- Synthesis and photophysical properties of benzoxazolyl-imidazole and benzothiazolyl-imidazole conjugates
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Materials that have higher fluorescence emission in the solid state than molecules in solution have recently been paid more attention by the scientific community due to their potential applications in various fields. In this work, we newly synthesized ben
- Chen, Hsing-Yu,Huang, He-Shin,Tseng, Tzu-Yu,Yao, Chen-Chen,Yeh, Mei-Yu,Yeh, Yao-Chun
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p. 40228 - 40234
(2021/12/31)
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- Structurally Modelling the 2-His-1-Carboxylate Facial Triad with a Bulky N,N,O Phenolate Ligand
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We present the synthesis and coordination chemistry of a bulky, tripodal N,N,O ligand, ImPh2NNOtBu (L), designed to model the 2-His-1-carboxylate facial triad (2H1C) by means of two imidazole groups and an anionic 2,4-di-tert-butyl-s
- Monkcom, Emily C.,de Bruin, Dani?l,de Vries, Annemiek J.,Lutz, Martin,Ye, Shengfa,Klein Gebbink, Robertus J. M.
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supporting information
p. 5191 - 5204
(2021/03/01)
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- Tuning the optical properties of BODIPY dyes by N-rich heterocycle conjugation using a combined synthesis and computational approach
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The increased number of N-atoms induced a blueshift in absorption and a gain in fluorescence quantum yield, from 750 nm and ~0% for pyrrole to 635 nm and ~40% for triazole, respectively. DFT calculations indicated a decrease in HOMO energy levels with the
- Banala, Srinivas,Kiessling, Fabian,Merkes, Jean Michel,Ostlender, Tobias,Sun, Haitao,Wang, Fufang
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supporting information
p. 19641 - 19645
(2021/11/12)
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- Formation of exceptionally weak C-C bonds by metal-templated pinacol coupling
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The ability of the bis(imidazolyl)ketone ligand BMdiPhIK (bis(1-methyl-4,5-diphenylimidazolyl)ketone) to function as a redox active ligand has been investigated. The reduction of [M(BMdiPhIK)Cl2] (M = Fe and Zn) complexes
- Folkertsma,Benthem,Witteman,Van Slagmaat,Lutz,Klein Gebbink,Moret
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supporting information
p. 6177 - 6182
(2017/07/10)
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- Synthesis of optically active polyheterocycles containing pyrrolidine, imidazole, and 1,2,3-triazole rings
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Optically active polyheterocycles containing pyrrolidine, imidazole, and 1,2,3-triazole units were obtained via a multistep synthesis with the [3+2] cycloaddition of Boc-protected (S)-(pyrrolidin-2-yl)methyl azide with 2-ethynylimidazoles in the presence of CuI (CuAAC reaction) as the key step. Typical for terminal alkynes, the reactions occurred regioselectively and 1,4-disubstituted 1,2,3-triazoles were formed exclusively. The deprotection of the pyrrolidine N-atom was performed by treatment with TFA under standard conditions.
