Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4237 - 4352

Опубликована: Янв. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Язык: Английский

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Enhanced Oxygen Activation Achieved by Robust Single Chromium Atom-Derived Catalysts in Aerobic Oxidative Desulfurization

ACS Catalysis, Год журнала: 2022, Номер 12(14), С. 8623 - 8631

Опубликована: Июль 5, 2022

Oxidative desulfurization (ODS) plays critical roles in the production of high-quality sulfur impurity-free fuels, especially procedures using molecular oxygen as sole oxidant. However, state-of-the-art systems still rely on noble metal nanocatalysts, with deactivation issues caused by coking and sintering present. Herein, leveraging merits single-atom catalysts (SACs) earth-abundant cores robust nanoporous supports, a series composed homogeneously distributed single chromium atoms anchored multiwalled carbon nanotubes were fabricated deployed to catalyze aerobic ODS transformation. Adopting aromatic compound (ASC)-containing alkanes model system oxidant, efficient oxygen-to-active O2•– transformation subsequent ASCs-to-sulfone conversion have been achieved, former benefiting from chromium-active sites latter arising robust, nanoporous, π-conjugated architecture supports. The attractive catalytic performance cycling stability chromium-based SACs make them promising candidates practical species removal liquid supplying an alternative guidance catalyst design toward cost-effective energy-efficient procedures.

Язык: Английский

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Electronic control over site-selectivity in hydrogen atom transfer (HAT) based C(sp³)–H functionalization promoted by electrophilic reagents

Chemical Society Reviews, Год журнала: 2022, Номер 51(6), С. 2171 - 2223

Опубликована: Янв. 1, 2022

Leveraging on electronic effects in both the substrate and HAT reagent, site-selectivity can be implemented C(sp 3 )–H bond functionalization.

Язык: Английский

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Endogenous Photosensitizers in Human Skin

Chemical Reviews, Год журнала: 2023, Номер 123(16), С. 9720 - 9785

Опубликована: Июль 17, 2023

Endogenous photosensitizers play a critical role in both beneficial and harmful light-induced transformations biological systems. Understanding their mode of action is essential for advancing fields such as photomedicine, photoredox catalysis, environmental science, the development sun care products. This review offers comprehensive analysis endogenous human skin, investigating connections between electronic excitation subsequent activation or damage organic biomolecules. We gather physicochemical photochemical properties key examine relationships chemical reactivity, location within primary biochemical events following solar radiation exposure, along with influence on skin physiology pathology. An important take-home message this that photosensitization allows visible light UV-A to have large effects skin. The presented here unveils potential causes continuous increase global cancer cases emphasizes limitations current protection approaches.

Язык: Английский

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Sustainable Aerobic Allylic C–H Bond Oxidation with Heterogeneous Iron Catalyst

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(4), С. 2769 - 2778

Опубликована: Янв. 19, 2024

Emerging techniques are revolutionizing the realm of chemical synthesis by introducing new avenues for C–H bond functionalization, which have been exploited pharmaceuticals, natural compounds, and functional materials. Allylic oxidation alkenes serves as possibly most employed functionalization reaction. However, sustainable selective approaches remain scarce, majority existing conditions still hinge on hazardous oxidants or costly metal catalysts. In this context, we introduce a heterogeneous iron catalyst that addresses above-mentioned concerns showcasing aerobic steroids, terpenes, simple olefins to corresponding enone products. This novel method provides powerful tool arsenal allylic while minimizing environmental concerns.

Язык: Английский

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Nitrogenative Degradation of Polystyrene Waste

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 8, 2025

Owing to massive production and poor end-of-life management, plastic waste pollution has become one of the most pressing environmental crises. In response mounting crisis, past several decades have witnessed development numerous methods technologies for recycling. However, current recycling often produce low-quality or low-value products, making it difficult recover operating costs. To this end, we report a novel preoxygenation-induced strategy nitrogenative degradation real-life polystyrene plastics into high-value aromatic nitrogen compounds in cost-effective manner. Thus, expensive highly demanding benzonitrile as well benzamide were obtained up 74% overall isolated yield from by using CuBr catalyst, O2 oxidant, CH3CN source. Detailed mechanistic investigations indicate that hydroxyl radicals activation play role selective aerobic process. Furthermore, multiple reaction pathways contribute formation benzamide.

Язык: Английский

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Iron-catalyzed ring-opening of cyclic carboxylic acids enabled by photoinduced ligand-to-metal charge transfer

Green Chemistry, Год журнала: 2022, Номер 24(14), С. 5553 - 5558

Опубликована: Янв. 1, 2022

A decarboxylative ring-opening reaction of cyclic tertiary carboxylic acids via an iron-catalyzed photoinduced ligand-to-metal charge transfer (LMCT) process is herein reported.

Язык: Английский

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Boosting Reactive Oxygen Species Generation Using Inter‐Facet Edge Rich WO₃ Arrays for Photoelectrochemical Conversion

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(1)

Опубликована: Ноя. 10, 2022

Water oxidation reaction leaves room to be improved in the development of various solar fuel productions, because kinetically sluggish 4-electron transfer process oxygen evolution reaction. In this work, we realize reactive species (ROS), H2 O2 and OH⋅, formations by water with total Faraday efficiencies more than 90 % using inter-facet edge (IFE) rich WO3 arrays an electrolyte containing CO32- . Our results demonstrate that IFE favors adsorption while reducing energy as well suppresses surface hole accumulation direct 1-electron indirect 2-electron pathways. Finally, present selective benzyl alcohol situ formed which delivers a benzaldehyde production rate ≈768 μmol h-1 near 100 selectivity. This work offers promising approach tune or control aqueous system towards high efficiency value-added product.

Язык: Английский

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Emerging Trends in Copper-Promoted Radical-Involved C–O Bond Formations

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(32), С. 17527 - 17550

Опубликована: Авг. 2, 2023

The C–O bond is ubiquitous in biologically active molecules, pharmaceutical agents, and functional materials, thereby making it an important group. Consequently, the development of bond-forming reactions using catalytic strategies has become increasingly research topic organic synthesis because more conventional methods involving strong base acid have many limitations. In contrast to ionic-pathway-based methods, copper-promoted radical-mediated formation experiencing a surge interest owing renaissance free-radical chemistry photoredox catalysis. This Perspective highlights appraises state-of-the-art techniques this burgeoning field. contents are organized according different reaction types working models.

Язык: Английский

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Synthesis of Axially Chiral Biaryls through Cobalt(II)‐Catalyzed Atroposelective C−H Arylation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(40)

Опубликована: Авг. 16, 2023

Highly efficient synthesis of axially chiral biaryl amines through cobalt-catalyzed atroposelective C-H arylation using easily accessible cobalt(II) salt and salicyloxazoline ligand has been reported. This methodology provides a straightforward sustainable access to broad range enantioenriched biaryl-2-amines in good yields (up 99 %) with excellent enantioselectivities % ee). The synthetic utility the unprecedented method is highlighted by its scalability diverse transformations.

Язык: Английский

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