Tailoring the Degradation of Cyanoarene‐Based Photocatalysts for Enhanced Visible‐Light‐Driven Halogen Atom Transfer

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(36)

Опубликована: Июнь 6, 2024

We present the strategic design of donor-acceptor cyanoarene-based photocatalysts (PCs) aiming to augment beneficial PC degradation for halogen atom transfer (XAT)-induced dehalogenation reactions. Our investigation reveals a competitive nature between catalytic cycle and pathway, with becoming dominant, particularly less activated alkyl halides. The behavior PCs significantly impacts efficiency XAT process, leading exploration into manipulating in desirable direction. Recognizing variation rate degradation, as well its influence on reaction across range structures, we carefully engineered develop pre-catalyst, named 3DP-DCDP-IPN. This pre-catalyst undergoes rapid an active form, 3DP-DCDP-Me-BN, exhibited enhanced reducing ability radical anion form induce better regeneration consequently effectively catalyzes reaction, even challenging substrate.

Язык: Английский

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Amidophosphine Boranes as Easy Reducing Agents for Efficient Conversion of Nitro Compounds to Primary Amines With Iron Catalyst

Applied Organometallic Chemistry, Год журнала: 2025, Номер 39(3)

Опубликована: Фев. 5, 2025

ABSTRACT We report a direct and efficient methodology for the hydroboration of aliphatic aryl nitro compounds using amidophosphine‐borane {(C 6 H 5 )CH 2 N(PPh) (BH 3 ) } in presence iron(II) chloride as catalyst under mild conditions to form primary amines after hydrolysis. Solid amidophosphine‐boranes are user‐friendly readily synthesized, revealing remarkable reducing properties toward comprehensive range compounds. The scalability present approach is defined by performing gram‐scale reactions synthesis different pharmaceuticals like paracetamol benzocaine, demonstrating synthetic applicability current strategy.

Язык: Английский

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Efficient N-Methylation of Primary Amides Using Methanol Under Mn(I)-Catalysis

Tetrahedron, Год журнала: 2025, Номер unknown, С. 134535 - 134535

Опубликована: Фев. 1, 2025

Язык: Английский

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Heterogeneous Cobalt Nanocatalyst for Reductive Transformation of Nitroarenes to Aryl Amines Using Isopropanol as a Hydrogen Source

Industrial & Engineering Chemistry Research, Год журнала: 2025, Номер unknown

Опубликована: Март 19, 2025

Herein, we introduce an efficient catalytic transfer hydrogenation method using inexpensive, environmentally friendly, and readily available isopropyl alcohol as a hydrogen donor for selectively reducing diverse nitroarenes. The process employs cobalt-based nanocatalyst (Co–N/Al2O3), synthesized via simple impregnation cobalt nitrate, 1,10-phenanthroline, γ-Al2O3 precursors. This proves highly effective in producing wide range of aryl amines (35 examples), pharmaceutical intermediates (4 late-stage functional group transformations (1 example), with yields ranging from moderate to excellent (70–98%) across various scales. catalyst was characterized HR-TEM, powder XRD, XPS, H2-TPR, N2 adsorption–desorption, Raman spectroscopy, ICP-OES techniques. These analyses confirmed the formation Co3O4 nanoparticles. exceptional performance Co–N/Al2O3 is attributed its optimized textural, morphological, acidic properties, which are superior other catalysts. Mechanistic studies provided insights into formed during different stages reaction indirect route (condensation mechanism). recyclability were validated through experimental testing, demonstrating consistent efficiency over three consecutive cycles. sustainable offers promising alternative conventional processes that use molecular hydrogen.

Язык: Английский

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Visible-light-induced iron-catalyzed reduction of nitroarenes to anilines

Chemical Communications, Год журнала: 2023, Номер 59(95), С. 14177 - 14180

Опубликована: Янв. 1, 2023

An efficient visible-light-induced iron-catalyzed reduction of nitroarenes to anilines by using N-ethylmorpholine (NEM) as a reductant under mild conditions has been developed. The reaction proceeds with photosensitizer-free and features good excellent yields broad functional group tolerance. Preliminary mechanistic investigations showed that this was conducted via ligand-to-metal (NEM Fe3+) charge transfer nitro triplet biradical-induced hydrogen atom processes.