- Wróblewska, Aneta,Mlostoń, Grzegorz,Heimgartner, Heinz
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p. 1448 - 1452
(2015/12/09)
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- Microwave-assisted conversion of carbonyl compounds into formylated secondary amines: New contribution to the Leuckart reaction mechanism in N-methylformamide
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The reductive amination of several carbonyl compounds (Leuckart reaction) has been performed using N-methylformamide and microwave technology. Under these conditions, a new mechanism is proposed via the initial formation of an imine, followed by reduction
- Barba, Fructuoso,Recio, Javier,Batanero, Belen
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p. 1835 - 1838
(2013/04/24)
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- Ruthenium piano-stool complexes bearing imidazole-based PN ligands
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A variety of piano-stool complexes of cyclopentadienyl ruthenium(II) with imidazole-based PN ligands have been synthesized starting from the precursor complexes [CpRu(C10H8)]PF6, [CpRu(NCMe) 3]PF6 and [CpRu(PPh3)2Cl]. PN ligands used are imidazol-2-yl, -4-yl and -5-yl phosphines. Depending on the ligand and precursor different types of coordination modes were observed; in the case of polyimidazolyl PN ligands these were κ1P-monodentate, κ2P,N-, κ2N,N- and κ3N,N,N- chelating and μ-κP:κ2N,N-brigding. The solid-state structures of [CpRu(1a)2Cl ]·H2O (5 .H2O) and [{CpRu(μ-κ2-N,N- κ'1-P-2b)}2](C6H5PO 3H)2(C6H5PO3H 2)2, a hydrolysis product of the as well determined [{CpRu(2b)}2](PF6)2.2CH 3CN (7b.2CH3CN) were determined (1a = imidazol-2-yldiphenyl phosphine, 2b = bis(1-methylimidazol-2-yl)phenyl phosphine, 3a = tris(imidazol-2-yl)phosphine). Furthermore, the complexes [CpRu(L)2]PF6 (L = imidazol-2-yl or imidazol-4-yl phosphine) have been screened for their catalytic activity in the hydration of 1-octyne.
- Kunz, Peter C.,Thiel, Indre,Noffke, Anna Louisa,Rei?, Guido J.,Mohr, Fabian,Spingler, Bernhard
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supporting information; experimental part
p. 33 - 40
(2012/01/06)
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- Asymmetric Copper(II)-catalysed nitroaldol (Henry) reactions utilizing a chiral C1-symmetric dinitrogen ligand
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A series of stable chiral C1-symmetric dinitrogen ligands were conveniently synthesized in high yields by condensation of chiral amines [(-)-exo-bornylamine or (+)-(1S,2S,5R)-menthylamine] with various substituted imidazolecarbaldehydes. With the assistance of base, the ligand L1 in combination with CuCl2·2H2O (2.5 mol-% or 5.0 mol-%) can efficiently promote nitroaldol (Henry) reactions between a variety of aldehydes and nitromethane. Both aromatic and aliphatic aldehydes were tolerated in our catalytic system, affording the expected nitroalcohol products in high yields (up to 97%) and with good enantioselectivities (up to 96%) under mild reaction conditions. A series of chiral C1-symmetric dinitrogen ligands were conveniently synthesized in high yields by condensations of chiralamines with various substituted imidazolecarbaldehydes. The ligand L1 in conjunction with CuCl2·2H2O can efficiently promote nitroaldol (Henry) reactions between various aldehydes and nitromethane in high yields (up to 97%) and with good enantioselectivities (up to 96%).
- Zhou, Yirong,Gong, Yuefa
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experimental part
p. 6092 - 6099
(2011/11/29)
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- Regioselective synthesis of 4,5-diaryl-1-methyl-1H-imidazoles including highly cytotoxic derivatives by Pd-catalyzed direct C-5 arylation of 1-methyl-1H-imidazole with aryl bromides
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A general and efficient three-step procedure for the highly regioselective synthesis of 1-methyl-1H-imidazoles possessing electron-rich, electron-neutral, and/or electron-deficient aryl moieties at their 4- and 5-positions is described. The first step involves the Pd-catalyzed direct C-5 arylation of commercially available 1-methyl-1H-imidazole with aryl bromides, and the second and third steps of the sequence involve the selective C-4 bromination of the resulting 5-aryl-1-methyl-1H-imidazoles with NBS, followed by a PdCl 2(dppf)-catalyzed Suzuki-type reaction between 5-aryl-4-bromo-1- methyl-1H-imidazoles and arylboronic acids under phase-transfer conditions. Two 4,5-diaryl-1-methyl-1H-imidazoles so prepared, which can be regarded as Z-restricted analogues of naturally occurring combretastatin A-4 (CA-4), proved to be highly cytotoxic against a variety of human tumor cell lines, and one of these derivatives has been shown to be more cytotoxic than CA-4 and all of the imidazole derivatives investigated in the literature thus far. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Bellina, Fabio,Cauteruccio, Silvia,Di Fiore, Annarita,Rossi, Renzo
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experimental part
p. 5436 - 5445
(2009/05/07)
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- Formation of a doubly C,N-bridged six-membered metallacyclic bis[(2-imidazolyl)zirconocene] dication
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Treatment of 1-methylimidazol-2-yl lithium with Cp2Zr(C1)CH3 (6) gave the corresponding methyl(1-methyl-2-imidazolyl)zirconocene complex 7. Treatment of 7 with B(C6F5)3 (8) led to selective methyl abstraction. The resulting (imidazolyl)zirconocene cation 9 dimerized under the reaction conditions to yield the dinuclear imidazolyl bridged bis(zirconocene) dication complex 10 that was structurally characterized by X-ray diffraction and by DFT calculations.
