Visible Light-Induced Transition Metal Catalysis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1543 - 1625

Published: Oct. 8, 2021

In recent years, visible light-induced transition metal catalysis has emerged as a new paradigm in organic photocatalysis, which led to the discovery of unprecedented transformations well improvement known reactions. this subfield complex serves double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via single catalytic cycle, thus contrasting established dual photocatalysis an exogenous photosensitizer is employed. addition, approach often synergistically combines catalyst–substrate interaction with photoinduced process, feature that uncommon conventional photoredox chemistry. This Review describes early development advances emerging field.

Language: Английский

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Merging Photoinduced Iron-Catalyzed Decarboxylation with Copper Catalysis for C–N and C–C Couplings

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(3), P. 1678 - 1685

Published: Jan. 13, 2023

We report a photoinduced iron/copper dual-catalytic strategy for the radical decarboxylation functionalization of aliphatic carboxylic acids. The ligand-to-iron charge transfer process under light was initially occurred to generate an unstabilized alkyl radical, and copper catalyst delivered enabled subsequent coupling reactions form C–N or C–C bonds. By merging iron-catalyzed with catalysis, this system allows smooth conversion wide range acids amination, decarboxylative dehydrogenation, alkylation efficiently. A variety complex drug natural molecules is applicable, suggesting that would facilitate rapid compound library synthesis benefit discovery pharmaceutical agents.

Language: Английский

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A review on sustainable iron oxide nanoparticles: syntheses and applications in organic catalysis and environmental remediation

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(13), P. 7579 - 7655

Published: Jan. 1, 2024

In this review paper, recent developments of iron oxide nanoparticles are highlighted and discussed in the field organic catalysis environmental remediation.

Language: Английский

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Mechanisms of Photoredox Catalysis Featuring Nickel–Bipyridine Complexes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 9055 - 9076

Published: May 29, 2024

Metallaphotoredox catalysis can unlock useful pathways for transforming organic reactants into desirable products, largely due to the conversion of photon energy chemical potential drive redox and bond transformation processes. Despite importance these processes cross-coupling reactions other transformations, their mechanistic details are only superficially understood. In this review, we have provided a detailed summary various photoredox mechanisms that been proposed date Ni-bipyridine (bpy) complexes, focusing separately on photosensitized direct excitation reaction By highlighting multiple key findings, depict how mechanisms, which ultimately define substrate scope, themselves defined by ground- excited-state geometric electronic structures Ni-based intermediates. We further identify knowledge gaps motivate future studies development synergistic research approaches spanning physical, organic, inorganic chemistry communities.

Language: Английский

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Aminative Suzuki–Miyaura coupling

Science, Journal Year: 2024, Volume and Issue: 383(6686), P. 1019 - 1024

Published: Feb. 29, 2024

The Suzuki-Miyaura and Buchwald-Hartwig coupling reactions are widely used to form carbon-carbon (C-C) carbon-nitrogen (C-N) bonds, respectively. We report the incorporation of a formal nitrene insertion process into reaction, altering products from C-C-linked biaryls C-N-C-linked diaryl amines thereby joining pathways same starting-material classes. A combination bulky ancillary phosphine ligand on palladium commercially available amination reagent enables efficient reactivity across aryl halides pseudohalides, boronic acids esters, many functional groups heterocycles. Mechanistic insights reveal flexibility order bond-forming events, suggesting potential for expansion aminative cross-coupling concept encompass diverse nucleophiles electrophiles as well four-component variants.

Language: Английский

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Ligand-Enabled “Two-in-One” Metallaphotocatalytic Cross Couplings

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1635 - 1654

Published: Jan. 15, 2025

Metallaphotoredox cross coupling (MCC) is ranking among the most advanced synthetic methodology as it can access chemical space that difficult to attain under conventional conditions. Earlier developed MCC mandates an independent transition metal catalyst and respective photocatalyst, thus constituting a dual catalytic manifold. Complementarily, paradigm-shifting metallaphotoredox strategy capitalizes on single photoreactive complex emerging, which brings not only operational simplification but also unexpected mechanistic insights. This perspective compiled recent advances in monocatalytic couplings categorized them based ligands confer distinct photoreactivities various mechanisms. To this end, ligand-enabled oxidative addition, transmetalation, reductive elimination other radical-involving pathways were summarized with notable examples. In way, we wish provide handy guideline for readers who are interested emerging field inspire more future endeavors MCCs beyond.

