Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4237 - 4352

Опубликована: Янв. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Язык: Английский

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Mechanochemistry: New Tools to Navigate the Uncharted Territory of “Impossible” Reactions

ChemSusChem, Год журнала: 2022, Номер 15(17)

Опубликована: Июль 21, 2022

Mechanochemical transformations have made chemists enter unknown territories, forcing a different chemistry perspective. While questioning or revisiting familiar concepts belonging to solution chemistry, mechanochemistry has broken new ground, especially in the panorama of organic synthesis. Not only does it foster "thinking outside box", but also opened reaction paths, allowing overcome weaknesses traditional exactly where use well-established solution-based methodologies rules out progress. In this Review, reader is introduced an intriguing research subject not yet fully explored and waiting for improved understanding. Indeed, study mainly focused on that, although impossible solution, become possible under mechanochemical processing conditions, simultaneously entailing innovation expanding chemical space.

Язык: Английский

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Electro-/photocatalytic alkene-derived radical cation chemistry: recent advances in synthetic applications

Chemical Society Reviews, Год журнала: 2022, Номер 51(16), С. 7206 - 7237

Опубликована: Янв. 1, 2022

This review covers the recent progress in electro-/photo-catalytic alkene-derived radical cation chemistry for organic synthesis, including synthetic strategies, plausible mechanisms and further research outlook.

Язык: Английский

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Recent developments in the difunctionalization of alkenes with C–N bond formation

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(18), С. 5206 - 5228

Опубликована: Янв. 1, 2021

Various alkene difunctionalization reactions involving nitridization, diamination, azidation, oxyamination, carboamination, aminohalogenation, and nitration are introduced in this review.

Язык: Английский

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Directed evolution of nonheme iron enzymes to access abiological radical-relay C(sp ³ )−H azidation

Science, Год журнала: 2022, Номер 376(6595), С. 869 - 874

Опубликована: Май 19, 2022

We report the reprogramming of nonheme iron enzymes to catalyze an abiological C(sp3)‒H azidation reaction through iron-catalyzed radical relay. This biocatalytic transformation uses amidyl radicals as hydrogen atom abstractors and Fe(III)‒N3 intermediates trapping agents. established a high-throughput screening platform based on click chemistry for rapid evolution catalytic performance identified enzymes. The final optimized variants deliver range products with up 10,600 total turnovers 93% enantiomeric excess. Given prevalence relay reactions in organic synthesis diversity enzymes, we envision that this discovery will stimulate future development metalloenzyme catalysts synthetically useful transformations unexplored by natural evolution.

Язык: Английский

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Enhanced Three-Component Chloro-/Azido-Fluoroalkylation of Unactivated Alkenes via the Proximity Effect in a Heterogenous Metallaphotocatalyst

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 2180 - 2191

Опубликована: Янв. 22, 2025

Heterogeneous metallaphotocatalytic chemical transformations employing a recyclable catalyst are highly desirable for organic synthesis. However, the rational design and controlled preparation of well-defined, site-isolated metal/photo bifunctional heterogeneous catalysts to achieve this goal remain significant challenge. In study, we demonstrate covalent attachment homogeneous molecular MnSalen complex (where Salen = N,N′-bis(salicylidene)ethylenediamine) onto surface graphitic carbon nitride (CN) via an amide bond visible-light-driven chloro- azido-fluoroalkylation unactivated alkenes. The linkage between CN not only facilitates electron delocalization enhances light-harvesting capabilities photosensitizer but also exerts proximity effect that markedly ability Mn sites capture alkyl radical intermediates during reaction process. A diverse set alkenes could be efficiently azido-fluoroalkylated their corresponding difunctionalized products in moderate high yields with good functional group compatibility. Furthermore, practicability protocol is illustrated through late-stage diversification various bioactive compounds pharmaceuticals. Notably, integrated photocatalyst demonstrates stability can recycled at least 10 times without loss activity selectivity.

Язык: Английский

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Iron-Catalyzed Enantioselective Radical Carboazidation and Diazidation of α,β-Unsaturated Carbonyl Compounds

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(30), С. 11856 - 11863

Опубликована: Июль 23, 2021

Azidation of alkenes is an efficient protocol to synthesize organic azides which are important structural motifs in synthesis. Enantioselective radical azidation, as a useful strategy install C–N3 bond, remains challenging due the inherently instability and unique structure radicals. Here, we disclose enantioselective carboazidation diazidation α,β-unsaturated ketones amides catalyzed by chiral N,N′-dioxide/Fe(OTf)2 complexes. An array substituted was transformed corresponding α-azido carbonyl derivatives good excellent enantioselectivities, benefiting preparation α-amino ketones, vicinal amino alcohols, diamines. Control experiments mechanistic studies proved pathway reaction process. The DFT calculations showed that azido transferred intermediate via intramolecular five-membered transition state with internal nitrogen Fe–N3 species.

Язык: Английский

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Electrophotochemical Decarboxylative Azidation of Aliphatic Carboxylic Acids

ACS Catalysis, Год журнала: 2022, Номер 12(17), С. 10661 - 10667

Опубликована: Авг. 16, 2022

We report an electrophotochemical metal-catalyzed strategy that harnesses the power of light and electricity for radical decarboxylative functionalization aliphatic carboxylic acids. This environmentally friendly protocol smoothly converts a diverse array acids into corresponding alkyl azides without using chemical oxidants or azido-group transfer reagents. The visible energy electric can be applied in spatially separated fashion with modular electro-flow-cell large-scale synthesis.

Язык: Английский

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Iron-Mediated Photochemical Anti-Markovnikov Hydroazidation of Unactivated Olefins

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(41), С. 22347 - 22353

Опубликована: Окт. 9, 2023

Unactivated olefins are converted to alkyl azides with bench-stable NaN3 in the presence of FeCl3·6H2O under blue-light irradiation. The products obtained anti-Markovnikov selectivity, and reaction can be performed mild ambient conditions air moisture. transformation displays broad functional group tolerance, which renders it suitable for functionalization complex molecules. Mechanistic investigations conducted provide insight into hydroazidation reveal role water from iron hydrate as H atom source.

Язык: Английский

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Asymmetric Three-Component Radical Alkene Carboazidation by Direct Activation of Aliphatic C–H Bonds

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(19), С. 13347 - 13355

Опубликована: Май 6, 2024

Azide compounds are widely present in natural products and drug molecules, their easy-to-transform characteristics make them used the field of organic synthesis. The merging transition-metal catalysis with radical chemistry offers a versatile platform for carboazidation alkenes, allowing rapid assembly highly functionalized azides. However, direct use readily available hydrocarbon feedstocks as sp

Язык: Английский

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