- Vagedes, Dominik,Erker, Gerhard,Kehr, Gerald,Fr?hlich, Roland,Grimme, Stefan,Mück-Lichtenfeld, Christian
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p. 305 - 310
(2007/10/03)
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- Design and novel synthesis of aryl-heteroaryl-imidazole MAP kinase inhibitors
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Inhibitors of the MAP kinase p38, potentially useful for the treatment of rheumatoid arthritis and inflammatory diseases, were found to exhibit antifungal activity. We have developed a new diversity-oriented strategy leading to concise and efficient syntheses of known and new members of this compound class. The strategy is based on carbon-carbon cross-coupling reactions using N-protected 4,5-diiodo-imidazoles as the starting templates.
- Dobler, Markus R.
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p. 7115 - 7117
(2007/10/03)
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- Photosensitized oxidation of 13C,15N-labeled imidazole derivatives
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An efficient synthesis of imidazoles with isotope labeling at different positions of the five-membered ring was developed. We carried out a detailed mechanistic study of the photosensitized oxidation of isotope-labeled imidazole derivatives. A new product, CO2, was observed in the photooxidation of 2-H,N1-H imidazoles, but not in 2-substitituted imidazoles. The carbon of CO2 derives from the 2C of imidazole. As shown by 18O experiments, both oxygen atoms of CO2 originate mainly from one molecule of oxygen. Transient intermediates were detected by low-temperature NMR in the photosensitized oxidation of the isotope-labeled imidazoles. Quantitative analysis of the 13C NMR at different temperatures and times correlates the formation of one intermediate with the loss of another, thus allowing the complete decomposition pathway of the transient intermediates to be established. Singlet oxygen reacts with 4,5-diphenylimidazole via a [4 + 2] cycloaddition to form a 2,5-endoperoxide, which, upon warming, decomposes to a hydroperoxide. The hydroperoxide in one pathway loses water to form an imidazolone 7, which is hydrolyzed to a hydroxyimidazol-2-one 11. In another pathway, the hydroperoxide rearranges to diol 8. The diol rearranges to a carbamate 9 by opening and reclosing the five-membered ring. 9 decomposes to CO2 and benzil diimine. A labile NH in the imidazole is crucial for the decomposition of the initially formed endoperoxide, otherwise the endoperoxide decomposes to regenerate starting material. Many similarities exist between the photooxidations of imidazole and guanosine in organic solvent, suggesting that the two reactions share a similar reaction mechanism with singlet oxygen.
- Kang, Ping,Foote, Christopher S.
