Syntheses of substituted anilines primarily rely on palladium-catalyzed coupling chemistry with prefunctionalized aryl electrophiles. While oxidative aminations have emerged as powerful alternatives, they largely produce undesired metal-containing by-products in stoichiometric quantities. In contrast, described herein is the unprecedented electrochemical C-H amination by cobalt-catalyzed C-H activation. The environmentally benign electrocatalysis avoids stoichiometric metal oxidants, can be conducted under ambient air, and employs a biomass-derived, renewable solvent for sustainable aminations in an atom- and step-economical manner with H as the sole byproduct.
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http://dx.doi.org/10.1002/anie.201802206 | DOI Listing |
J Org Chem
January 2025
Jiangxi Provincial Key Laboratory of Organic Functional Molecules, Institute of Organic Chemistry, Jiangxi Science & Technology Normal University, Nanchang 330013, China.
Herein, an efficient electrochemical three-component C-H functionalization of indoles with sodium bisulfite and alcohols is described, providing a sustainable and convenient synthetic route for the construction of structurally valuable indole-containing sulfonate esters in moderate to good yields. This protocol proceeds in an undivided cell without any metal catalysts or oxidants, features a broad substrate scope, and has an excellent functional group tolerance. Preliminary mechanistic studies suggest that a radical-radical pathway may be involved in this three-component reaction system.
View Article and Find Full Text PDFNat Commun
January 2025
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Republic of Singapore.
Employing electrochemistry for the selective functionalization of liquid alkanes allows for sustainable and efficient production of high-value chemicals. However, the large potentials required for C(sp)-H bond functionalization and low water solubility of such alkanes make it challenging. Here we discover that a Pt/IrO electrocatalyst with optimized Cl binding energy enables selective generation of Cl free radicals for C-H chlorination of alkanes.
View Article and Find Full Text PDFJ Xenobiot
December 2024
Department of Chemical Engineering, University of Pretoria, Pretoria 0028, South Africa.
The direct discharge of cationic surfactants into environmental matrices has exponentially increased due to their wide application in many products. These compounds and their degraded products disrupt microbial dynamics, hinder plant survival, and affect human health. Therefore, there is an urgent need to develop electroanalytical assessment techniques for their identification, determination, and monitoring.
View Article and Find Full Text PDFACS Appl Mater Interfaces
December 2024
State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, P. R. China.
Proton-electron transfer (PET) processes play a pivotal role in numerous electrochemical reactions; yet, effectively harnessing them remains a formidable challenge. Consequently, unveiling the PET pathway is imperative to elucidate the factors influencing the efficiency and selectivity of small molecule electrochemical conversion. In this study, a Zn-NC model catalyst with N and C vacancies was synthesized using a hydriding method to investigate the universal impact of PET on CO electroreduction.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Purdue University, Davidson School of Chemical Engineering, 480 Stadium Mall, 47907, West Lafayette, UNITED STATES OF AMERICA.
C-H bond activation is the first step in manufacturing chemical products from readily available light alkane feedstock and typically proceeds via carbon-intensive thermal processes. The ongoing emphasis on decarbonization via electrification motivates low-temperature electrochemical alternatives that could lead to sustainable chemicals production. Platinum (Pt) electrocatalysts have shown activity towards reacting alkanes; however, little is known about propane electrocatalytic activation and conditions suitable for enabling selective oxidation to valuable products.
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