Technological Innovations in Photochemistry for Organic Synthesis: Flow Chemistry, High-Throughput Experimentation, Scale-up, and Photoelectrochemistry

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2752 - 2906

Опубликована: Авг. 10, 2021

Photoinduced chemical transformations have received in recent years a tremendous amount of attention, providing plethora opportunities to synthetic organic chemists. However, performing photochemical transformation can be quite challenge because various issues related the delivery photons. These challenges barred widespread adoption steps industry. past decade, several technological innovations led more reproducible, selective, and scalable photoinduced reactions. Herein, we provide comprehensive overview these exciting advances, including flow chemistry, high-throughput experimentation, reactor design scale-up, combination photo- electro-chemistry.

Язык: Английский

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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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Carbon–sulfur bond formation via photochemical strategies: An efficient method for the synthesis of sulfur-containing compounds

Chinese Chemical Letters, Год журнала: 2021, Номер 33(4), С. 1798 - 1816

Опубликована: Сен. 27, 2021

Язык: Английский

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A general electron donor–acceptor complex for photoactivation of arenes via thianthrenation

Chemical Science, Год журнала: 2022, Номер 13(19), С. 5659 - 5666

Опубликована: Янв. 1, 2022

General photoactivation of EDA complexes between arylsulfonium salts and 1,4-diazabicyclo[2.2.2]octane was discovered. This practical mode enables the generation aryl radicals for C–H functionalization arenes.

Язык: Английский

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Cu-Mediated Thianthrenation and Phenoxathiination of Arylborons

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(18), С. 10431 - 10440

Опубликована: Апрель 26, 2023

Great success in synthetic chemistry is motivated by the development of novel and reactive linchpins for carbon-carbon carbon-heteroatom bond formation reactions, which has dramatically altered chemists' approach to building molecules. Herein, we report ready synthesis aryl sulfonium salts, a versatile electrophilic linchpin, via Cu-mediated thianthrenation phenoxathiination commercially available arylborons with thianthrene phenoxathiine, providing series salts high efficiency. More importantly, leveraging sequential Ir-catalyzed C-H borylation arylborons, formal arenes also achieved. The undirected normally occurred at less steric hindrance position, thus complementary method comparison thianthrenation. This process capable late-stage functionalization pharmaceuticals, might find wide applications both industry academic sectors.

Язык: Английский

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Recent Advances in Electron Donor‐Acceptor (EDA)‐Complex Reactions involving Quaternary Pyridinium Derivatives

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(10), С. 1538 - 1564

Опубликована: Март 6, 2023

Abstract Quaternary pyridinium compounds are valuable intermediates in organic synthesis, which have gained immense popularity the synthetic community. The application of transition metal or photoredox catalysis transforming quaternary into various C−C and C−X bonds is well established. A majority these methods require high temperatures, expansive catalysts, delicate conditions for successful execution. On other hand, use metal‐free photocatalysis‐free strategies constructing using derivatives has been sought‐after. In this context, electron‐donor‐acceptor (EDA)‐complex reactions emerged as a state‐of‐the‐art methodology, do not any photocatalyst their EDA‐complex photochemistry takes advantage electron‐acceptor ability derivatives, can quickly generate radical precursor via deaminative process. These newly generated useful several transformations. We hereby, review, discuss an area major progress mediated involving with mechanism, substrate scope, limitations. magnified image

Язык: Английский

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An overview on copper in industrial chemistry: From ancient pigment to modern catalysis

Coordination Chemistry Reviews, Год журнала: 2025, Номер 529, С. 216438 - 216438

Опубликована: Янв. 17, 2025

Язык: Английский

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Copper‐Catalyzed Difluoromethylation of Alkyl Iodides Enabled by Aryl Radical Activation of Carbon–Iodine Bonds

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(52), С. 27070 - 27077

Опубликована: Окт. 15, 2021

Abstract The engagement of unactivated alkyl halides in copper‐catalyzed cross‐coupling reactions has been historically challenging, due to their low reduction potential and the slow oxidative addition copper(I) catalysts. In this work, we report a novel strategy that leverages halogen abstraction ability aryl radicals, thereby engaging diverse range iodides Negishi‐type at room temperature. Specifically, radicals generated via copper catalysis efficiently initiate cleavage carbon–iodide bonds iodides. thus enter catalytic cycles couple with difluoromethyl zinc reagent, furnishing difluoromethane products. This unprecedented difluoromethylation approach applied late‐stage modification densely functionalized pharmaceutical agents natural

Язык: Английский

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Biosynthesis of Tasikamides via Pathway Coupling and Diazonium-Mediated Hydrazone Formation

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(4), С. 1622 - 1633

Опубликована: Янв. 21, 2022

Naturally occurring hydrazones are rare despite the ubiquitous usage of synthetic in preparation organic compounds and functional materials. In this study, we discovered a family novel microbial metabolites (tasikamides) that share unique cyclic pentapeptide scaffold. Surprisingly, tasikamides A–C (1–3) contain hydrazone group (C═N─N) joins peptide scaffold to an alkyl 5-hydroxylanthranilate (AHA) moiety. We biosynthesis 1–3 requires two discrete gene clusters, with one encoding nonribosomal synthetase (NRPS) pathway for assembling another AHA-synthesizing pathway. The AHA cluster encodes three ancillary enzymes catalyze diazotization yield aryl diazonium species (diazo-AHA). electrophilic diazo-AHA undergoes nonenzymatic Japp–Klingemann coupling β-keto aldehyde-containing precursor furnish 1–3. studies together unraveled mechanism whereby specialized formed by biosynthetic pathways via unprecedented vivo reaction. findings raise prospect exploiting arylamine-diazotizing (AAD) synthesis modification biological macromolecules.

Язык: Английский

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Meerwein‐type Bromoarylation with Arylthianthrenium Salts

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(47)

Опубликована: Сен. 7, 2022

Herein, we report a photocatalyzed Meerwein-type bromoarylation of alkenes with stable arylthianthrenium salts, formed by site-selective C-H thianthrenation. This protocol can be applied to late-stage functionalization variety biomolecules that are difficult access other aryl coupling reagents. Halogen introduction allows for follow-up transformations, affording numerous biologically active skeletons.

Язык: Английский

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