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p. 9629 - 9638
(2007/10/03)
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- Thermodynamic study on dioxygen binding of diiron(II) and dicobalt(II) complexes containing various dinucleating ligands
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A new dinucleating ligand containing a sterically bulky imidazolyl group, Ph-Htidp (N,N,′,N′-tetrakis[(1-methyl-4, 5-diphenyl-2-imidazolyl)methyl]-1,3-diamino-2-propanol), and its μ-alkoxo-diiron(II) complexes [Fe2(Ph-tidp)(RCO2)]-(C
- Sugimoto, Hideki,Nagayama, Toshihiko,Maruyama, Sachihito,Fujinami, Shuhei,Yasuda, Yuichi,Suzuki, Masatatsu,Uehara, Akira
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p. 2267 - 2279
(2007/10/03)
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- Synthesis, structural and magnetic characterisation of tris(1-methyl-4,5-diphenylimidazol-2-yl)methanol (L) and [{CuL(NO3)}2][NO3]2
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Tris(1-methyl-4,5-diphenylimidazol-2-yl)methanol (L) has been synthesized and characterised. It crystallises as L·0.5 1,2-Cl2C2H4 from 1,2-Cl2C2H4-light petroleum and its crystal structure
- Higgs, Timothy C.,Helliwell, Madeleine,McInnes, Eric J.L.,Mabbs, Frank E.,Harding, Charles J.,Garner, C. David
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p. 927 - 933
(2007/10/03)
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- Synthesis and structure of a 2 CuII 2 CuI constellation ligated by the new biimidazole, bis(1-methyl-4,5-diphenylimidaz-2-oyl)carbinol
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The new biimidazole, bis(1-methyl-4,5-diphenylimidaz-2-oyl)carbinol, BimOH, is synthesized and employed to form the novel tetrameric constellation [Cu4(BimOH)2(BimO)2]4+, involving an (Nim)2CuII(OR)2Cu II(Nim)2 centre with a CuII...CuII separation of 2.998(4) A and two CuI(Nim)2 moieties ca. 5 A from the Cu2 centre, each with an N-Cu-N angle of 169.3(4)°.
- Bhalla, Rajiv,Helliwell, Madeleine,Garner, C. David
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p. 921 - 922
(2007/10/03)
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- A Bis(diimidazole)copper Complex Possessing a Reversible CuII/CuI Couple with a High Redox Potential
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The new diimidazole ligand, bis(1-methyl-4,5-diphenylimidazol-2-yl)ketone (BIMDPK), has been synthesised, characterised and shown to form four-coordinate bis(diimidazole) CuII and CuI complexes in the salts 2 and , the structures of which have been determined by X-ray crystallography.The cations of these salts have a very similar geometry with CuII-Nav=1.949 and CuI-Nav=1.999 Angstroem; the N-Cu-N interbond angles are constrained by 1) the bite angle of the BIMDPK ligand to 94+/-2 deg and 2) the interligand steric interactions, which lead to the dihedral angle of the interligand CuN2 planes of 68.2 deg for CuII and 74.9 for CuI-that is, a CuN4 geometry intermediate between tetrahedral and square planar.The X-band EPR spectrum for the powdered CuII compound is typical of an approximately D2 CuN4 centre possessing a dxy ground state (gx=2.080, gy=2.075, gz=2.291; Az=112.3*10-4 cm-1).The UV/vis spectra are dominated by charge-transfer bands, and both the CuII and CuI systems are intensely coloured.The EPR and electronic spectra indicate that these cations have a very similar structure in the solid state and in solution; the potential of the 2+/+ couple is 0.59 V vs.SCE in MeCN and 0.80 V vs.SCE in CH2Cl2, and the made electron self-exchange constant in MeCN is 1.9*104M-1s-1.Comparisons are between the properties of the 2+/+ centers and related Cu centers in chemical and biological systems; the results of this study reinforce the view that a centre should not be precluded from consideration in biological electron transport. - Keywords: copper complexes; imidazole ligands; redox systems; structure elucidation; enzyme models
- McMaster, Jonathan,Beddoes, Roy L.,Collison, David,Eardley, David R.,Helliwell, Madeleine,Garner, C. David
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p. 685 - 693
(2007/10/03)
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- 4- and 5-Trifluoromethylimidazoles. Novel Cyclization of Trifluoroacetylated Aldehyde Dimethylhydrazones
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Thermally induced cyclization reaction of trifluoroacetylated arylaldehyde dimethylhydrazones 1 in refluxing toluene afforded 1-methyl-4-aryl-5-trifluoromethylimidazoles 2 in good yields.In contrast thermal cyclization of 1 in the presence of silica gel gave regioisomeric 1-methyl-4-trifluoromethyl-5-aryl-imidazoles 5 as major products.These reactions could be extended to the synthesis of related several 1,4,5-trisubstituted imidazoles.
