Polymer-Supported Oxidovanadium(IV) Complexes and Their Catalytic Applications in One-Pot Multicomponent Reactions Producing Biologically Active 2,4,5-Trisubstituted-1H-imidazoles

Two new monobasic tridentate O⁀N⁀N donor ligands, HL1 (I) and HL2 (II) have been obtained in two steps by reacting phenylhydrazine and salicylaldehyde or 3,5-di-tert-butylsalicylaldehyde and then reacting the resulting compounds with 2-chloromethylbenzimidazole in the presence of triethylamine. The reaction of [VIVO(acac)2] with these ligands in a 1:1 molar ratio in dry methanol led to the formation of homogeneous oxidovanadium(IV) complexes [VIVO(acac)L1] (1) and [VIVO(acac)L2] (2). Immobilization of these complexes on chloromethylated polystyrene (PS-Cl) cross-linked with divinyl benzene resulted in corresponding polymer-supported heterogeneous complexes PS-[VIVO(acac)L1] (3) and PS-[VIVO(acac)L2] (4). Ligands (I and II), homogeneous complexes (1 and 2) and heterogeneous complexes (3 and 4) have been characterized using elemental analysis and various spectroscopic techniques. A single crystal X-ray diffraction study of I and 1 further confirms their structures. The oxidation state IV of vanadium in these complexes was assured by recording their EPR spectra while heterogeneous complexes were further characterized using field emission-scanning electron microscopy (FE-SEM) combined with energy dispersive X-ray analysis (EDS) and atomic force microscopy (AFM). All vanadium complexes have been explored for their catalytic potential to one-pot-three-component reactions (reagents: benzil, ammonium acetate and various aromatic aldehydes) for the efficient synthesis of 2,4,5-triphenyl-1H-imidazole derivatives (nine examples). Various reaction conditions have been optimized to obtain a maximum yield (up to 96%) of catalytic products. It has been found that heterogeneous complexes show excellent catalytic activity and are recyclable up to five catalytic cycles.

[1]  K. Ghosh,et al.  Polymer-Supported Dioxidovanadium(V) Complex-Based Heterogeneous Catalyst for Multicomponent Biginelli Reaction Producing Biologically Active 3,4-Dihydropyrimidin-2-(1H)-ones , 2023, Catalysts.

[2]  H. Naeimi,et al.  An efficient and eco-compatible multicomponent synthesis of 2,4,5-trisubstituted imidazole derivatives using modified-silica-coated cobalt ferrite nanoparticles with tungstic acid. , 2023, Dalton transactions.

[3]  A. Poursattar Marjani,et al.  Microwave-assisted preparation of polysubstituted imidazoles using Zingiber extract synthesized green Cr2O3 nanoparticles , 2022, Scientific Reports.

[4]  A. Sánchez-González,et al.  Relationship between structure and cytotoxicity of vanadium and molybdenum complexes with pyridoxal derived ligands. , 2022, Journal of inorganic biochemistry.

[5]  Na Li,et al.  Discovery of Novel Celastrol-Imidazole Derivatives with Anticancer Activity In Vitro and In Vivo. , 2022, Journal of medicinal chemistry.

[6]  M. Maurya,et al.  Triazole based oxidovanadium(V) complex supported on chloromethylated polymer and its catalytic activity for the synthesis of dihydropyrimidinones (DHPMs) , 2022, Catalysis Today.

[7]  M. Hasanin,et al.  Newly Synthesized Imidazolotriazole, Imidazolotriazine, and Imidazole-Pyrazole Hybrid Derivatives as Promising Antimicrobial Agents , 2021, Journal of Molecular Structure.

[8]  Cheng‐Chung Wang,et al.  TMSOTf-catalyzed synthesis of trisubstituted imidazoles using hexamethyldisilazane as a nitrogen source under neat and microwave irradiation conditions , 2021, RSC advances.

[9]  K. Werbovetz,et al.  Imidazoles as Potential Anticancer Agents: An Update on Recent Studies , 2021, Molecules.

[10]  Jianguo Yang,et al.  Chemoselective hydroborative reduction of nitro motifs using a transition-metal-free catalyst , 2021, Organic Chemistry Frontiers.

[11]  P. Verma,et al.  Synthesis and therapeutic potential of imidazole containing compounds , 2021, BMC Chemistry.

