Knoevenagel condensation reaction counts as a vital condensation in organic chemistry due to the synthesis of valuable intermediates, heterocycles, and fine chemicals from commercially available reactants through forming new CC bonds between an aldehyde or ketone and active methylene compounds. Therefore, the catalytic Knoevenagel condensation reaction has continuously received significant interest in different aspects, , investigating the catalytic efficiency of new heterogeneous and homogeneous catalysts. Furthermore, metal-free catalysis has recently attracted considerable attention because of environmental concerns. This review summarizes the most recent studies on utilizing metal-free nitrogen-based catalysts in the Knoevenagel condensation reaction, including organocatalysts, polymers, ionic liquids, and bio- and carbon-based catalysts. The substrate scope, the optimal reaction conditions, selectivity, the desired product yield, merits, and limitations of each method are discussed. In addition, the recyclability, biocompatibility, and biodegradability of catalysts are reported. This review also covers the approaches that influence the selectivity of the Knoevenagel products.
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http://dx.doi.org/10.1039/d2ob00135g | DOI Listing |
J Hazard Mater
January 2025
State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023, China. Electronic address:
In nuclear wastewater treatment, ion-scavenging materials designed to trap TcO is urgently needed. However, strong acid/base, high radiation and high salt concentration of nuclear wastewater usually result in inadequate stability and adsorption capacity of the adsorbent. Herein, we report a new class of bifunctional anion-exchange olefin-linked COF (BPDC-MTMP) prepared via Knoevenagel condensation reactions, the first example exploring the synergistic integration of positively charged fragments at both nodes and linkers.
View Article and Find Full Text PDFACS Appl Polym Mater
January 2025
Department of Chemistry, Faculty of Science and Engineering, Swansea University, Grove Building, Singleton Park, Swansea SA2 8PP, U.K.
Heterogeneous catalysis is significantly enhanced by the use of highly porous polymers with specific functionalities, such as basic groups, which accelerate reaction rates. Polymers of intrinsic microporosity (PIMs) provide a unique platform for catalytic reactions owing to their high surface areas and customizable pore structures. We herein report a series of Tröger's base polymers (TB-PIMs) with enhanced basicity, achieved through the incorporation of nitrogen-containing groups into their repeat units, such as triazine and triphenylamine.
View Article and Find Full Text PDFRSC Adv
January 2025
Department of Organic Chemistry, University of Debrecen Egyetem Square 1 Debrecen 4032 Hungary
Domino Knoevenagel-cyclization reactions of styrene substrates, containing an -(-formyl)aryl subunit, were carried out with -substituted 2-cyanoacetamides to prepare tetrahydro-4-pyrano[3,4-]quinolone and hexahydrobenzo[]phenanthridine derivatives by competing IMHDA and IMSDA cyclization, respectively. The diastereoselective IMHDA step with α,β-unsaturated amide, thioamide, ester and ketone subunits as a heterodiene produced condensed chiral tetrahydropyran or thiopyran derivatives, which in the case of Meldrum's acid were reacted further with amine nucleophiles in a multistep domino sequence. In order to simplify the benzene-condensed tricyclic core of the targets and get access to hexahydro-1-pyrano[3,4-]pyridine derivatives, a truncated substrate was reacted with cyclic and acyclic active methylene reagents in diastereoselective Knoevenagel-IMHDA reactions to prepare novel condensed heterocyclic scaffolds.
View Article and Find Full Text PDFChemSusChem
January 2025
Polish Academy of Sciences, Institute of Organic Chemistry, Kasprzaka 44/52, 01-224, Warsaw, POLAND.
We demonstrate the application of mechanochemistry in the synthesis of indolone-based photoswitches (hemiindigos, hemithioindigos, and oxindoles) via Knoevenagel condensation reactions. Utilizing ball-milling and an organic base (piperidine) acting as catalyst and solvent for liquid assisted grinding (LAG) conditions, we achieve rapid, solvent-free transformations, obtaining a set of known and previously unreported photoswitches, including highly functional amino acid-based photoswitches, multichromophoric derivatives and photoswitchable cavitands based on resorcin[4]arenes. The reaction under mechanochemical conditions gives moderate-to-high yields and is highly stereoselective leading to Z-isomers of hemiindigos and hemithioindigos and E-isomers of oxindoles.
View Article and Find Full Text PDFMacromol Rapid Commun
January 2025
State Key Laboratory of Applied Organic Chemistry (SKLAOC), Key Laboratory of Special Function Materials and Structure Design, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China.
Conjugated polymers have attracted extensive attention as semiconducting materials in wearable and flexible electronics. In this study, we utilize atom-economical Knoevenagel reaction to construct two conjugated polymers, PTDPP-CNTT and PFDPP-CNTT, based on dialdehyde-thiophene/furan-flanked diketopyrrolopyrrole (DPP) and 2,2'-(thieno[3,2-b]thiophene-2,5-diyl)diacetonitrile (CNTT). The resulting polymers exhibited suitable highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) energy levels, small bandgaps, and broad UV-vis-NIR absorptions (≈400-1000 nm), endowing them with photothermal and balanced ambipolar semiconducting properties with hole and electron mobilities over 10 cmVs.
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