Organophotoelectrocatalytic C(sp²)–H alkylation of heteroarenes with unactivated C(sp³)–H compounds

Chemical Communications, Год журнала: 2024, Номер 60(42), С. 5502 - 5505

Опубликована: Янв. 1, 2024

An organophotoelectrocatalytic method for the C(sp 2 )–H alkylation of heteroarenes with unactivated 3 compounds via dehydrogenation cross-coupling was developed.

Язык: Английский

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Alkanes in Minisci-Type Reaction under Photocatalytic Conditions with Hydrogen Evolution

Organic Letters, Год журнала: 2023, Номер 25(48), С. 8541 - 8546

Опубликована: Окт. 11, 2023

We report herein a protocol for the selective activation of C(sp3)–H bonds based on interplay two readily available organic catalysts and their successful implementation in cross-coupling azaarenes with alkanes. This Minisci-like reaction is promoted by visible light at room temperature free from chemical oxidants, metals, chlorinated solvents. A wide range substrates are compatible, including some bioactive molecules. Mechanistic studies support dual catalytic cycle H2 evolution.

Язык: Английский

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Minisci reaction of heteroarenes and unactivated C(sp³)–H alkanes via a photogenerated chlorine radical

Chemical Communications, Год журнала: 2023, Номер 59(12), С. 1637 - 1640

Опубликована: Янв. 1, 2023

Minisci reaction of heteroarenes and unactivated C(sp 3 )–H alkanes via a photogenerated chlorine radical from FeCl seawater.

Язык: Английский

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C–C bond formationviaphotocatalytic direct functionalization of simple alkanes

Chemical Communications, Год журнала: 2023, Номер 59(62), С. 9424 - 9444

Опубликована: Янв. 1, 2023

This article reviews the methodologies available to achieve C–C bond formation via photocatalytic and photo-electrocatalytic direct functionalization of simple alkanes.

Язык: Английский

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C(sp³)‐H Functionalization Using Chlorine Radicals

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(13), С. 2898 - 2918

Опубликована: Май 18, 2024

Abstract Converting any desired C−H bond to the intended C−Z in a given organic molecule could be final peak of functionalization methodology. Among three types bonds, ubiquitous C( sp 3 )−H has gained particular attention, especially last two decades. There are different ways transform bonds into bonds. The use chlorine radicals is one these methods with promising future. literature review shows that sources have been used for chlorine, including chloride ions (HCl or salts), coordinated chlorides (transition metal complexes), and (organochlorine compounds). However, HCl FeCl most attention among sources. major convert from radicals: 1) oxidation hydrogen salts, 2) photolysis chloride, 3) transition insertion C−Cl This summarizes published research papers on functionalization. Therefore, chlorination reactions which do not play direct role cleavage within scope this review.

Язык: Английский

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Enhanced Reactivity of Acridinium Perchlorate: Harnessing Redox Mediators for Trace Chloride Activation in Hydrogen Atom Transfer Photocatalysis

ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9364 - 9373

Опубликована: Июнь 5, 2024

Acridinium perchlorates and tetrafluoroborates are commonly employed photocatalysts with similar photophysical characteristics. Nevertheless, perchlorate salts consistently exhibit superior catalytic performance relative to their tetrafluoroborate counterparts. In a serendipitous discovery, we unveiled the latent potential of trace chloride anions originating from acridinium salts. When coupled redox mediators like diphenyl ether or biphenyl, displayed remarkable hydrogen atom transfer (HAT) catalysis capabilities. This innovative approach enabled efficient activation diverse range unactivated C–H bonds, especially primary C(sp3)–H via Giese additions Minisci-type cross-dehydrogenative coupling reactions. Our system stands as one most HAT systems for bond activation, showcasing substrate diversity. Additionally, use stop-flow microtubing (SFMT) reactor enhanced reaction efficiency, enabling gram-scale synthesis seamless transition continuous flow processes practical-scale production.

Язык: Английский

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Brønsted Acid-Promoted Intermolecular Dearomative Photocycloaddition of Bicyclic Azaarenes with Olefins under Aerobic Conditions

Organic Letters, Год журнала: 2023, Номер 25(17), С. 3089 - 3093

Опубликована: Апрель 25, 2023

Herein, we present a simplified reaction protocol for the dearomatization of bicyclic azaarenes via photochemical cycloaddition with alkenes using an Ir(III) photosensitizer, trifluoroacetic acid (TFA), dichloroethane, and blue light-emitting diode. An efficient protonation TFA enhances reactivity triplet azaarene toward olefins, enabling photocycloaddition under aerobic conditions. The applies to broad range substrates. Control experiments indicate strong correlation between degree product yield.

Язык: Английский

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Organophotoredox-Catalyzed Oxidative C(sp2)–H Alkylation of N-Heteroarenes with Dihydroquinazolinones by C–C Cleavage

Synlett, Год журнала: 2023, Номер 34(11), С. 1241 - 1246

Опубликована: Фев. 8, 2023

Abstract We report a visible-light-mediated, organophotoredox-catalyzed, C(sp2)–H alkylation of N-heteroarenes with dihydroquinazolines, prepared from aliphatic ketones, under oxidative conditions. This protocol represents metal-free approach to the effective construction C–C bonds through Minisci-type reaction, formally activating native C–H bond N-heteroarene and an α-C–C readily available ketone. The mild nature this method accommodates wide variety tolerating range functional groups.

Язык: Английский

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Heterogeneous Photocatalysis as a Potent Tool for Organic Synthesis: Cross-Dehydrogenative C–C Coupling of N-Heterocycles with Ethers Employing TiO2/N-Hydroxyphthalimide System under Visible Light

Molecules, Год журнала: 2023, Номер 28(3), С. 934 - 934

Опубликована: Янв. 17, 2023

Despite the obvious advantages of heterogeneous photocatalysts (availability, stability, recyclability, ease separation from products and safety) their application in organic synthesis faces serious challenges: generally low efficiency selectivity compared to homogeneous photocatalytic systems. The development strategies for improving catalytic properties semiconductor materials is key introduction into synthesis. In present work, a hybrid system involving both catalyst (TiO2) organocatalyst (N-hydroxyphthalimide, NHPI) was proposed cross-dehydrogenative C–C coupling electron-deficient N-heterocycles with ethers employing t-BuOOH as terminal oxidant. It should be noted that each catalysts completely ineffective when used separately under visible light this transformation. occurrence absorption upon interaction NHPI TiO2 surface generation reactive phthalimide-N-oxyl (PINO) radicals irradiation are considered main factors determining high efficiency. method suitable π-deficient pyridine, quinoline, pyrazine, quinoxaline heteroarenes various non-activated ethers.

Язык: Английский

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Metal- and photosensitizer-free cross-dehydrogenative coupling through photoinduced energy transfer

Green Chemistry, Год журнала: 2024, Номер 26(8), С. 4742 - 4748

Опубликована: Янв. 1, 2024

This study introduces a novel, eco-friendly method for Minisci alkylation without harmful catalysts, advancing sustainable pharmaceutical synthesis through energy transfer from heteroarenes to peroxide, offering significant environmental benefits.

Язык: Английский

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