A π-conjugated covalent organic framework enables interlocked nickel/photoredox catalysis for light-harvesting cross-coupling reactions

Chemical Science, Journal Year: 2023, Volume and Issue: 14(32), P. 8624 - 8634

Published: Jan. 1, 2023

Covalent organic frameworks (COFs) are an outstanding platform for heterogeneous photocatalysis. Herein, we synthesized a pyrene-based two-dimensional C[double bond, length as m-dash]C linked π-conjugated COF via Knoevenagel condensation and anchored Ni(ii)-centers through bipyridine moieties. Instead of traditional dual metallaphotoredox catalysis, the mono-metal decorated Ni@Bpy-sp2c-COF interlocked catalysis mediated by light transition metal. Under irradiation, enhanced energy electron transfer in backbone, delineated photoluminescence, electrochemical, control experiments, expedited excitation Ni centers to efficiently catalyze diverse photocatalytic C-X (X = B, C, N, O, P, S) cross-coupling reactions with efficiencies orders magnitude higher than homogeneous controls. The catalyst tolerated range coupling partners various steric electronic properties, delivering products up 99% yields. Some were performed on gram scale applied diversify pharmaceuticals complex molecules demonstrate synthetic utility.

Language: Английский

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Visible light-induced functionalization of indazole and pyrazole: a recent update

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(28), P. 4435 - 4455

Published: Jan. 1, 2022

Indazole and pyrazole are renowned as a prodigious class of heterocycles having versatile uses in medicinal well industrial chemistry. Considering sustainable approaches, recently, photocatalysis has become an indispensable tool organic chemistry due to its application for the activation small molecules use clean energy source. In this review, we have highlighted metal-based photocatalysts, photoredox catalysts, transfer photocatalysts electron-donor-acceptor complexes functionalization indazole pyrazole. This perspective is arranged based on types reactions A detailed discussion regarding reaction mechanism each given provide comprehensive guide reader. Finally, summary existing challenges future outlook towards development efficient photocatalytic methods these also presented.

Language: Английский

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Photoinduced Halogen-Atom Transfer by N-Heterocyclic Carbene-Ligated Boryl Radicals for C(sp³)–C(sp³) Bond Formation

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 145(2), P. 991 - 999

Published: Dec. 30, 2022

Herein, we present a comprehensive study on the use of N-heterocyclic carbene (NHC)-ligated boryl radicals to enable C(sp3)–C(sp3) bond formation under visible-light irradiation via Halogen-Atom Transfer (XAT). The methodology relies an acridinium dye generate boron-centered from corresponding NHC-ligated boranes single-electron transfer (SET) and deprotonation. These subsequently engage with alkyl halides in XAT step, delivering desired nucleophilic radicals. strategy is very mild accommodates broad scope halides, including medicinally relevant compounds biologically active molecules. key role operative reaction mechanism has been elucidated through combination experimental, spectroscopic, computational studies. This stands as significant advancement chemistry radicals, which had long restricted radical reductions, enabling C–C photoredox conditions.

Language: Английский

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Visible-light-induced metal-free coupling of C(sp³)–H sources with heteroarenes

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(8), P. 3056 - 3080

Published: Jan. 1, 2022

This critical review chronologically summarizes the metal-free coupling methodologies of C(sp 3 )–H sources with heteroarenes induced by visible light. The articles which are published up to January 2022 on this topic enclosed here.

Language: Английский

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Visible light-induced organophotoredox-catalyzed difunctionalization of alkenes and alkynes

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(21), P. 8459 - 8493

Published: Jan. 1, 2023

This review comprehensively summarizes visible light-induced difunctionalization strategies for alkene and alkyne systems in metal-free conditions with literature coverage up to July 2023.

Language: Английский

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Visible-light-induced cascade reaction: a sustainable approach towards molecular complexity

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(8), P. 1591 - 1628

Published: Jan. 1, 2023

Photoredox catalysis has demonstrated rapid evolution in the field of synthetic organic chemistry. On other hand, splendour cascade reactions providing complex molecular architectures renders them a cutting-edge research area. Therefore, merging photocatalysis with synthesis brings out paradigm immense potential. The development photocascade for target molecule particular skeleton and stereochemical framework presents certain challenges but provides robust environmentally benign alternative. This comprehensive review assembles all accomplishments highlights visible-light-induced literature coverage up to October 2022.

Language: Английский

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Halogen Atom Transfer-Induced Homolysis of C–F Bonds by the Excited-State Boryl Radical

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 22874 - 22880

Published: Aug. 2, 2024

A novel reactivity toward C-F bond functionalization has been developed, which could be designated as fluorine atom transfer (FAT). photoexcited state of an

Language: Английский

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Photocatalytic generation of ligated boryl radicals from tertiary amine-borane complexes: An emerging tool in organic synthesis

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(5), P. 957 - 966

Published: April 12, 2022

Language: Английский

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Recent Advances in Microwave‐assisted Cross‐Coupling Reactions

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(8)

Published: June 13, 2022

Abstract The carbon–carbon and carbon–heteroatom bond forming coupling reactions have a fundamental value for the organic chemistry, and, therefore, these been always among most valuable basic studies evolution of synthesis are extensively used practically compounds. Currently, greener techniques pulled in consideration researchers due to rising environmental concern. Nowadays, modern synthetic chemists both academia industry trying design desired target molecules by using eco‐friendly methods. In this context, microwave‐assisted (MAOS) is known as one convenient emerging technologies chemistry. Microwave activation/heating very technique from viewpoint green chemistry because it speeds up reaction rates provides higher yield reducing side reactions. present review represents literature survey 2008 2021 that covers latest trends C−C C−heteroatom with prospects.

Language: Английский

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A Unified Synthetic Strategy to Introduce Heteroatoms via Electrochemical Functionalization of Alkyl Organoboron Reagents

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(20), P. 9149 - 9160

Published: May 16, 2022

Based on systematic electrochemical analysis, an integrated synthetic platform of C(sp3)-based organoboron compounds was established for the introduction heteroatoms. The electrochemically mediated bond-forming strategy shown to be highly effective functionalization sp3-hybridized carbon atoms with significant steric hindrance. Moreover, virtually all nonmetallic heteroatoms could utilized as reaction partners using one unified protocol. observed reactivity stems from two consecutive single-electron oxidations substrate, which eventually generates extremely reactive carbocation key intermediate. detailed profile elucidated through multifaceted studies. Ultimately, a new dimension in activation strategies accomplished driven development.

Language: Английский

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