Challenges and recent advancements in the transformation of CO₂into carboxylic acids: straightforward assembly with homogeneous 3d metals

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(22), P. 9371 - 9423

Published: Jan. 1, 2022

The transformation of carbon dioxide (CO2) into useful chemicals, advanced materials, and energy is a long-standing challenge in both fundamental science industry. In recent years, utilization CO2 the presence inexpensive non-negligible environmentally friendly 3d metal-based catalysts (Fe, Mn, Co, Ni, Cu Ti) has become one most attractive topics. Particular attention been given to synthesis carboxylic acids their derivatives since these molecules serve as key intermediates chemical, fertilizer, pharmaceutical sectors. Considering numerous challenges linked with reactivity, number research groups have recently focused on by following thermo-, photo-, electrochemical strategies. However, facile access such remains vital catalysis organic owing high stability molecule which atom highest oxidation state. Another hurdle solve selectivity issue caused reaction different catalytic systems reactive functional group-containing molecules. Despite all issues, wide range transition applied this direction, but cheaper price inherent metals are at forefront domain. these, we aim summarise advances (over past five years) 3d-metal complexes reactivity towards activation for acids. Furthermore, discuss current trends, knowledge gaps, invigorating perspectives future advances.

Language: Английский

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Counter Electrode Reactions—Important Stumbling Blocks on the Way to a Working Electro‐organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(47)

Published: June 7, 2022

Over the past two decades, electro-organic synthesis has gained significant interest, both in technical and academic research as well terms of applications. The omission stoichiometric oxidizers or reducing agents enables a more sustainable route for redox reactions organic chemistry. Even if it is well-known that every electrochemical oxidation only viable with an associated reduction reaction vice versa, relevance counter often less addressed. In this Review, importance corresponding highlighted how can affect performance selectivity electrolytic conversion. A selection common strategies unique concepts to tackle issue are surveyed provide guide select appropriate synthesis.

Language: Английский

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A guide to organic electroreduction using sacrificial anodes

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(4), P. 1168 - 1188

Published: Jan. 1, 2023

This review focuses on recent advances in sacrificial anode-enabled organic electroreductions.

Language: Английский

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Nickel/biimidazole-catalyzed electrochemical enantioselective reductive cross-coupling of aryl aziridines with aryl iodides

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 22, 2023

Here, we report an asymmetric electrochemical organonickel-catalyzed reductive cross-coupling of aryl aziridines with iodides in undivided cell, affording β-phenethylamines good to excellent enantioselectivity broad functional group tolerance. The combination cyclic voltammetry analysis the catalyst reduction potential as well electrode study provides a convenient route for reaction optimization. Overall, high efficiency this method is credited electroreduction-mediated turnover nickel instead metal reductant-mediated turnover. Mechanistic studies suggest radical pathway involved ring opening aziridines. statistical serves compare different design requirements photochemically and electrochemically mediated reactions under type mechanistic manifold.

Language: Английский

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

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8689 - 8699

Published: April 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.

Language: Английский

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Organo‐Mediator Enabled Electrochemical Deuteration of Styrenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 12, 2023

Despite widespread use of the deuterium isotope effect, selective labeling chemical molecules remains a major challenge. Herein, facile and general electrochemically driven, organic mediator enabled deuteration styrenes with oxide (D2 O) as economical source was reported. Importantly, this transformation could be suitable for various electron rich mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition-metal catalysts, affording desired products in good yields excellent D-incorporation (D-inc, up to >99 %). Mechanistic investigations means experiments cyclic voltammetry tests provided sufficient support transformation. Notably, method proved powerful tool late-stage biorelevant compounds.

Language: Английский

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Room Temperature Construction of Vicinal Amino Alcohols via Electroreductive Cross-Coupling of N-Heteroarenes and Carbonyls

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 10967 - 10973

Published: April 19, 2023

Despite the widespread applications of α-hydroxyalkyl cyclic amines, direct and diverse access to such a class unique vicinal amino alcohols still remains, date, challenge. Here, through strategy electroreductive α-hydroxyalkylation inactive N-heteroarenes with ketones or electron-rich arylaldehydes, we describe room temperature approach for construction which features broad substrate scope, operational simplicity, high chemoselectivity, no need pressurized H2 gas transition metal catalysts. The zinc ion generated from anode oxidation plays crucial role in activation both reactants by decreasing their reduction potentials. electroreduction combination Lewis acids this work is anticipated develop more useful transformations.

Language: Английский

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Electroreduction of unactivated alkenes using water as hydrogen source

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 30, 2024

Abstract Herein, we report an electroreduction of unactivated alkyl alkenes enabled by [Fe]-H, which is provided through the combination anodic iron salts and silane generated in situ via cathodic reduction, using H 2 O as H-source. The catalytic amounts Si-additive work H-carrier from to generate a highly active species under continuous electrochemical conditions. This approach shows broad substrate scope good functional group compatibility. In addition hydrogenation, use D instead provides desired deuterated products yields with excellent D-incorporation (up >99%). Further late-stage hydrogenation complex molecules drug derivatives demonstrate potential application pharmaceutical industry. Mechanistic studies are performed provide support for proposed mechanistic pathway.

Language: Английский

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General C(sp²)–C(sp³) Cross-Electrophile Coupling Reactions Enabled by Overcharge Protection of Homogeneous Electrocatalysts

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(12), P. 5884 - 5893

Published: Feb. 29, 2020

Cross-electrophile coupling (XEC) of alkyl and aryl halides promoted by electrochemistry represents an attractive alternative to conventional methods that require stoichiometric quantities high-energy reductants. Most importantly, electroreduction can readily exceed the reducing potentials chemical reductants activate catalysts with improved reactivities selectivities over systems. This work details mechanistically-driven development electrochemical methodology for XEC utilizes redox-active shuttles developed energy-storage community protect reactive from overreduction. The resulting electrocatalytic system is practical, scalable, broadly applicable reductive a wide range aryl, heteroaryl, or vinyl bromides primary secondary bromides. impact overcharge protection as strategy electrosynthetic methodologies underscored dramatic differences in yields reactions added redox (generally >80%) those without <20%). In addition excellent substrates, protected overreduction be performed at high currents on multigram scales.

Language: Английский

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Chemical‐Reductant‐Free Electrochemical Deuteration Reaction using Deuterium Oxide

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(33), P. 13962 - 13967

Published: May 12, 2020

We report a method for the electrochemical deuteration of α,β-unsaturated carbonyl compounds under catalyst- and external-reductant-free conditions, with rates as high 99 % yields up to 91 in 2 h. The use graphite felt both cathode anode was key ensuring chemoselectivity deuterium incorporation neutral conditions without need an external reductant. This has number advantages over previously reported reactions that stoichiometric metallic reductants. Mechanistic experiments showed O2 evolution at not only eliminates reductant but also regulates pH reaction mixture, keeping it approximately neutral.

Language: Английский

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