Reductive Functionalization of Pyridine-Fused N-Heteroarenes

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(5), P. 795 - 813

Published: Feb. 23, 2024

ConspectusThe selective functionalization/transformation of ubiquitous pyridine-fused N-heteroarenes is a practical method to synthesize structurally novel N-heterocycles, which important for the development medicines, bioactive agents, agrochemicals, materials, ligands, sensors, pigments, dyes, etc. However, owing thermodynamic stability, kinetic inertness, and lone electron pair–induced catalyst deactivation N-heteroarenes, limited strategies (e.g., C–H activation/functionalization, electrophilic substitution, Minisci reaction) are available realize synthetic purpose maintain aromaticity final products. Moreover, relevant transformations have limitations such as needing harsh reaction conditions, requiring preinstallation specific coupling agents containing transformable functionalities or directing groups, using less environmentally benign oxidants and/or acidic activators, poor selectivity. Herein, considering that imines, enamines, radicals, cyclic amines generated during reduction precise transformation these reductive intermediates offers fundamental basis developing tandem reactions. Our group revealed slow rate, synergistic catalysis, controlled electroreduction effective fulfilling functionalization N-heteroarenes. Thus, we established series new methods provide diverse construction modalities functionalized N-heterocycles. The striking features include high efficiency, atom economy, use readily accessible feedstocks in absence flammable pressurized H2 gas, alongside promising potential obtained N-heterocyclic present study would be appealing fields organic chemistry, biomedical functional materials. This Account describes application dearomatization substrate-activating reaction-initiating modes summarizes via alkylation, arylation, annulation at nitrogen, α, β, other remote carbon sites achieved over past 8 years. Details regarding reactions their plausible mechanisms perspectives discussed. We hope our contributions this field will aid further tackle intractable challenges area.

Language: Английский

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Reductive Coupling of Nitroarenes and HCHO for General Synthesis of Functional Ethane-1,2-diamines by a Cobalt Single-Atom Catalyst

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(31), P. 17329 - 17336

Published: July 7, 2023

Despite the extensive applications, selective and diverse access to N,N'-diarylethane-1,2-diamines remains, date, a challenge. Here, by developing bifunctional cobalt single-atom catalyst (CoSA-N/NC), we present general method for direct synthesis of such compounds via reductive coupling cheap abundant nitroarenes formaldehyde, featuring good substrate functionality compatibility, an easily accessible base metal with excellent reusability, high step atom efficiency. Mechanistic studies reveal that N-anchored single atoms (CoN4) serve as catalytically active sites reduction processes, N-doped carbon support enriches HCHO timely trap in situ formed hydroxyamines affords requisite nitrones under weak alkaline conditions, subsequent inverse electron demand 1,3-dipolar cycloaddition imines followed hydrodeoxygenation cycloadducts furnishes products. In this work, concept catalyst-controlled nitroarene create specific building blocks is anticipated develop more useful chemical transformations.

Language: Английский

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Utilizing Nitroarenes and HCHO to Directly Construct Functional N‐Heterocycles by Supported Cobalt/Amino Acid Relay Catalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(22)

Published: March 22, 2023

Due to the generation of multiple intermediates during nitroarene reduction, precise interception single one develop tandem reactions involving both C-C and C-N bond formations still remains a significant challenge. Herein, relay catalysis supported bifunctional cobalt catalyst with l-proline has been successfully applied establish bran-new reductive annulation reaction nitroarenes formaldehyde, which enables direct diverse construction symmetrical unsymmetrical 1,3-diaryl imidazolines. It proceeds operational simplicity, good substrate functionality compatibility, excellent step atom-efficiency. Mechanistic studies reveal that Co-catalyst exhibits synergistic effect on formation key N-hydroxy imine, subsequently facilitates formation. The current work opens door useful transformations by reduction-interrupted strategy.

