Structurally Well-Defined PC(sp³)P Osmium Pincer Catalysts for Methylation of Alcohols, Indoles, Phenols, and Sulfonamides Using Methanol as a C₁ Source

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1629 - 1638

Published: Jan. 17, 2024

Recent findings show pincer catalysts of osmium superior in a broad spectrum synthetically valuable transformations. This article reports structurally well-defined Os(II)PCsp3P complexes stabilized by functional dibenzobarrelene-based ligand. We describe their organometallic and catalytic properties the hydride transfer reactions. demonstrate that center, covalently locked within 3-dimensional ligand pocket, exhibits strictly predictable coordination behavior redox rigidity while remaining catalytically active owing to potential cooperation with proximate side arm. The described were found as mild selective methylation alcohols, indoles, phenols, sulfonamides using methanol C1 source.

Language: Английский

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Engineering a Photoenzyme to Use Red Light

Published: March 18, 2024

Photoenzymatic catalysis is an emerging platform for asymmetric synthesis. In most of these reactions, the protein templates a charge transfer complex between cofactor and substrate, which absorbs in blue region electromagnetic spectrum. Here, we report engineering photoenzymatic ‘ene’-reductase to utilize red light (620 nm) radical cyclization reaction. Mechanistic studies indicate that ac-tivity achieved by introducing broadly absorbing shoulder off previously identified cyan absorption feature. Molecular dynamics simulations, docking, excited-state calculations suggest 𝜋→ 𝜋* transition from flavin while feature red-shift transition, occurs upon substrate binding. Differences excitation event help disfavor alkylation cofactor, pathway catalyst decomposition observed with but not red.

Language: Английский

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Bimetallic Porphyrin Metal–Organic Framework as Photocatalyst for Red-Light-Driven Selective Reduction of Nitroarenes to Aromatic Amines

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

It is a great challenge to construct green catalytic system for the reduction of nitro compounds corresponding amines under mild conditions. Due low energy red light, it challenging develop photocatalytic selective nitroaromatics aromatic driven by light. A bimetallic porphyrin metal–organic framework (Bi-P(Co)MOF) was characterized Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, scanning and energy-dispersive techniques. The constructed photocatalyst Bi-PMOF-Co shows excellent activity conversion in high yields with NaBH4 as reducing agent at room temperature light irradiation. Moreover, protocol showed functional group compatibility, recyclability demonstrated five-cycle tests.

Language: Английский

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Shining a Light on the Advances, Challenges and Realisation of Utilising Photoredox Catalysis in Pharmaceutical Development

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(15)

Published: July 5, 2023

Abstract Photoredox catalysis has advanced significantly over the last fifteen years, with improvements in technology facilitating implementation both academic and industrial settings. Despite these advances, uptake of photoredox pharmaceutical development manufacture been slow, part due to challenge developing a robust, transferable process. This perspective provides insight on successes difficulties encountered when applying development. It is hoped greater understanding challenges faced by industry will inform future research encourage collaboration.

Language: Английский

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A Unified Method for Oxidative and Reductive Decarboxylative Arylation with Orange Light-Driven Ir/Ni Metallaphotoredox Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25780 - 25787

Published: Sept. 5, 2024

Carboxylic acids and their derivatives are powerful building blocks in dual Ir/Ni metallaphotoredox methods of decarboxylative arylation due to abundance as feedstock compounds. However, the library accessible carboxylic is limited by trends radical stability, often necessitating development specific systems for challenging substrates. Herein, we disclose application a new Ir(III) photocatalyst low-energy orange light system with broad applicability activating both native redox-active esters (RAEs). This method represents first known example complementary oxidative reductive paradigms broadly similar reaction conditions, unlocking reactivity We further show wide scope aryl halide acid coupling partners regimes, added advantages over blue-light-catalyzed alkylation photosensitive

Language: Английский

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Visible-Light-Mediated Rose Bengal- or [Ru(bpy)₃]²⁺-Catalyzed Radical [4 + 2] Cycloaddition: An Efficient Route to Tetrahydrocarbazoles

ACS Omega, Journal Year: 2025, Volume and Issue: 10(10), P. 10713 - 10723

Published: March 7, 2025

A visible-light-induced Rose Bengal- or [Ru(bpy)3]2+-catalyzed radical [4 + 2] cycloaddition of redox-active indole N-hydroxyphthalimide esters with electron-deficient alkenes has been developed. This base-free protocol provides a facile and powerful route for the synthesis functionalized biologically significant tetrahydrocarbazoles under mild conditions. On one hand, when an organic photocatalyst-Rose Bengal was employed green light, desired were obtained in up to 82% yield. other reaction yield increased 93% presence [Ru(bpy)3Cl2]·6H2O blue light. The success gram-scale transformation experiments, as well photopromoted [5 further highlight practicality robustness this protocol. Mechanistic studies also support generation crucial alkyl intermediate.

Language: Английский

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Near-Infrared-Light-Induced Iron(I) Dimer Enabled Abstraction of Ester Group from Cycloketone Oxime Esters

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

Photoinduced dimeric metal complexes have been extensively utilized in halogen atom transfer (XAT) reactions. In this study, we successfully achieved the abstraction of ester group from cyclobutanone oxime esters via iron(I)-dimer catalysis under near-infrared (NIR) light (730 nm) excitation, enabling efficient synthesis cyanoalkylated alkenes, quinazolinones, and 3,3-disubstituted oxindoles. Mechanistic investigations confirmed NIR-induced functional process.

Language: Английский

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Arylation of C=C bonds via non-cross-coupling reactions: historical evolution of the Meerwein arylation mechanisms

ChemTexts, Journal Year: 2025, Volume and Issue: 11(2)

Published: March 20, 2025

Language: Английский

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Red-Light-Induced Cysteine Modifications Suitable for Protein Labeling

ACS Organic & Inorganic Au, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

Language: Английский

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High‐Performance 721 nm‐Excitable Photon Upconversion Porous Aromatic Frameworks for Broad‐Range Oxygen Sensing and Efficient Heterogeneous Photoredox Catalysis

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 10, 2025

Abstract The development of long‐wavelength excitable solid upconversion materials and the regulation exciton behavior is important for solar energy harvesting, photocatalysis, other emerging applications. However, approaches regulating diffusion are very limited, resulting in extremely poor photonic performance solid‐state. Here, annihilation unit integrated into porous aromatic frameworks (PAFs) loaded with photosensitizer to construct efficient 721 nm‐excitable material (upconversion quantum yield up 1.5%, upper limit 50%). Most importantly, we found that steric hindrance annihilator units breaks π‐conjugation between PAFs framework form homogeneous triplet energy, which conducive diffusion. After increasing constant from 2.0 × 10 −6 1.34 −5 cm 2 s −1 , increased ≈ 50‐fold. Further, this utilized demonstrate, first time, a broad‐range oxygen sensing nm‐driven heterogeneous recyclable photoredox catalysis. These findings provide an approach disorder gain better performance, will advance practical applications organic photon chemistry, photonics.

Language: Английский

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