Recent Advances in Electrochemical Carboxylation with CO₂

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(18), P. 2728 - 2745

Published: Sept. 3, 2024

ConspectusCarbon dioxide (CO

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Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1224 - 1243

Published: Jan. 4, 2024

Efficient and streamlined synthetic methods that facilitate the rapid build-up of structurally diverse π-conjugated systems are paramount importance in quest for organic optoelectronic materials. Among these methods, transition-metal-catalyzed oxidative Ar–H/Ar–H coupling reactions between two (hetero)arenes have emerged as a concise effective approach generating wide array bi(hetero)aryl fused heteroaryl structures. This innovative bypasses challenges associated with substrate pre-activation processes, thereby allowing creation frameworks were previously beyond reach using conventional Ar–X/Ar–M reactions. These inherent advantages ushered new design patterns molecules deviate from traditional methods. ground-breaking enables transcendence limitations repetitive material structures, ultimately leading to discovery novel high-performance In this Perspective, we provide an overview recent advances development materials through utilization We introduce several notable strategies domain, covering both directed non-directed strategies, dual chelation-assisted strategy ortho-C–H arylation/cyclization strategy. Additionally, shed light on role advancement Finally, discuss current existing protocols offer insights into future prospects field.

Language: Английский

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Enantioselective Nickel-Electrocatalyzed Reductive Propargylic Carboxylation with CO₂

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14864 - 14874

Published: May 16, 2024

The exploitation of carbon dioxide (CO2) as a sustainable, plentiful, and harmless C1 source for the catalytic synthesis enantioenriched carboxylic acids has long been acknowledged pivotal task in synthetic chemistry. Herein, we present current-driven nickel-catalyzed reductive carboxylation reaction with CO2 fixation, facilitating formation C(sp3)–C(sp2) bonds by circumventing handling moisture-sensitive organometallic reagents. This electroreductive protocol serves practical platform, paving way propargylic (up to 98% enantiomeric excess) from racemic carbonates CO2. efficacy this transformation is exemplified its successful utilization asymmetric total (S)-arundic acid, (R)-PIA, (S)-chizhine D, (S)-cochlearin G, (S,S)-alexidine, thereby underscoring potential electrosynthesis achieve complex molecular architectures sustainably.

Language: Английский

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Molecular Photoelectrocatalysis for Radical Reactions

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

ConspectusMolecular photoelectrocatalysis, which combines the merits of photocatalysis and organic electrosynthesis, including their green attributes capacity to offer novel reactivity selectivity, represents an emerging field in chemistry that addresses growing demands for environmental sustainability synthetic efficiency. This synergistic approach permits access a wider range redox potentials, facilitates transformations under gentler electrode decreases use external harsh reagents. Despite these potential advantages, this area did not receive significant attention until 2019, when we others reported first examples modern molecular photoelectrocatalysis. These studies showcased immense hybrid strategy, only inherits strengths its parent fields but also unlocks unprecedented enabling challenging mild conditions while minimizing reliance on stoichiometric oxidants or reductants.In Account, present our efforts develop photoelectrocatalytic strategies leverage homogeneous catalysts facilitate diverse radical reactions. By integrating electrocatalysis with key photoinduced processes such as single electron transfer (SET), ligand-to-metal charge (LMCT), hydrogen atom (HAT), have established methods transform substrates organotrifluoroborates, arenes, carboxylic acids, alkanes into reactive intermediates. intermediates subsequently engage heteroarene C-H functionalization Importantly, photoelectrochemical catalysts, generated bulk solution readily participate efficient reactions without undergoing further overoxidation carbocations, common challenge conventional electrochemical systems.By integration photoelectrocatalysis asymmetric catalysis, developed catalysis (PEAC), proves be enantioselective synthesis chiral nitriles. involves two relay catalytic cycles: initial process engenders benzylic radicals from precursors alkyl aryl alkenes, C-radicals are then subjected cyanation subsequent copper-electrocatalytic cycle.Within realm oxidative transformations, anode serves crucial component recycling generating photocatalyst, cathode promotes proton reduction. dual functionality enables via H

Language: Английский

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Recent Advances in Green Multi-Component Reactions for Heterocyclic Compound Construction

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review highlights the recent advances in multi-component reactions for synthesizing heterocyclic compounds via green approaches including photoredox catalysis, electrochemical activation, catalyst-free methods and use of water as sole solvent.

Language: Английский

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Adoption of Electrochemistry within the Pharmaceutical Industry: Insights from an Industry-Wide Survey

Organic Process Research & Development, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

Language: Английский

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The green chemistry paradigm in modern organic synthesis

Russian Chemical Reviews, Journal Year: 2023, Volume and Issue: 92(12), P. RCR5104 - RCR5104

Published: Dec. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Language: Английский

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Regioselective Hydro(deutero)silylation of 1,3-Enynes Enabled by Photoredox/Nickel Dual Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(2), P. 536 - 541

Published: Jan. 5, 2024

In the presence of visible light irradiation, organophoto/nickel dual catalysts, and mild base K2HPO4, 1,3-enynes react with silanecarboxylic acids to give corresponding α-silylallenes high selectivity. this uniquely decarboxylative hydrosilylation 1,3-enynes, a silyl radical process is involved diverse electron-rich -poor substrates proceed smoothly in moderate excellent yields. This transformation particularly synthetically worthwhile when using MeOD as solvent, which furnishes new access α-silyldeuteroallenes.

Language: Английский

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Site-Selective Electrochemical Arene C–H Amination

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 3591 - 3597

Published: Jan. 31, 2024

Here we present the discovery and development of a highly selective aromatic C–H amination reaction. This electrochemical strategy involves cathodic reduction process that generates electrophilic dicationic N-centered radicals can efficiently engage in functionalization channel regioselectivity substitution. The nitrogen-radical cation–pi interaction with arenes used throughout nature leads to charge transfer mechanism, subsequent C–N bond formation. aryl DABCOnium salts excellent yields regioselectivities (single regioisomer most cases). scope reaction on arene is broad where various functionalities such as halides (bromides, chlorides, fluorides), carbonyls (ketones, esters, imides), sulfonamides, heteroarenes (pyridines, bipyridines, terpyridines) are well tolerated. Moreover, disclose synthetic utility salt adducts leading direct access diverse piperazines chemoselective cleavage exocyclic C(sp2)–N over C(sp3)–N+ bonds via photoredox catalysis afford synthetically useful C–C C–P

Language: Английский

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Electrochemical recycling of polymeric materials

Chemical Science, Journal Year: 2024, Volume and Issue: 15(23), P. 8606 - 8624

Published: Jan. 1, 2024

Electrochemistry shows promising new avenues in the recycling of polymeric materials. This work reviews electrochemical depolymerization, post-polymerization functionalization, and paired catalysis, highlighting future challenges opportunities.

Language: Английский

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