[12]  Anshu Singh,et al.  Design and synthesis of base-metal nickel(II) based catalysts: studies on nearly selective formation of 1-butene from ethylene , 2020 .

[13]  Luis Pedro Coelho,et al.  Imidazole propionate is increased in diabetes and associated with dietary patterns and altered microbial ecology , 2020, Nature Communications.

[14]  Aiguo Zhong,et al.  Transition-metal-free catalytic hydroboration reduction of amides to amines , 2020, Organic Chemistry Frontiers.

[15]  Shijun Shao,et al.  An HBT-based fluorescent probe for nitroreductase determination and its application in Escherichia coli cell imaging , 2020 .

[16]  Zoleikha Hajizadeh,et al.  Development of novel and green NiFe2O4/geopolymer nanocatalyst based on bentonite for synthesis of imidazole heterocycles by ultrasonic irradiations , 2020, Scientific Reports.

[17]  J. Camp,et al.  Recent advances in the synthesis of imidazoles. , 2020, Organic & biomolecular chemistry.

[18]  B. Larijani,et al.  Design and synthesis of 4,5-diphenyl-imidazol-1,2,3-triazole hybrids as new anti-diabetic agents: in vitro α-glucosidase inhibition, kinetic and docking studies , 2020, Molecular Diversity.

[19]  Shiyang Zhou,et al.  Synthesis and biological activities of local anesthetics , 2019, RSC advances.

[20]  T. T. Nguyen,et al.  An efficient multicomponent synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles catalyzed by a magnetic nanoparticle supported Lewis acidic deep eutectic solvent , 2019, RSC advances.

[21]  R. Almeer,et al.  Anti-Inflammatory and Anti-Hyperuricemic Functions of Two Synthetic Hybrid Drugs with Dual Biological Active Sites , 2019, International journal of molecular sciences.

[22]  Kiran R Kharat,et al.  An efficient method for the synthesis of 2,4,5-trisubstituted imidazoles using lactic acid as promoter , 2019, SN Applied Sciences.

[23]  Zheng Huang,et al.  A BEt3-Base Catalyst for Amide Reduction with Silane. , 2019, The Journal of organic chemistry.

[24]  J. K. Sahu,et al.  Biological Significance of Imidazole-Based Analogues in New Drug Development. , 2019, Current drug discovery technologies.

[25]  A. Nanda,et al.  A Review on Heterocyclic: Synthesis and Their Application in Medicinal Chemistry of Imidazole Moiety , 2018 .

[26]  G. Abu Sheikha,et al.  Synthesis and in Vivo Lipid-Lowering Activity of Novel Imidazoles-5-carboxamide Derivatives in Triton-WR-1339-Induced Hyperlipidemic Wistar Rats. , 2018, Chemical & pharmaceutical bulletin.

[27]  B. Salehi,et al.  Antiulcer Agents: From Plant Extracts to Phytochemicals in Healing Promotion , 2018, Molecules.

[28]  Xiaobin Wang,et al.  Synthesis, Characterization, and Antifungal Activity of Novel Benzo[4,5]imidazo[1,2-d][1,2,4]triazine Derivatives , 2018, Molecules.

[29]  L. Shimon,et al.  Imidazole synthesis by transition metal free, base-mediated deaminative coupling of benzylamines and nitriles. , 2017, Chemical communications.

[30]  Injae Shin,et al.  Small molecule-induced cellular conversion. , 2017, Chemical Society reviews.

[31]  Seyyed Emad Hooshmand,et al.  Molecularly Imprinted Polymer as an Eco-Compatible Nanoreactor in Multicomponent Reactions: A Remarkable Synergy for Expedient Access to Highly Substituted Imidazoles , 2017 .

[32]  Seyyed Emad Hooshmand,et al.  Crosslinked chitosan nanoparticle-anchored magnetic multi-wall carbon nanotubes: a bio-nanoreactor with extremely high activity toward click-multi-component reactions , 2017 .

[33]  Y. Mary,et al.  Modification of benzoxazole derivative by bromine-spectroscopic, antibacterial and reactivity study using experimental and theoretical procedures , 2017 .

[34]  Nitin Kumar,et al.  Synthesis of 3-(4, 5-dihydro-1-phenyl-5-substituted phenyl-1H-pyrazol-3-yl)-2H-chromen-2-one derivatives and evaluation of their anticancer activity , 2017 .