Language: Английский

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Site-specific Umpolung amidation of carboxylic acids via triplet synergistic catalysis

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

Published: July 30, 2021

Abstract Development of catalytic amide bond-forming methods is important because they could potentially address the existing limitations classical using superstoichiometric activating reagents. In this paper, we disclose an Umpolung amidation reaction carboxylic acids with nitroarenes and nitroalkanes enabled by triplet synergistic catalysis FeI 2 , P(V)/P(III) photoredox catalysis, which avoids production byproducts from stoichiometric coupling A wide range acids, including aliphatic, aromatic alkenyl participate smoothly in such reactions, generating structurally diverse amides good yields (86 examples, up to 97% yield). This strategy opens a method challenging regioselectivity issues between nucleophilic functional groups, complements group compatibility protocols. The synthetic robustness demonstrated late-stage modification complex molecules gram-scale applications.

Language: Английский

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Chiral Arylated Amines via C−N Coupling of Chiral Amines with Aryl Bromides Promoted by Light

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(39), P. 21536 - 21542

Published: July 14, 2021

Abstract The Buchwald‐Hartwig C‐N coupling reaction has found widespread applications in organic synthesis. Over the past two decades or so, many improved catalysts have been introduced, allowing various amines and aryl electrophiles to be readily used nowadays. However, there lacks a protocol that could couple wide range of chiral halides, without erosion enantiomeric excess ( ee ). Reported this article is method based on molecular Ni catalysis driven by light, which enables stereoretentive optically active amines, amino alcohols, acid esters with bromides, no need for any external photosensitizer. effective variety partners, including those bearing functional groups sensitive bases nucleophiles, thus providing viable alternative accessing synthetically important N ‐aryl acids esters. Its viability demonstrated 92 examples up 99 % .

Language: Английский

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Decarboxylative tandem C-N coupling with nitroarenes via SH2 mechanism

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 4, 2022

Abstract Aromatic tertiary amines are one of the most important classes organic compounds in chemistry and drug discovery. It is difficult to efficiently construct from primary via classical nucleophilic substitution due consecutive overalkylation. In this paper, we have developed a radical tandem C-N coupling strategy aromatic commercially available carboxylic acids nitroarenes. A variety can be furnished good yields (up 98%) with excellent functional group compatibility under mild reaction conditions. The use two different also allows for concise synthesis nonsymmetric satisfactory yields. Mechanistic studies suggest intermediacy arylamine–(TPP)Fe(III) species might provide possible evidence an S H 2 (bimolecular homolytic substitution) pathway critical bond formation step.

Language: Английский

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Intraligand Charge Transfer Enables Visible‐Light‐Mediated Nickel‐Catalyzed Cross‐Coupling Reactions**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(46)

Published: Sept. 26, 2022

We demonstrate that several visible-light-mediated carbon-heteroatom cross-coupling reactions can be carried out using a photoactive NiII precatalyst forms in situ from nickel salt and bipyridine ligand decorated with two carbazole groups (Ni(Czbpy)Cl2 ). The activation of this towards follows hitherto undisclosed mechanism is different previously reported light-responsive complexes undergo metal-to-ligand charge transfer. Theoretical spectroscopic investigations revealed irradiation Ni(Czbpy)Cl2 visible light causes an initial intraligand transfer event triggers productive catalysis. Ligand polymerization affords porous, recyclable organic polymer for heterogeneous catalysis reactions. catalyst shows stable performance packed-bed flow reactor during week continuous operation.

Language: Английский

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