Use of tetrahydropyrimidinium salts for highly efficient palladium-catalyzed cross-coupling reactions of aryl bromides and chlorides

New, sterically demanding 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (2) as NHC precursors have been synthesized and characterized. These salts, in combination with palladium acetate, provided active catalysts for the cross-coupling of aryl chlorides and bromides under mild conditions. The catalytic system was applied to the Heck, Suzuki and benzaldehyde (Kumada) coupling reactions. Catalyst activity was found to be influenced by the presence of a methoxy group on the ring of the p-position of benzyl substituent of the ligand precursor.     

Eta6-mesityl,eta1-imidazolinylidene-carbene-ruthenium(II) complexes: catalytic activity of their allenylidene derivatives in alkene metathesis and cycloisomerisation reactions

The reaction of electron-rich carbene-precursor olefins containing two imidazolinylidene moieties [(2,4,6-Me(3)C(6)H(2)CH(2))NCH(2)CH(2)N(R)Cdbond;](2) (2a: R=CH(2)CH(2)OMe, 2 b R=CH(2)Mes), bearing at least one 2,4,6-trimethylbenzyl (R=CH(2)Mes) group on the nitrogen atom, with [RuCl(2)(arene)](2) (arene=p-cymene, hexamethylbenzene) selectively leads to two types of complexes. The cleavage of the chloride bridges occurs first to yield the expected (carbene) (arene)ruthenium(II) complex 3. Then a further arene displacement reaction takes place to give the chelated eta(6)-mesityl,eta(1)-carbene-ruthenium complexes 4 and 5. An analogous eta(6)-arene,eta(1)-carbene complex with a benzimidazole frame 6 was isolated from an in situ reaction between [RuCl(2)(p-cymene)](2), the corresponding benzimidazolium salt and cesium carbonate. On heating, the RuCl(2)(imidazolinylidene) (p-cymene) complex 8, with p-methoxybenzyl pendent groups attached to the N atoms, leads to intramolecular p-cymene displacement and to the chelated eta(6)-arene,eta(1)-carbene complex 9. On reaction with AgOTf and the propargylic alcohol HCtbond;CCPh(2)OH, compounds 4-6 were transformed into the corresponding ruthenium allenylidene intermediates (4-->10, 5-->11, 6-->12). The in situ generated intermediates 10-12 were found to be active and selective catalysts for ring-closing metathesis (RCM) or cycloisomerisation reactions depending on the nature of the 1,6-dienes. Two complexes [RuCl(2)[eta(1)-CN(CH(2)C(6)H(2)Me(3)-2,4,6)CH(2)CH(2)N- (CH(2)CH(2)OMe)](C(6)Me(6))] 3 with a monodentate carbene ligand and [RuCl(2)[eta(1)-CN[CH(2)(eta(6)-C(6)H(2)Me(3)-2,4,6)]CH(2)CH(2)N-(CH(2)C(6)H(2)Me(3)-2,4,6)]] 5 with a chelating carbene-arene ligand were characterised by X-ray crystallography.     

Hydrophobic cryogels for DNA adsorption: Effect of embedding of monosize microbeads into cryogel network on their adsorptive performances

As alternative hydrophobic adsorbent for DNA adsorption, supermacroporous cryogel disks were synthesized via free radical polymerization. In this study, we have prepared two kinds of cryogel disks: (i) poly(2‐hydroxyethyl methacrylate‐N‐methacryloyl‐l ‐tryptophan) [p(HEMA‐MATrp)] cryogel containing specific hydrophobic ligand MATrp; and (ii) monosize p(HEMA‐MATrp) particles synthesized via suspension polymerization embedded into p(HEMA) cryogel structure to obtain p(HEMA‐MATrp)/p(HEMA) composite cryogel disks. These cryogel disks containing hydrophobic functional group were characterized via swelling studies, Fourier transform infrared spectroscopy, elemental analysis, surface area measurements and scanning electron microscopy. DNA adsorption onto both p(HEMA‐MATrp) cryogel and p(HEMA‐MATrp)/p(HEMA) composite cryogels was investigated. Maximum adsorption of DNA on p(HEMA‐MATrp) cryogel was found to be 15 mg/g polymer. Otherwise, p(HEMA‐MATrp)/p(HEMA) composite cryogels significantly increased the DNA adsorption capacity to 38 mg/g polymer. Composite cryogels could be used repeatedly without significant loss on adsorption capacity after 10 repetitive adsorption–desorption cycles. Copyright © 2013 John Wiley & Sons, Ltd.     

