Photoexcitation of Distinct Divalent Palladium Complexes in Cross‐Coupling Amination Under Air

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(3)

Опубликована: Ноя. 13, 2023

Abstract The development of metal complexes that function as both photocatalyst and cross‐coupling catalyst remains a challenging research topic. So far, progress has been shown in palladium(0) excited‐state transition catalysis for the construction carbon‐carbon bonds where oxidative addition alkyl/aryl halides to zero‐valent palladium (Pd 0 ) is achievable at room temperature. In contrast, analogous process with divalent II uphill endothermic. For first time, we report can act light‐absorbing species undergoes double excitation realize carbon‐nitrogen (C−N) cross‐couplings under air. Differently substituted aryl be applied mild, selective amination using acetate Density functional theory studies supported by mechanistic investigations provide insight into reaction mechanism.

Язык: Английский

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Nickel-Catalyzed Reductive Cross-Coupling of Propargylic Acetates with Chloro(vinyl)silanes: Access to Silylallenes

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(5), С. 2885 - 2894

Опубликована: Фев. 14, 2024

Because of their various reactivities, propargyl acetates are refined chemical intermediates that extensively applied in pharmaceutical synthesis. Currently, reactions between and chlorosilanes may be the most effective method for synthesizing silylallenes. Nevertheless, owing to adaptability selectivity substrates, transition metal catalysis is difficult achieve. Herein, nickel-catalyzed reductive cross-coupling substituted vinyl synthesis tetrasubstituted silylallenes described. Therein, metallic zinc a crucial reductant effectively enables two electrophilic reagents selectively construct C(sp2)–Si bonds. Additionally, Ni-catalyzed mechanism involving radical process proposed on basis deuteration-labeled experiments.

Язык: Английский

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Axial Ligand Enables Synthesis of Allenylsilane through Dirhodium(II) Catalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(38)

Опубликована: Июнь 18, 2024

Described herein is a dirhodium(II)-catalyzed silylation of propargyl esters with hydrosilanes, using tertiary amines as axial ligands. By adopting this strategy, range versatile and useful allenylsilanes can be achieved good yields. This reaction not only represents S

Язык: Английский

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Cobalt-Promoted Electroreductive Cross-Coupling of Prop-2-yn-1-yl Acetates with Chloro(vinyl)silanes

Organic Letters, Год журнала: 2023, Номер 25(39), С. 7263 - 7267

Опубликована: Сен. 27, 2023

An electroreductive cross-coupling of prop-2-yn-1-yl acetates with chloro(vinyl)silanes for producing tetrasubstituted silylallenes is developed. The method enables the formation a new C─Si bond through cathodic reduction silyl radical, radical addition across C≡C bond, alkenyl anion intermediate formation, and deacetoxylation represents mild, practical route to synthesis silylallenes. Mechanistic studies reveal that CoCl2 acts as mediator promote via electron transfer.

Язык: Английский

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Ni-catalyzed reductive alkylgermylation of activated alkenes: Modular access to polyfunctionalized alkyl germanes

Chem Catalysis, Год журнала: 2023, Номер 3(12), С. 100819 - 100819

Опубликована: Ноя. 22, 2023

Язык: Английский

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Photoinduced Nickel-Catalyzed Demethylative Cyanation and Decarboxylative Cyanomethylation of Aryl Halides

ACS Catalysis, Год журнала: 2023, Номер 13(24), С. 16279 - 16285

Опубликована: Дек. 6, 2023

Photoinduced nickel-catalyzed demethylative cyanation and decarboxylative cyanomethylation of aryl halides are described here. Commercially available bromoacetonitrile was found to act as an efficient cyanating reagent for the photoinduced reaction in absence a photocatalyst. Moreover, photoredox nickel dual-catalyzed has also been realized using cesium cyanoacetate under mild conditions. A series benzyl nitriles bearing diverse functional groups were prepared with good high efficiency.

Язык: Английский

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Electrochemically mediated synthesis of trifluoromethylallenes

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(12), С. 3485 - 3490

Опубликована: Янв. 1, 2024

Herein, we report electrochemically mediated trifluoromethylallene synthesis via the rearrangement of trifluoromethyl-containing 1,3-enynes under action silicon or boron radicals, with good selectivity and without external oxidants.

Язык: Английский

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Electrochemical Skeletal Indole Editing via Nitrogen Atom Insertion by Sustainable Oxygen Reduction Reaction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(41)

Опубликована: Июль 3, 2024

Skeletal molecular editing gained considerable recent momentum and emerged as a uniquely powerful tool for late-stage diversifications. Thus far, superstoichiometric amounts of costly hypervalent iodine(III) reagents were largely required skeletal indole editing. In contrast, we herein show that electricity enables sustainable nitrogen atom insertion reactions to give bio-relevant quinazoline scaffolds without stoichiometric chemical redox-waste product. The transition metal-free electro-editing was enabled by the oxygen reduction reaction (ORR) proved robust on scale, while tolerating variety valuable functional groups.

Язык: Английский

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Multimodal Precise Control Over Multiselective Carbonylation of 1,3-Enynes

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(9), С. 7950 - 7964

Опубликована: Фев. 19, 2025

Efficiently constructing structurally diverse and complex organic molecules through selective catalytic functionalization is a central goal in synthetic chemistry, yet achieving precise control over multiple reactive centers multisite substrates remains formidable challenge. Building on foundational advances single- dual-selective transformations, we report multimodal strategy for the carbonylation of 1,3-enynes, versatile class substrates. Through meticulous fine-tuning conditions, our approach enables five distinct regio- stereoselective carbonylative including direct (1,2- 2,1-hydroaminocarbonylation) tandem cyclization pathways (2,4-, 1,3-, 2,3-carbonylation). Furthermore, mechanistic studies suggested that multidimensional regulation seamless relay up to three reactions (hydroaminocarbonylation-hydroamination-transamination) with exceptional accuracy. This unified platform not only establishes robust framework tackling enduring challenges selectivity but also broadens chemical space accessible 1,3-enyne exemplifying atom- step-economic principles paving way transformative advancements drug discovery, materials science, beyond.

Язык: Английский

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Facile, general allylation of unactivated alkyl halides via electrochemically enabled radical-polar crossover

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

We present a facile, general and transition-metal-catalyst free electrochemical allylation of unactivated alkyl halides. Broad substrate scopes, excellent functional group tolerance late-stage functionalization showcase its synthetic utility.

Язык: Английский

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