Recent advances of visible-light photocatalysis in the functionalization of organic compounds

Journal of Photochemistry and Photobiology C Photochemistry Reviews, Год журнала: 2022, Номер 50, С. 100488 - 100488

Опубликована: Фев. 2, 2022

Язык: Английский

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Electrophilic Halospirocyclization of N-Benzylacrylamides to Access 4-Halomethyl-2-azaspiro[4.5]decanes

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(19), С. 13610 - 13621

Опубликована: Сен. 11, 2023

An electrophilic spirocyclization of N-benzylacrylamides with N-halosuccinimides (NXS) as the halogenating reagents has been developed. This reaction is carried out at room temperature under simple conditions without relying on metal reagents, photochemistry, or electrochemistry, providing a fast and efficient route to synthesize wide variety 4-halomethyl-2-azaspiro[4.5]decanes satisfactory yields. The approach further highlighted through gram-scale synthesis diverse transformations spiro products.

Язык: Английский

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Visible-Light-Enabled Ortho-Selective Aminopyridylation of Alkenes with N-Aminopyridinium Ylides

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(28), С. 12420 - 12429

Опубликована: Июль 2, 2020

By utilizing an underexplored reactivity mode of N-aminopyridinium ylides, we developed the visible-light-induced ortho-selective aminopyridylation alkenes via radical-mediated 1,3-dipolar cycloaddition. The photocatalyzed single-electron oxidation ylides generates corresponding radical cations that enable previously inaccessible 1,3-cycloaddition with a broader range alkene substrates. resulting cycloaddition adducts rapidly undergo subsequent homolytic cleavage N-N bond, conferring substantial thermodynamic driving force to yield various β-aminoethylpyridines. Remarkably, amino and pyridyl groups can be installed into both activated unactivated modular control ortho-selectivity 1,2-syn-diastereoselectivity under metal-free mild conditions. Combined experimental computational studies are conducted clarify detailed reaction mechanism origins site selectivity diastereoselectivity.

Язык: Английский

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Organophotocatalytic selective deuterodehalogenation of aryl or alkyl chlorides

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Май 17, 2021

Abstract Development of practical deuteration reactions is highly valuable for organic synthesis, analytic chemistry and pharmaceutic chemistry. Deuterodehalogenation chlorides tends to be an attractive strategy but remains a challenging task. We here develop photocatalytic system consisting aryl-amine photocatalyst disulfide co-catalyst in the presence sodium formate as electron hydrogen donor. Accordingly, many aryl chlorides, alkyl other halides are converted deuterated products at room temperature air (>90 examples, up 99% D-incorporation). The mechanistic studies reveal that amine serves reducing photoredox catalyst initiate cleavage C-Cl bond, same time energy transfer induce homolysis consequent deuterium process. This economic environmentally-friendly method can used site-selective D-labeling number bioactive molecules direct H/D exchange some drug molecules.

Язык: Английский

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Visible-Light-Induced Radical Carbo-Cyclization/gem-Diborylation through Triplet Energy Transfer between a Gold Catalyst and Aryl Iodides

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(23), С. 10485 - 10493

Опубликована: Апрель 30, 2020

Geminal diboronates have attracted significant attention because of their unique structures and reactivity. However, benzofuran-, indole-, benzothiophene-based benzylic gem-diboronates, building blocks for biologically relevant compounds, are unknown. A promising protocol using visible light aryl iodides constructing valuable blocks, including via radical carbo-cyclization/gem-diborylation alkynes with a high functional group tolerance is presented. The utility these gem-diboronates has been demonstrated by 10 g scale conversion, versatile transformations, the synthesis approved drug scaffolds two drugs, even polymer synthesis. mechanistic investigation indicates that merging dinuclear gold catalyst (photoexcitation 315–400 nm UVA light) Na2CO3 directly responsible photosensitization 254 UV blue LED (410–490 nm, λmax = 465 nm) through an energy transfer (EnT) process, followed homolytic cleavage C–I bond in iodide substrates.