Язык: Английский

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Cobalt catalyzed condensation interrupted selective transfer hydrogenation using methanol

Journal of Catalysis, Год журнала: 2024, Номер unknown, С. 115759 - 115759

Опубликована: Сен. 1, 2024

Язык: Английский

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Sustainable and selective transfer hydrogenation using waste shrimp shell‐based tetrazene‐Ru (II) para‐cymene catalyst with ethanol as a hydrogen source

Applied Organometallic Chemistry, Год журнала: 2023, Номер 37(10)

Опубликована: Авг. 22, 2023

Sustainable chemical research emphasizes chitosan‐based catalysts and the need to explore direct utilization of waste shrimp shells, whereas use ethanol as a hydrogen source in transfer hydrogenation is less explored due its unfavorable redox potential, higher energy barriers, generation reactive intermediates, catalyst poising via metal carbonyl species or decarbonylation. Herein, we disclosed an efficient synthetic approach, conducted at ambient temperature, for surface functionalization shells with 3‐(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)‐1,2,4,5‐tetrazine ( DMPZ‐Tz ) nucleophilic substitution using 3,6‐bis(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)‐1,2,4,5‐tetrazine BDMPZ‐Tz ). This method results color change 75% increase nitrogen content, eliminating multiple syntheses harsh reaction conditions. We utilized strong coordination property between [Ru( p ‐cym)Cl 2 ] /RuCl 3 .3H O develop ruthenium‐embedded supported on shells. These were employed selective unsaturated carbonyl/aldehydes saturated carbonyl/alcohols, utilizing potassium carbonate base. The performance, selectivity, reusability thoroughly assessed through spectroscopic studies, in‐situ monitoring progress, initial rate kinetics, control experiments. obtained strongly indicated that anchoring played crucial role achieving superior performance compared synthesized without it homogeneous counterparts. exhibits reactivity, broad substrate scope.

Язык: Английский

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Two-Chamber-Enabled Hydrogenation Reactions Using Al-H₂O/NaOH: Access to Pharmaceuticals

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(24), С. 17047 - 17061

Опубликована: Ноя. 21, 2023

In this study, an efficient method for hydrogenation reactions has been reported in a short reaction time using two-chamber reactor. This process involves the ex situ generation of H2 gas aluminum-water presence NaOH. technique was applied to reduce various functional groups, including carbonyl, nitro, alkene, alkyne, and azide. The is also utilized chemoselective reduction double bonds α, β-unsaturated carbonyl compounds. potential demonstrated through quick delivery several key starting materials marketed drugs. Additionally, further extended isotope labeling D2O. entire safe operated standard fume hood settings, ensuring practicality convenience researchers field organic synthesis.

Язык: Английский

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Co-SAC catalyzed utilization of methanol and ethanol in the transfer hydrogenation of azo bonds: experimental and theoretical studies

Green Chemistry, Год журнала: 2023, Номер 25(22), С. 9374 - 9387

Опубликована: Янв. 1, 2023

An efficient protocol for the transfer hydrogenation of –NN– bonds using methanol and ethanol as H 2 sources is reported.

Язык: Английский

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B2(OH)4 and Et3N-BH3: A New Combination of Reagents for the Mild and Efficient Photoreduction of Nitro(hetero)arenes

Synthesis, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 11, 2024

Abstract Anilines are a common motif in many bioactive compounds and their production through the reduction of nitroarenes has become an essential method for synthesis. We demonstrate that combination amine-borane complex hypoboric acid (tetrahydroxydiborane) under visible light irradiation can accomplish to corresponding anilines. Preliminary mechanistic studies suggest generation boryl radicals via hydrogen atom transfer (HAT) step from photoexcited nitroarene. Involvement parallel thermal pathway is demonstrated with high reaction efficiency being partially attributed both routes.

Язык: Английский

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