[35]  G. Shi,et al.  Conducting Polymer-Based Catalysts. , 2016, Journal of the American Chemical Society.

[36]  Yan Ran,et al.  β–Cyclodextrin–Propyl Sulfonic Acid Catalysed One-Pot Synthesis of 1,2,4,5-Tetrasubstituted Imidazoles as Local Anesthetic Agents , 2015, Molecules.

[37]  M. Mokhtary,et al.  Tin oxide nanoparticles (SnO2-NPs): An efficient catalyst for the one-pot synthesis of highly substituted imidazole derivatives , 2015 .

[38]  H. Eshghi,et al.  Silica coated magnetic NiFe2O4 nanoparticle supported phosphomolybdic acid; synthesis, preparation and its application as a heterogeneous and recyclable catalyst for the one-pot synthesis of tri- and tetra-substituted imidazoles under solvent free conditions , 2015 .

[39]  Rangappa S. Keri,et al.  Comprehensive Review in Current Developments of Benzimidazole‐Based Medicinal Chemistry , 2015, Chemical biology & drug design.

[40]  P. D. de Jongh,et al.  Recent developments in the synthesis of supported catalysts. , 2015, Chemical reviews.

[41]  A. Ghorbani‐Choghamarani,et al.  Aspartic acid as a highly efficient and nontoxic organocatalyst for the one-pot synthesis of tri- and tetrasubstituted imidazoles under solvent-free conditions , 2015, Russian Journal of Organic Chemistry.

[42]  M. Maurya,et al.  Oxidovanadium(IV) and dioxidovanadium(V) complexes of hydrazones of 2-benzoylpyridine and their catalytic applications. , 2015, Dalton transactions.

[43]  R. Badri,et al.  Tributylhexadecylphosphonium bromide: an efficient reagent system for the one-pot synthesis of 2,4,5-trisubstituted imidazoles , 2015 .

[44]  J. Safari,et al.  Catalytic activity of Cu nanoparticles supported on Fe3O4–polyethylene glycol nanocomposites for the synthesis of substituted imidazoles , 2014 .

[45]  Vinod Kumar,et al.  Imidazole Containing Natural Products as Antimicrobial Agents: A Review , 2014 .

[46]  Erik Serrao,et al.  Discovery of a novel 5-carbonyl-1H-imidazole-4-carboxamide class of inhibitors of the HIV-1 integrase-LEDGF/p75 interaction. , 2013, Bioorganic & medicinal chemistry.

[47]  Michael O’Keeffe,et al.  The Chemistry and Applications of Metal-Organic Frameworks , 2013, Science.

[48]  Jin-Ming Gao,et al.  Synthesis and antifungal activity of 2-chloromethyl-1H-benzimidazole derivatives against phytopathogenic fungi in vitro. , 2013, Journal of agricultural and food chemistry.

[49]  O. Firuzi,et al.  Synthesis and antiproliferative activity evaluation of imidazole-based indeno[1,2-b]quinoline-9,11-dione derivatives , 2013, Archives of pharmacal research.

[50]  A. Ogunlaja,et al.  Oxovanadium(IV)-catalysed oxidation of dibenzothiophene and 4,6-dimethyldibenzothiophene. , 2012, Dalton transactions.

[51]  Duane D. Miller,et al.  Discovery of novel 2-aryl-4-benzoyl-imidazole (ABI-III) analogues targeting tubulin polymerization as antiproliferative agents. , 2012, Journal of medicinal chemistry.

[52]  S. Rajam,et al.  Synthesis , characterization and biological evaluation of benzoxazole derivatives , 2012 .

[53]  A. Teimouri,et al.  An efficient and one-pot synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles catalyzed via solid acid nano-catalyst , 2011 .

[54]  Y. Nageswar,et al.  DABCO as a mild and efficient catalytic system for the synthesis of highly substituted imidazoles via multi-component condensation strategy , 2010 .

[55]  J. Reek,et al.  Supramolecular catalysis beyond enzyme mimics. , 2010, Nature chemistry.

[56]  Z. Tshentu,et al.  Polymer-anchored oxovanadium(IV) complex for the oxidation of thioanisole, styrene and ethylbenzene , 2010 .

