Electrocatalytic Anaerobic Oxidation of Benzylic Amines Enabled by Ferrocene-Based Redox Mediators DOI Creative Commons
Amy L. Waldbusser, Shabnam Hematian

Organometallics, Journal Year: 2024, Volume and Issue: 43(20), P. 2557 - 2564

Published: Aug. 11, 2024

The generation and functionalization of carbon- or nitrogen-centered radicals are great interest for their potential synthetic utility. Here, we report the anaerobic electrocatalytic oxidation two primary benzylic amines, benzylamine 2-picolylamine, in presence a catalytic quantity an electron deficient ferrocene derivative as single-electron redox mediator. use appropriate mediator prevented fouling electrode surface significantly decreased at which reaction occurred. Simulation electrochemical results revealed E

Language: Английский

Enantioselective electrochemical nickel-catalyzed vinylogous radical reactions DOI Creative Commons

Jiayin Zhang,

Minghao Liu,

Wenyuan Zhang

et al.

Science Advances, Journal Year: 2025, Volume and Issue: 11(12)

Published: March 19, 2025

Highly functionalized structural motifs with extended chiral carbon chains are prevalent in a wide range of bioactive compounds and play critical roles the production various molecules. Here, we describe nickel-catalyzed asymmetric radical-based electrochemical functionalization silyl polyenolates at α-, γ-, ε-, η-positions. Driven by electric current, this methodology provides sustainable route to access enantioenriched dicarbonyls via vinylogous radical pathways. It demonstrates excellent functional groups tolerance, mild reaction conditions, broad substrate compatibility, formation quaternary stereocenters remote positions, high levels regio- enantioselectivity (up 98% enantiomeric excess). Mechanistic investigations indicate that ferrocene-based electron transfer mediators pivotal anodic oxidation process, facilitating generation nickel-bound α-carbonyl radicals while suppressing undesired polyenolates, thus guiding selection for electrocatalytic systems. The versatility catalytic electrosynthesis is highlighted preparation valuable building blocks total synthesis (-)-ethosuximide.

Language: Английский

Citations

0
When transition-metal catalysis meets electrosynthesis: a recent update DOI
Fei Lian, Jiuling Li, Kun Xu

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(22), P. 4390 - 4419

Published: Jan. 1, 2024

The merger of organic electrosynthesis with 3d transition-metal catalysis has offered huge opportunities for modern synthesis. This review summarizes the key advancements in this direction published recent two years.

Language: Английский

Citations

3
Electrocatalytic Ammonia Oxidation by Pyridyl-Substituted Ferrocenes DOI Creative Commons
Md Estak Ahmed, Richard J. Staples, Thomas R. Cundari

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 14, 2025

Ammonia (NH3) is a promising carbon-free fuel when prepared from sustainable resources. First-row transition metal electrocatalysts for ammonia oxidation are an enabling technology energy production. We describe electrocatalytic using robust molecular complexes based on Earth-abundant iron. Electrochemical studies of ferrocenes with covalently attached pyridine arms reveal facile in DMSO (2.4 M NH3) modest overpotentials (η = 770–820 mV) and turnover frequencies (125–560 h–1). Experimental computational indicate that the pendant pyridyl base serves as H-bond acceptor N–H bond transfers proton to following by ferrocenium moiety proton-coupled electron transfer (PCET) step. This generates amidyl (•NH2) radical stabilized via H-bonding pyridinium rapidly dimerizes hydrazine (H2N–NH2), which easily oxidized nitrogen (N2) at glassy carbon working electrode. report identifies general strategy oxidize (B:), thereby activating [B···H-NH2] toward PCET proximal oxidant form [BH···NH2]+/• cations, susceptible dimerization hydrazine.

Language: Английский

Citations

0
Recent Strategies for the Synthesis of Ferrocene Derivatives and Their Applications to Electrochemistry DOI
Jung Min Joo, Soo Eun Park, Sohyeon Park

et al.

