Relay Photocatalytic Reaction of N-Aryl Amino Acids and 2-Bromo-3,3,3-trifluoropropene: Synthesis of 4-(Difluoromethylidene)-tetrahydroquinolines DOI
Weidi Zeng, Weiyu Li,

Haoguo Chen

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(17), P. 3265 - 3269

Published: April 25, 2022

The bulk industrial chemical 2-bromo-3,3,3-trifluoropropene (BTP) was first employed as a coupling partner in photocatalytic defluorinative reactions with N-aryl amino acids. Photoredox activation of the C(sp2)–Br bond resultant 2-bromo-1,1-difluoroalkenes generates gem-difluoro vinyl radicals for further radical cyclization. Various 4-(difluoromethylidene)-tetrahydroquinolines were assembled good yields by combining two photoredox cycles single photocatalyst.

Language: Английский

Recent advances of visible-light photocatalysis in the functionalization of organic compounds DOI
Vishal Srivastava, Pravin K. Singh, Praveen P. Singh

et al.

Journal of Photochemistry and Photobiology C Photochemistry Reviews, Journal Year: 2022, Volume and Issue: 50, P. 100488 - 100488

Published: Feb. 2, 2022

Language: Английский

Citations

135
Electrophilic Halospirocyclization of N-Benzylacrylamides to Access 4-Halomethyl-2-azaspiro[4.5]decanes DOI
Zhongyi Zhang, Wei Zhang,

Zhong‐Wei Hou

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(19), P. 13610 - 13621

Published: Sept. 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.

Language: Английский

Citations

58
Visible-Light-Enabled Ortho-Selective Aminopyridylation of Alkenes with N-Aminopyridinium Ylides DOI
Yonghoon Moon, Wooseok Lee, Sungwoo Hong

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(28), P. 12420 - 12429

Published: July 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.

Language: Английский

Citations

109
Organophotocatalytic selective deuterodehalogenation of aryl or alkyl chlorides DOI Creative Commons
Yanjun Li, Ziqi Ye, Yu‐Mei Lin

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: May 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.

Language: Английский

Citations

90
Visible-Light-Induced Radical Carbo-Cyclization/gem-Diborylation through Triplet Energy Transfer between a Gold Catalyst and Aryl Iodides DOI
Lumin Zhang,

Xiaojia Si,

Frank Röminger

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(23), P. 10485 - 10493

Published: April 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.

Language: Английский

Citations

73
Two‐Dimensional Metal–Organic Framework Nanosheets: Synthesis and Applications in Electrocatalysis and Photocatalysis DOI

Ya‐Long Liu,

Xiang‐Yue Liu,

Li Feng

et al.

ChemSusChem, Journal Year: 2022, Volume and Issue: 15(10)

Published: Jan. 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.

Language: Английский

Citations

69
Photochemical Alkene Trifluoromethylimination Enabled by Trifluoromethylsulfonylamide as a Bifunctional Reagent DOI
Yu Zheng,

Zihao Liao,

Zhenzhen Xie

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(12), P. 2129 - 2133

Published: March 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.

Language: Английский

Citations

27
Photocatalytic Reductive Functionalization of Aryl Alkynes via Alkyne Radical Anions DOI
Xiaogang Tong, Zugen Wu, Hwee Ting Ang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9283 - 9293

Published: June 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.

Language: Английский

Citations

11
Visible‐Light‐Induced Cysteine‐Specific Bioconjugation: Biocompatible Thiol–Ene Click Chemistry DOI
Hangyeol Choi, Myojeong Kim, Jaebong Jang

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(50), P. 22514 - 22522

Published: Aug. 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

Language: Английский

Citations

57
An integrated giant polyoxometalate complex for photothermally enhanced catalytic oxidation DOI Creative Commons

Xiaofei Chen,

Guohua Zhang, Bao Li

et al.

Science Advances, Journal Year: 2021, Volume and Issue: 7(30)

Published: July 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.

Language: Английский

Citations

47