Ruthenium(II) complexes derived from 2‐phenylthiazoline‐4‐carboxylic acid: structure and catalytic activity for transfer hydrogenation reaction

Piano‐stool ([(p‐cymene)Ru(thz)Cl], 2 ) and six‐coordinated ([Ru(thz)₂(PPh₃)₂], 3 ) ruthenium complexes derived from 2‐phenylthiazoline‐4‐carboxylic acid (Hthz, 1 ) were synthesized for the first time, and fully characterized using conventional methods. Also, the molecular structure of complex 3 was determined using X‐ray analysis. These complexes were evaluated as catalysts for transfer hydrogenation of carbonyl compounds in the presence of isopropyl alcohol and KO^tBu. Complex 2 was found to be more active than 3 in transfer hydrogenation. Copyright © 2016 John Wiley & Sons, Ltd.     

The Different Effects of Metal Ions on the Synthesis of Macroacyclic Compounds: X-ray Crystal Structure,Theoretical Studies,Antibacterial and Antifungal Activities

Russian Journal of Coordination Chemistry - In this work, we have been involved studying the synthesis of some new macroacyclic complexes I–VIII, so we tried to get propoesed results...     

Theoretical analysis of frontier orbitals,electronic transitions,and global reactivity descriptors of M(CO)4L2 type metal carbonyl complexes: a DFT/TDDFT study

Structural Chemistry - Metal carbonyl complexes, which have been known as effective catalysts since early days, find use in many fields both directly and indirectly. Although the use of metal...     

Preparation of New Calix[4]arene-Immobilized Biopolymers for Enhancing Catalytic Properties of Candida rugosa Lipase by Sol–Gel Encapsulation

The article describes preparation of new calixarene biopolymers consisting of the immobilization of convenience calixarene derivative onto cellulose and chitosan biopolymers, and the encapsulation of these calixarene biopolymers with Candida rugosa lipase within a chemical inert sol–gel supported by polycondensation with tetraethoxysilane and octyltriethoxysilane. The catalytic properties of immobilized lipase were evaluated into model reactions employing the hydrolysis of p-nitrophenylpalmitate and the enantioselective hydrolysis of naproxen methyl esters from racemic prodrugs in aqueous buffer solution/isooctane reaction system. The resolution studies using sol–gel support have observed more improvement in the enantioselectivity of naproxen E?=?300 with Cel-Calix-E than with encapsulated lipase without calixarene-based materials. Furthermore, the encapsulated lipase (Cel-Calix-E) was still retained about 39 % of their conversion ratios after the fifth reuse in the enantioselective reaction.     

Preparation of calix[4]arene-based sporopollenin and examination of its dichromate sorption ability

The present study describes the preparation of a new calix[4]arene-based sporopollenin material and its application for the removal of Na₂Cr₂O₇ from aqueous solution. The novel calix[4]arene-based sporopollenin material was prepared via the immobilization of dihydrazine amide derivative of p-tert-butylcalix[4]arene (3) onto the modified sporopollenin. The newly prepared calix[4]arene-based sporopollenin is characterized by using different analytical techniques such as FT-IR spectroscopy, scanning electron microscope and Elemental analysis. The batch wise sorption study was carried out to optimize various experimental parameters such as the effect of sorbent dosage, pH, temperature and Cr(VI) anion concentration. It has been found that the sorption of Cr(VI) anion on calix[4]arene-based sporopollenin was highly pH dependent and maximum sorption was achieved at pH 1.5. The sorption behavior was also evaluated by Langmuir, Freundlich and Dubinin Radushkevich isotherms. The value of correlation coefficient (R ²) showed a good agreement with Freundlich isotherm model. Result of study demonstrated that calix[4]arene-based sporopollenin proved to be highly effective for the removal of Cr(VI).