensitizers are necessary for generation their excited states to perform successive oxidative reductive reactions through single electron transfer (SET) energy (ET) process. Furthermore, exploration colored donor‐acceptor (EDA) complex charge (CT) between an electron‐rich electron‐poor substrate provides chance deliver intermediate under irradiation light, resulting formation radical activate species induce various reactions. These were performed without need any external photocatalysts mild reaction conditions. Herein, this review focuses on recent progress photoinduced addition reactions, borylations, radical‐radical cross‐coupling degradation cascade cyclization via EDA complexes. We highlight these novel methodologies applications, as well mechanisms. This will help provide references medicinal chemists who charmed by photochemical transformations based

Language: Английский

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Ligand Modification of Au₂₅ Nanoclusters for Near-Infrared Photocatalytic Oxidative Functionalization

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(9), P. 3787 - 3792

Published: Feb. 28, 2022

The inorganic-organic interface between metal catalysts and their substrates greatly influences reaction processes, but few studies of this have been conducted for a detailed understanding its structure. Herein, we describe the synthesis structural determination an arylthiolated Au25(F-Ph)18- nanocluster characterize in detail key roles ligands photocatalyzed oxidative functionalization reactions. most significant findings are that (i) interactions established to avoid distortion geometric structure, limit Jahn-Teller effect, protect from oxidization (ii) low energy gap (HOMO-LUMO) synthetic clusters enables three types photocatalytic reactions by near-infrared light (850 nm).

Language: Английский

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Additive-free synthesis of S-substituted isothioureas via visible-light-induced four-component reaction of α-diazoesters, aryl isothiocyanates, amines and cyclic ethers

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(2), P. 109107 - 109107

Published: Sept. 16, 2023

Language: Английский

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Visible-light-induced four-component difunctionalization of alkenes to construct phosphorodithioate-containing quinoxalin-2(1H)-ones

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(11), P. 110112 - 110112

Published: June 25, 2024

Language: Английский

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Carbon-carbon triple bond cleavage and reconstitution to achieve aryl amidation using nitrous acid esters

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 24, 2025

C–C bond cleavage and recombination provide an efficient strategy for the modification reconstruction of molecule structures. Herein, we present a method achieving amidation aryl C(sp2)–H through triple with involvement nitrous acid esters. This marks instance precise controlled stepwise bond, offering fresh perspective such bonds. Nitrous ester serves as both radical source hydrogen atom transfer (HAT) reagent to functionalize utilize two carbon atoms bond. The alkoxy captures from or N-hydroxyl induce 1,3-oxygen migration, which is crucial subsequent molecular authors report achieve bonds by participation

Language: Английский

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Aryl acyl peroxides for visible-light induced decarboxylative arylation of quinoxalin-2(1H)-ones under additive-, metal catalyst-, and external photosensitizer-free and ambient conditions

Green Chemistry, Journal Year: 2020, Volume and Issue: 23(1), P. 374 - 378

Published: Oct. 23, 2020

Aryl radicals were generated for the first time from aryl acyl peroxides in ethyl acetate under ambient conditions and visible-light illumination absence of any additive, metal catalyst, or external photosensitizer.

Language: Английский

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