- Kamitori, Yasuhiro,Hojo, Masaru,Masuda, Ryoichi,Ohara, Seiji,Kawasaki, Kazuyoshi,et al.
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p. 487 - 495
(2007/10/02)
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- Reactions with Dimethyl Carbonate, 2. - N-Methylation of Imidazole and Derivatives
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The use of dimethyl carbonate as methylating agent for imidazole derivatives is demonstrated by selected examples.The comparison of the toxicological values of dimethyl carbonate and dimethyl sulfate should inspire to replace the highly toxic dimethyl sulfate by dimethyl carbonate.
- Lissel, Manfred
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- Cyclometallated compounds of manganese(I) with 1-methylphenylimidazoles
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Cyclometallated complexes of manganese(1) with 1-methylphenylimidazoles have been prepared.IR and 1H NMR spectroscopic studies show they are octahedral complexes in which the imidazole ligand is bound to the metal through the nitrogen and phenyl C(6) atom
- Suarez, Antonio,Vila, Jose Manuel,Pereira, Maria Teresa,Gayoso, Eduardo,Gayoso, Miguel
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p. 359 - 364
(2007/10/02)
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- 4,5-DIPHENYLIMIDAZOLES FROM THE CYCLIZATION OF BENZIL N-ALKYLMONOHYDRAZONES
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The thermal cyclization of monodisubstituted hydrazones (1) affords the corresponding N-substituted-4,5-diphenylimidazoles in good to excellent yields; possible mechanisms for this unusual cyclization are presented.
- Collibee, William L.,Anselme, Jean-Pierre
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p. 655 - 662
(2007/10/02)
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- THE UNUSUAL CYCLIZATION OF BENZIL MONOHYDRAZONES TO 4,5-DIPHENYLIMIDAZOLES
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Benzil monodisubstituted hydrazones (2) have been shown to undergo cyclodehydration to the corresponding imidazoles (10) and not to pyrazoles as previously reported.
- Collibee, William L.,Anselme, Jean-Pierre
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p. 1595 - 1596
(2007/10/02)
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- Studies in Heterocyclics: Novel Synthesis of 4,5-Diarylimidazoles
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A novel synthesis of substituted 4,5-diarylimidazoles from N-(arylmethylene)methylamine N-oxides and cold aqueous ethanolic potassium cyanide is reported.A mechanism for the reaction is suggested.All the imidazoles have been screened for antibacterial, fu
- Soni, R. P.
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p. 1493 - 1496
(2007/10/02)
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- The Copper-Catalysed Reaction of 2-Chloroimidazoles and 2-Chlorobenzimidazoles with Dimethylamine
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The preparation of 2-dimethylamino-benzimidazoles and -imidazoles from the corresponding 2-chloro compounds by reaction with dimethylamine is assisted by the presence of copper salts.In the absence of a copper catalyst, 2-chloroimidazoles fail to react.Ki
- Whittle, Chrostopher P.
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p. 1545 - 1551
(2007/10/02)
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- The Reaction between Cyanide Ion and Nitrones; a Novel Imidazole Synthesis
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By contrast with the CN-diphenylnitrones, cold aqueous ethanolic potassium cyanide converts N-methyl-C-phenylnitrone into 1-methyl-4,5-diphenylimidazole.The scope of this reaction has been investigated, and shown to proceed via intermediate cyano-imines, some of which have been synthesised by alternative routes.
- Cawkill, Eric,Clark, Nigel G.
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p. 244 - 248
(2007/10/02)
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