Language: Английский

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Access of arylmethanes via iridium-catalyzed deoxygenative cross-coupling of aryl ketones with anilines/phenols

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 433, P. 115492 - 115492

Published: April 11, 2024

Language: Английский

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Direct Construction of Julolidines via Reductive Annulation of Quinolines and Conjugated Enones by a MOF-Derived Hierarchically Porous Iridium Catalyst

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(16), P. 10294 - 10303

Published: Aug. 5, 2022

Here, we describe the development of a MOF-derived hierarchically porous ZrO2-supported iridium catalyst (Ir-N@HP-mesoZrO2), featuring sufficient accessible catalytic sites even with ultralow loading. Such was successfully applied to selective and direct construction julolidines via reductive annulation readily available quinolines conjugated enones, proceeding good substrate functional group compatibility, reusable catalyst, high step atom efficiency, easy applicability for fabrication molecules. The present work opens door further develop useful transformations by merging hydrogen transfer-mediated activation in situ incorporation coupling sequence under heterogeneous catalysis.

Language: Английский

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Preparation of reusable copper-based biomass-carbon aerogel catalysts and their application in highly selective reduction of maleimides to succinimides with hydrosilane as a hydrogen source

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(5), P. 2592 - 2598

Published: Jan. 1, 2024

A novel copper-based biomass-carbon aerogel catalyst was prepared as a highly efficient and selective for maleimides reduction the first time with excellent catalytic activity, chemo-selectivity, recyclability.

Language: Английский

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Direct access to functional phenazines via oxidative annulation of anilines and o-phenylenediamines with a reusable cobalt catalyst

Green Chemistry, Journal Year: 2022, Volume and Issue: 25(2), P. 678 - 683

Published: Dec. 14, 2022

By single electron oxidation (SEO) induced tandem dual C–H amination, a mild approach enabling direct and diverse construction of amino phenazines via oxidative annulation readily available anilines o -phenylenediamines is presented.

Language: Английский

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Hydride transfer-initiated synthesis of 3-functionalized quinolines by deconstruction of isoquinoline derivatives

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(27), P. 4380 - 4383

Published: Jan. 1, 2022

Under transition metal catalyst-free conditions, we herein present a hydride transfer-initiated construction of novel 3-(2-aminomethyl)aryl quinolines from N-isoquinolinium salts and 2-aminobenzaldehydes, proceeding with the merits operational simplicity, high step atom efficiency, good substrate functional group compatibility, mild conditions. The products are formed by reacting isoquinolyl motif as two-carbon synthon along cleavage its C3-N bond. Given interesting applications 3-aryl quinolines, developed chemistry is anticipated to be further applied develop new products.

Language: Английский

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Diastereoselective construction of bridged piperidines through an interrupted dearomative reduction

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(57), P. 7964 - 7967

Published: Jan. 1, 2022

An interrupted dearomative reduction strategy was developed to transform planar chalcone-based pyridinium salts into structurally intriguing bridged piperidines in a completely regio- and diastereoselective manner. This reaction proceeded successfully by using cheap easily accessible NaBH4 as the reductant under mild conditions without exclusion of oxygen or use special equipment.

Language: Английский

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Recyclable Metallic Imidazolium-Based Ionic Liquid-Catalyzed Selective Mono- and Double-Hydroboration in Water

ACS Sustainable Chemistry & Engineering, Journal Year: 2022, Volume and Issue: 10(41), P. 13742 - 13749

Published: Sept. 30, 2022

The recyclable metallic imidazolium-based ionic liquid-catalyzed mono-hydroboration of imines, double-hydroboration imine with aldehyde, and aniline glutaric dialdehyde in the presence HBpin water is described for first time. liquid [BMIm][FeCl4] showed excellent activity, high selectivity, good recyclability catalytic hydroborations. This system widely tolerated various functional rings unsaturated groups without additional reduction. Furthermore, could be reused more than 15 runs decay activity.

Language: Английский

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