A General Photocatalytic Strategy for Nucleophilic Amination of Primary and Secondary Benzylic C–H Bonds

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(33), С. 18487 - 18496

Опубликована: Авг. 11, 2023

We report a visible-light photoredox-catalyzed method that enables nucleophilic amination of primary and secondary benzylic C(sp3)-H bonds. A novel amidyl radical precursor organic photocatalyst operate in tandem to transform bonds into carbocations via sequential hydrogen atom transfer (HAT) oxidative radical-polar crossover. The resulting carbocation can be intercepted by variety N-centered nucleophiles, including nitriles (Ritter reaction), amides, carbamates, sulfonamides, azoles, for the construction pharmaceutically relevant C(sp3)-N under unified reaction conditions. Mechanistic studies indicate HAT is radical-mediated operates reductive quenching pathway. These findings establish mild, metal-free, modular protocol rapid diversification library aminated products.

Язык: Английский

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Enhancing electrochemical reactions in organic synthesis: the impact of flow chemistry

Chemical Society Reviews, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Utilizing electrons directly offers significant potential for advancing organic synthesis by facilitating novel reactivity and enhancing selectivity under mild conditions. As a result, an increasing number of chemists are exploring electrosynthesis. However, the efficacy electrochemical transformations depends critically on design cell. Batch cells often suffer from limitations such as large inter-electrode distances poor mass transfer, making flow promising alternative. Implementing cells, however, requires foundational understanding microreactor technology. In this review, we briefly outline applications electrosynthesis before providing comprehensive examination existing reactor technologies. Our goal is to equip with insights needed tailor their meet specific requirements effectively. We also highlight application designs in scaling up processes integrating high-throughput experimentation automation. These advancements not only enhance synthetic community but hold promise both academia industry.

Язык: Английский

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Accelerated Electrophotocatalytic C(sp³)−H Heteroarylation Enabled by an Efficient Continuous‐Flow Reactor**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(52)

Опубликована: Ноя. 17, 2023

Electrophotocatalytic transformations are garnering attention in organic synthesis, particularly for accessing reactive intermediates under mild conditions. Moving these methodologies to continuous-flow systems, or flow ElectroPhotoCatalysis (f-EPC), showcases potential scalable processes due enhanced irradiation, increased electrode surface, and improved mixing of the reaction mixture. Traditional methods sequentially link photochemical electrochemical reactions, using reactors connected series, yet struggle accommodate transient species. In this study, we introduce a new reactor concept electrophotocatalysis (EPC) that simultaneously utilizes photons electrons. The is designed with transparent employs cost-effective materials. We used technology develop an efficient process electrophotocatalytic heteroarylation C(sp3 )-H bonds. Importantly, same setup can also facilitate purely transformations. This represents significant advancement electrophotocatalysis, providing framework its application complex synthetic

Язык: Английский

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A fruitful century for the scalable synthesis and reactions of biphenyl derivatives: applications and biological aspects

RSC Advances, Год журнала: 2023, Номер 13(27), С. 18262 - 18305

Опубликована: Янв. 1, 2023

This review provides recent developments in the current status and latest synthetic methodologies of biphenyl derivatives.

Язык: Английский

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Unconventional approaches for organic electrosynthesis: Recent progress

Current Opinion in Electrochemistry, Год журнала: 2022, Номер 35, С. 101050 - 101050

Опубликована: Май 14, 2022

Язык: Английский

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Introducing Phenalenyl-Based Organic Lewis Acid as a Photocatalyst to Facilitate Oxidative Azolation of Unactivated Arenes

Organic Letters, Год журнала: 2023, Номер 25(11), С. 1895 - 1900

Опубликована: Март 9, 2023

By revealing the robust photooxidant properties of phenalenyl-based organic Lewis acid, we have introduced this moiety as an effective organophotocatalyst for oxidative azolation unactivated and feedstock arenes. In addition to its tolerance various functional groups scalability, photocatalyst was shown be promising defluorinative fluoroarenes.

Язык: Английский

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Arenes and Heteroarenes C−H Functionalization Under Enabling Conditions: Electrochemistry, Photoelectrochemistry & Flow Technology

The Chemical Record, Год журнала: 2023, Номер 23(10)

Опубликована: Май 31, 2023

Abstract C−H bond functionalization generates molecular complexity in single‐step transformation. However, the activation of bonds requires expensive metals or stoichiometric amounts oxidizing/reducing species. In many cases, they often require pre‐functionalization starting molecules. Such pre‐activating measures cause waste generation and their separation from final product is also troublesome. such a scenario, reactions activating elements generating renewable energy resources as electricity light would be more efficient, green, cost‐effective. Further, incorporation growing flow technology chemical transformation processes will accelerate safer accesses valuable products. Arenes & heteroarenes are ubiquitous pharmaceuticals, natural products, medicinal compounds, other biologically important Herein, we discussed enabling tools technologies used for recent arenes heteroarenes.

Язык: Английский

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Recent Advance in Electrochemical C(sp²)—H Amination of Arenes

Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(3), С. 871 - 871

Опубликована: Янв. 1, 2024

Язык: Английский

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Amination of Phenols and Halophenols via Pyridinium–Iridium Dual Photocatalysis

ACS Catalysis, Год журнала: 2024, Номер 14(16), С. 12173 - 12180

Опубликована: Июль 30, 2024

In this study, we present a photochemical method for the amination of phenols (C–H) and halophenols (SNAr), facilitated by dual catalytic pathways involving both Ir(III) photocatalysis phenol–pyridinium electron donor–acceptor complexation. By incorporating pyridinium additive, achieved efficient C–N coupling between diverse aromatic nitrogen nucleophiles, delivering high yields (up to 99%) across wide range substrates, including pharmaceuticals natural products. We investigate reaction selectivity substrate compatibility/limitations through combination experimental computational techniques. Moreover, highlight synthetic versatility products various late-stage functionalizations grafting two different heteroarenes onto one phenol scaffold.

Язык: Английский

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Flow Electroreductive Nickel‐Catalyzed Cyclopropanation of Alkenes Using gem‐Dichloroalkanes

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Янв. 31, 2025

Abstract Cyclopropanes are valuable motifs in organic synthesis, widely featured pharmaceuticals and functional materials. Herein, we report an efficient electrochemical methodology for the cyclopropanation of alkenes, leveraging a nickel‐catalyzed process continuous‐flow. The developed protocol demonstrates broad substrate scope, accommodating both electron‐rich electron‐poor alkenes with high group tolerance. Beyond dichloromethane as feedstock methylene source, enables synthesis methylated, deuterated, chloro‐substituted cyclopropanes. Mechanistic investigations suggest electro‐generation nickel carbene key intermediate. Notably, reaction operates under ambient conditions, tolerates air moisture, achieves scalability through continuous‐flow technology, offering straightforward route to multi‐gram quantities enhanced throughput.

Язык: Английский

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