Interrogating the Mechanistic Features of Ni(I)-Mediated Aryl Iodide Oxidative Addition Using Electroanalytical and Statistical Modeling Techniques

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8689 - 8699

Опубликована: Апрель 4, 2023

While the oxidative addition of Ni(I) to aryl iodides has been commonly proposed in catalytic methods, an in-depth mechanistic understanding this fundamental process is still lacking. Herein, we describe a detailed study using electroanalytical and statistical modeling techniques. Electroanalytical techniques allowed rapid measurement rates for diverse set iodide substrates four classes catalytically relevant complexes (Ni(MeBPy), Ni(MePhen), Ni(Terpy), Ni(BPP)). With >200 experimental rate measurements, were able identify essential electronic steric factors impacting through multivariate linear regression models. This led classification mechanisms, either three-center concerted or halogen-atom abstraction pathway based on ligand type. A global heat map predicted was created shown applicable better reaction outcome case Ni-catalyzed coupling reaction.

Язык: Английский

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Electrochemically Driven Hydrogen Atom Transfer Catalysis: A Tool for C(sp³)/Si–H Functionalization and Hydrofunctionalization of Alkenes

ACS Catalysis, Год журнала: 2023, Номер 13(13), С. 8731 - 8751

Опубликована: Июнь 16, 2023

Electrochemically driven hydrogen atom transfer (HAT) catalysis provides a complementary approach for the transformation of redox-inactive substrates that would be inaccessible to conventional electron (ET) catalysis. Moreover, electrochemically HAT could promote organic transformations with either abstraction or donation as key step. It versatile and effective tool direct functionalization C(sp3)–H/Si–H bonds hydrofunctionalization alkenes. Despite these attractive properties, has been largely overlooked due lack understanding both catalytic mechanism how catalyst selection should occur. In this Review, we give an overview applications in The mechanistic pathways, physical properties mediators, state-of-the-art examples are described discussed.

Язык: Английский

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Paired Oxidative and Reductive Catalysis: Breaking the Potential Barrier of Electrochemical C(sp³)−H Alkenylation**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(24)

Опубликована: Апрель 1, 2023

Due to the intrinsic inertness of alkanes, strong oxidative conditions are typically required enable their C(sp3 )-H functionalization. Herein, a paired electrocatalysis strategy was developed by integrating catalysis with reductive in one cell without interference, which earth-abundant iron and nickel employed as anodic cathodic catalysts, respectively. This approach lowers previously high oxidation potential for alkane activation, enabling electrochemical functionalization at ultra-low ≈0.25 V vs. Ag/AgCl under mild conditions. Structurally diverse alkenes, including challenging all-carbon tetrasubstituted olefins, can be accessed using readily available alkenyl electrophiles.

Язык: Английский

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Electrocatalytic three-component reactions: synthesis of tellurium-containing oxazolidinone for anticancer agents

Green Chemistry, Год журнала: 2023, Номер 25(13), С. 5024 - 5029

Опубликована: Янв. 1, 2023

A new synthetic method involving electrochemical catalysis were used to synthesize various tellurium-containing oxazolidinones which showed better antitumor activity compared other oxazolidinones.

Язык: Английский

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Electrochemical gold-catalysed biocompatible C(sp2)–C(sp) coupling

Nature Synthesis, Год журнала: 2023, Номер 2(4), С. 338 - 347

Опубликована: Янв. 12, 2023

Язык: Английский

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Comprehensive Comparisons between Directing and Alternating Current Electrolysis in Organic Synthesis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(50)

Опубликована: Авг. 22, 2023

Abstract Organic electrosynthesis has consistently aroused significant interest within both academic and industrial spheres. Despite the considerable progress achieved in this field, majority of electrochemical transformations have been conducted through utilization direct‐current (DC) electricity. In contrast, application alternating current (AC), characterized by its polarity‐alternating nature, remains infancy sphere organic synthesis, primarily due to absence a comprehensive theoretical framework. This minireview offers an overview recent advancements AC‐driven seeks elucidate differences between DC AC electrolytic methodologies probing into their underlying physical principles. These encompass ability preclude deposition metal catalysts, precision modulating oxidation reduction intensities, mitigation mass transfer processes.

Язык: Английский

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Recent Advances in Electrochemical Carboxylation with CO₂

Accounts of Chemical Research, Год журнала: 2024, Номер 57(18), С. 2728 - 2745

Опубликована: Сен. 3, 2024

ConspectusCarbon dioxide (CO

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Catalyst Selection over an Electrochemical Reductive Coupling Reaction toward Direct Electrosynthesis of Oxime from NO_x and Aldehyde

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(9), С. 6294 - 6306

Опубликована: Фев. 20, 2024

Aqueous electrochemical coupling reactions, which enable the green synthesis of complex organic compounds, will be a crucial tool in synthetic chemistry. However, lack informed approaches for screening suitable catalysts is major obstacle to its development. Here, we propose pioneering reductive reaction toward direct electrosynthesis oxime from NOx and aldehyde. Through integrating experimental theoretical methods, screen out optimal catalyst, i.e., metal Fe that facilitates enrichment C–N key intermediates, all leading high yields (e.g., ∼99% yield benzaldoxime) over Fe. With divided flow reactor, achieve benzaldoxime production 22.8 g h–1 gcat–1 ∼94% isolated yield. This work not only paves way industrial mass via but also offers references catalyst selection other reactions.

Язык: Английский

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Coordination complexes of Bipyridines (CCBs): Chemistry, bonding and applications

Coordination Chemistry Reviews, Год журнала: 2025, Номер 529, С. 216433 - 216433

Опубликована: Янв. 13, 2025

Язык: Английский

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Recent Advances in Asymmetric Organometallic Electrochemical Synthesis (AOES)

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 19, 2025

ConspectusIn recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with transition metal catalysis. On one hand, we have rationalized that compounds can serve as molecular electrocatalysts (mediators) reduce overpotentials and enhance both reactivity selectivity reactions. other conditions for catalysis be substantially improved through electrochemistry, enabling precise modulation metal's oxidation state by controlling potentials regulating electron transfer rate via current adjustments. This synergistic approach addresses key challenges inherent in traditional catalysis, particularly those related use redox-active chemical reagents. Furthermore, redox conveniently tuned modifying their ligands, thereby governing reaction regioselectivity stereoselectivity. As a result, AOES emerged powerful promising tool chiral compounds.In this Account, summarize contextualize efforts AOES. Our primary strategy involves leveraging controllability potential regulate organometallics, facilitating desired An efficient platform was established under mild conditions, significantly reducing reliance on been systematically categorized into three sections based distinct electrolysis modes: combined anodic oxidation, cathodic reduction, paired electrolysis. In each section, highlight innovative discoveries tailored unique characteristics respective modes.In many transformations, metal-catalyzed reactions involving reagents utilizing exhibit similar reactivities. However, also observed notable differences certain cases. These findings include following: (1) Enhanced efficiency synthesis: instance, Rh-catalyzed enantioselective functionalization C–H bonds demonstrates superior efficiency. (2) Expanded scope transformations: previously challenging achieved due tunability potentials. A example is reductive coupling aryl chlorides, expands range accessible transformations. Additionally, mechanistic studies explore techniques intrinsic such controlled experiments, impact electrode materials catalyst performance, cyclic voltammetry studies. investigations provide more intuitive understanding behavior catalysts study mechanisms, guide design new catalytic systems.The advancements offer robust environmentally friendly sustainable selective By integrating developed versatile organic not only enhances but reduces environmental impact. We anticipate Account will stimulate further innovation realm AOES, leading discovery systems development synthetic methodologies.

Язык: Английский

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