[57]  Hamed I. Ali,et al.  Synthesis, antitumor activity and molecular docking study of novel sulfonamide-Schiff's bases, thiazolidinones, benzothiazinones and their C-nucleoside derivatives. , 2010, European journal of medicinal chemistry.

[58]  G. Nandi,et al.  L-Proline: an efficient catalyst for the one-pot synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles , 2009 .

[59]  K. Makimura,et al.  In vitro antifungal activities of luliconazole, a new topical imidazole. , 2009, Medical mycology.

[60]  Umesh Kumar,et al.  Vanadium-salen and -salan complexes: Characterization and application in oxygen-transfer reactions , 2009 .

[61]  Aneesa,et al.  Synthesis and antimicrobial activity of novel analogs of trifenagrel , 2009 .

[62]  Suman Gupta,et al.  Aryloxy cyclohexyl imidazoles: a novel class of antileishmanial agents. , 2009, Bioorganic & medicinal chemistry letters.

[63]  K. Srinivasan,et al.  Antibacterial Activity of Synthesized 2,4,5‐Trisubstituted Imidazole Derivatives , 2008, Chemical biology & drug design.

[64]  Parasa Hazarika,et al.  An efficient and one-pot synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles catalyzed by InCl3·3H2O , 2008 .

[65]  R. Rossi,et al.  Synthesis and biological activity of vicinal diaryl-substituted 1H-imidazoles , 2007 .

[66]  Jennifer A. Natoli,et al.  Optimization of imidazole amide derivatives as cannabinoid-1 receptor antagonists for the treatment of obesity. , 2007, Bioorganic & medicinal chemistry letters.

[67]  Yoshinori Yamamoto,et al.  Recent progress in the catalytic synthesis of imidazoles. , 2007, Chemistry, an Asian journal.

[68]  W. Fernelius,et al.  Vanadium(IV) Oxy(acetylacetonate) , 2007 .

[69]  M. Salunkhe,et al.  Potential of Ionic Liquids in Greener Methodologies Involving Biocatalysis and Other Synthetically Important Transformations , 2006 .

[70]  P. Arnold,et al.  F-block N-heterocyclic carbene complexes. , 2006, Chemical communications.

[71]  Martin Ebel,et al.  Synthesis, characterization, reactivity, and catalytic potential of model vanadium(IV, V) complexes with benzimidazole-derived ONN donor ligands. , 2006, Inorganic chemistry.

[72]  Zhong Jin.  Imidazole, oxazole and thiazole alkaloids. , 2006, Natural product reports.

[73]  A. Shaabani,et al.  Silica sulfuric acid as an efficient and recoverable catalyst for the synthesis of trisubstituted imidazoles , 2006 .

[74]  J. Wepsiec,et al.  Synthesis of Imidazole Based p38 MAP (Mitogen-Activated Protein) Kinase Inhibitors under Buffered Conditions , 2006 .

[75]  P. Baures,et al.  Imidazole-4,5-dicarboxamide derivatives with antiproliferative activity against HL-60 cells. , 2005, Journal of medicinal chemistry.

[76]  K. Srinivasan,et al.  Room temperature ionic liquid promoted improved and rapid synthesis of 2,4,5-triaryl imidazoles from aryl aldehydes and 1,2-diketones or α-hydroxyketone , 2005 .

[77]  A. Wierzbicki.  Imidazole derivatives as cholesterol-lowering agents , 2003 .

[78]  P. Suarez,et al.  Ionic liquid (molten salt) phase organometallic catalysis. , 2002, Chemical reviews.

[79]  B. Szabo.  Imidazoline antihypertensive drugs: a critical review on their mechanism of action. , 2002, Pharmacology & therapeutics.

[80]  D. Bourissou,et al.  Stable Carbenes. , 2000, Chemical reviews.

[81]  D. Wolan,et al.  Antifungal Imidazoles Block Assembly of Inducible NO Synthase into an Active Dimer* , 1999, The Journal of Biological Chemistry.

[82]  Jerry L. Adams,et al.  A protein kinase involved in the regulation of inflammatory cytokine biosynthesis , 1994, Nature.

[83]  H. Takasugi,et al.  Studies on antiulcer drugs. I. Synthesis and antiulcer activities of imidazo[1,2-alpha]pyridinyl-2-oxobenzoxazolidines-3-oxo-2H-1,4-benzoxaz ines and related compounds. , 1991, Chemical & pharmaceutical bulletin.