Язык: Английский

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Two‐Dimensional Metal–Organic Framework Nanosheets: Synthesis and Applications in Electrocatalysis and Photocatalysis

ChemSusChem, Год журнала: 2022, Номер 15(10)

Опубликована: Янв. 29, 2022

Two-dimensional metal-organic nanosheets (2D MONs) are an emerging class of ultrathin, porous, and crystalline materials. The organic/inorganic hybrid nature offers MONs distinct advantages over other inorganic in terms diversity organic ligands metal notes. Compared to bulk three-dimensional frameworks, 2D possess merits high density readily accessible catalytic sites, reduced diffusion pathways for reactants/products, fast electron transport. These features endow with enhanced physical/chemical properties ideal heterogeneous catalysis. In this Review, state-of-the-art synthetic methods the fabrication were summarized. advances MONs-based materials electrocatalysis photocatalysis, including hydrogen evolution reaction (HER), oxygen (OER), reduction (ORR), carbon dioxide (CO2 RR), electro-/photocatalytic transformations systematically discussed. Finally, challenges perspectives regarding future design synthesis high-performance photocatalysis provided.

Язык: Английский

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Photochemical Alkene Trifluoromethylimination Enabled by Trifluoromethylsulfonylamide as a Bifunctional Reagent

Organic Letters, Год журнала: 2023, Номер 25(12), С. 2129 - 2133

Опубликована: Март 21, 2023

Herein, we disclose a facile and versatile trifluoromethylimination of alkene with rationally designed N-(diphenylmethylene)-1,1,1-trifluoromethanesulfonamide as bench-stable readily accessible carboamination reagent. Enabled by an energy transfer (EnT) process, array alkenes were able to be facilely CF3-iminated under metal-free photocatalytic conditions. The mild reaction conditions good functional group compatibility render this protocol highly valuable for the difunctionalization olefins structural complexity diversity.

Язык: Английский

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Photocatalytic Reductive Functionalization of Aryl Alkynes via Alkyne Radical Anions

ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9283 - 9293

Опубликована: Июнь 4, 2024

The direct reductive functionalization of alkynes under mild conditions presents a promising yet challenging avenue for accessing value-added molecules. Alkyne radical anions represent distinct class reactive intermediates characterized by both charge and an unpaired electron, thus holding great potential facilitating diverse bond formations, particularly in alkyne functionalization. However, the synthetic utility is limited, primarily due to difficulty their generation formation highly unstable vinyl intermediates. In this study, we accomplished from aryl feedstocks via single electron transfer (SET) reduction with photogenerated CO2 anion (CO2•–), enabling hydroalkylation, arylalkenylation, hydrocarboxylation alkynes. Our photocatalytic strategy features metal-free catalysis, reaction conditions, employment traceless reductant, good functional group compatibility, step- atom-economy, high regioselectivity. This study not only paves way leveraging underexplored but also catalyzes ongoing exploration bifunctional CO2•– species chemistry.

Язык: Английский

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Visible‐Light‐Induced Cysteine‐Specific Bioconjugation: Biocompatible Thiol–Ene Click Chemistry

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(50), С. 22514 - 22522

Опубликована: Авг. 31, 2020

Abstract Bioconjugation methods using visible‐light photocatalysis have emerged as powerful synthetic tools for the selective modification of biomolecules under mild reaction conditions. However, number photochemical transformations that allow successful protein bioconjugation is still limited because need stringent Herein, we report a newly developed water‐compatible fluorescent photosensitizer Q PEG can be used visible‐light‐induced cysteine‐specific installation by exploiting its intrinsic photosensitizing ability to activate S−H bond cysteine. The slightly modified CAT enables effective photocatalytic conjugation biologically relevant groups. superior reactivity and cysteine selectivity this methodology was further corroborated traceless with series complex peptides proteins biocompatible

Язык: Английский

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An integrated giant polyoxometalate complex for photothermally enhanced catalytic oxidation

Science Advances, Год журнала: 2021, Номер 7(30)

Опубликована: Июль 23, 2021

A strategy integrating near infrared (NIR) photothermal and catalytic effects within one active center beyond ultraviolet visible light is proposed without the combination of separated transformation components. giant polyoxomolybdate, which has high NIR conversion efficiency, selected as model catalyst, while a cationic β-cyclodextrin used to cover its negatively charged surface electrostatically. Under radiation, designed catalyst increases activity cyclohexene oxidation under O2 atmosphere in water. The reaches about pentaploid reaction radiation. By excluding heating effect from external heater at same temperature, twice much enhancement, can be attributed sole action, still observed. While shielded by organic porous layer, cavity allows integrated conduct selective catalysis screening molecules size over channel.

Язык: Английский

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