Synthesis, Journal Year: 2025, Volume and Issue: unknown

Published: May 5, 2025

Abstract Ferrocene, a highly redox-stable organometallic compound with distinctive sandwich-like structure, has significantly influenced the fields of electrochemistry, materials science, and medicinal chemistry. Modifying ferrocene core its side chains is crucial for fine-tuning redox properties, solubility, stability, thereby enhancing performance in various applications. This review discusses synthesis compounds potentially relevant to electrochemical applications, focusing on recent strategies nondirected C–H functionalization diverse reactions side-chain modifications. Advances activation ferrocenes have been facilitated by catalytic methods utilizing Pd, Ir, Au, In, Fe catalysts, as well through photoredox techniques. Furthermore, are modified via range mild transformations compatible core, including substitution annulation. These advancements synthesizing derivatives broadened their potential notably electron-transfer mediators, energy-storage systems, sensors. 1 Introduction 2 Nondirected Activation Ferrocene Its Derivatives 3 Side-Chain Modification 4 Applications Electrochemistry 5 Conclusion

Language: Английский

Citations

0
The merger of electro-reduction and hydrogen bonding activation for a radical Smiles rearrangement DOI Creative Commons

Liyuan Lan,

Kun Xu, Cheng‐Chu Zeng

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(33), P. 13459 - 13465

Published: Jan. 1, 2024

An unprecedented radical smiles rearrangement of N -arylpropiolamides was realized by merging electro-reduction with hydrogen bonding activation. Enabled this dual activation strategy, the reduction potential shifted positively 218 mV.

Language: Английский

Citations

2
Recent Catalytic Applications of Ferrocene and Ferrocenium Cations in the Syntheses of Organic Compounds DOI Creative Commons
Eike B. Bauer

Molecules, Journal Year: 2024, Volume and Issue: 29(23), P. 5544 - 5544

Published: Nov. 23, 2024

Ferrocene and its oxidized counterpart, the ferrocenium cation, represent a fascinating class of organometallic compounds with broad utility across various fields, including organic synthesis, pharmaceuticals, materials science. Over years, ferrocene, cations, their derivatives have also gained prominence for versatility in catalytic processes. This review article offers an overview research last decade into ferrocene- ferrocenium-based catalysis. Key developments are highlighted oxidation, cross-coupling, polymerization reactions, redox-switchable catalysis, as well application cations Lewis acid catalysts.

Language: Английский

Citations

1
Electrochemical Decarboxylation Coupling Reactions DOI
Jiaxiu Liu, Haoran Li, Wei‐Si Guo

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(66)

Published: Oct. 16, 2024

Abstract Carboxylic acids are attractive synthetic feedstocks with stable, non‐toxic, and inexpensive properties that can be easily obtained from natural sources or through synthesis. have long been considered environmentally friendly coupling agents in various organic transformations. In recent years, electrochemically mediated decarboxylation reactions of decarboxylic their derivatives (NHPI) emerged as effective new methods for constructing carbon‐carbon carbon‐heterocarbon chemical bonds. Compared transition metal photochemistry‐mediated catalytic reactions, which do not require the addition oxidants strong bases, electrochemically‐mediated decarboxylative transformations a sustainable strategy. addition, functional groups tolerate electrochemical conversion strategy well. Here, we summarize to better elucidate advantages reactions.

Language: Английский

Citations

1
Electrocatalytic Anaerobic Oxidation of Benzylic Amines Enabled by Ferrocene-Based Redox Mediators DOI Creative Commons
Amy L. Waldbusser, Shabnam Hematian

Organometallics, Journal Year: 2024, Volume and Issue: 43(20), P. 2557 - 2564

Published: Aug. 11, 2024

The generation and functionalization of carbon- or nitrogen-centered radicals are great interest for their potential synthetic utility. Here, we report the anaerobic electrocatalytic oxidation two primary benzylic amines, benzylamine 2-picolylamine, in presence a catalytic quantity an electron deficient ferrocene derivative as single-electron redox mediator. use appropriate mediator prevented fouling electrode surface significantly decreased at which reaction occurred. Simulation electrochemical results revealed E

Language: Английский

Citations

0