Hydrogen Donor (hydrogen + donor)

Distribution by Scientific Domains
Distribution within Chemistry

Selected Abstracts

ChemInform Abstract: Thermal- and Microwave-Assisted Hydrogenation of Electron-Deficient Alkenes Using a Polymer-Supported Hydrogen Donor.

CHEMINFORM, Issue 49 2001
Bimbisar Desai
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]

Ruthenium (II) complexes immobilized on swellable polyacrylate matrices: Synthesis and catalytic applications

Z. S. Liu
Abstract RuH2(PPh3)4 has been immobilized on swellable polyacrylate matrices to provide heterogenized carboxylate-derivatives. These swellable polymer supported ruthenium (II) complex catalysts have been used in the transfer hydrogenation of aldehydes. Hydrogen donors are formate salt, cyclohexanol, and benzyl alcohol. The catalysts exhibit good activity for hydrogen transfer reduction of aldehydes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source]

Promiscuous Substrate Binding Explains the Enzymatic Stereo- and Regiocontrolled Synthesis of Enantiopure Hydroxy Ketones and Diols

Marcela Kurina-Sanz
Abstract Regio- and stereoselective reductions of several diketones to afford enantiopure hydroxy ketones or diols were accomplished using isolated alcohol dehydrogenases (ADHs). Results could be rationalised taking into account different (promiscuous) substrate-binding modes in the active site of the enzyme. Furthermore, interesting natural cyclic diketones were also reduced with high regio- and stereoselectivity. Some of the 1,2- and 1,3-diketones used in this study were reduced by employing a low excess of the hydrogen donor (2-propanol) due to the quasi-irreversibility of these ADH-catalysed processes. Thus, using lower quantities of co-substrate, scale-up could be easily achieved. [source]

Highly Enantioselective Transfer Hydrogenation of ,-Imino Esters by a Phosphoric Acid

Qiang Kang
Abstract Chiral phosphoric acids have been identified as highly efficient organocatalysts for the asymmetric transfer hydrogenation of ,-imino esters and amide. Utilizing Hantzsch esters as the hydrogen donor, versatile highly enantioenriched ,-amino esters and their derivatives were obtained with up to 98,% ee. [source]

Peroxidatic activity in heart effluent: a biochemical parameter for the assessment of experimental ischemia-reperfusion injury

M.V. Leabu
Abstract Peroxidatic activity in heart effluent was defined as a new biochemical parameter for the experimental study of myocardial ischemia. The peroxidatic reaction was determined by dot blot analysis with 3,3,-diaminobenzidine as hydrogen donor. After ischemia, the level of peroxidatic activity in heart effluent was 2-3 times higher than before. The effects in experimental modulation of ischemia, such as nicorandil or aprikalim protection, and the reversibility of protection by glibenclamide, could accurately be noted using the level of peroxidatic activity in heart effluent as a biochemical parameter. The results were in good agreement with those obtained for other enzymes used as biochemical parameters in experimental heart ischemia-reperfusion studies. [source]

Ab initio investigation on the reaction path and rate for the gas-phase reaction of HO + H2O , H2O + OH

Tadafumi Uchimaru
Abstract This article describes an ab initio investigation on the potential surfaces for one of the simplest hydrogen atom abstraction reactions, that is, HO + H2O , H2O + OH. In accord with the findings in the previously reported theoretical investigations, two types of the hydrogen-bonding complexes [HOHOH] and [H2OHO] were located on the potential energy surface. The water molecule acts as a hydrogen donor in the [HOHOH] complex, while the OH radical acts as a hydrogen donor in the [H2OHO] complex. The energy evaluations at the MP2(FC) basis set limit, as well as those through the CBS-APNO procedure, have provided estimates for enthalpies of association for these complexes at 298 K as ,2.1 , ,2.3 and ,4.1 , ,4.3 kcal/mol, respectively. The IRC calculations have suggested that the [H2OHO] complex should be located along the reaction coordinate for the hydrogen abstraction. Our best estimate for the classical barrier height for the hydrogen abstraction is 7.8 kcal/mol, which was obtained from the CBS-APNO energy evaluations. After fitting the CBS-APNO potential energy curve to a symmetrical Eckart function, the rate constants were calculated by using the transition state theory including the tunneling correction. Our estimates for the Arrhenius parameters in the temperature region from 300 to 420 K show quite reasonable agreement with the experimentally derived values. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1538,1548, 2003 [source]

Photochemically Cross-linked Poly(aryl ether ketone) Rings

Ian Teasdale
Abstract Summary: Macrocyclic phenyl ether ketones were prepared via pseudo high dilution condensation. Irradiation of these rings with UV light in a solution containing isopropyl alcohol as hydrogen donor resulted in a photo-induced reduction of benzophenone to benzopinacol and the formation linked macrocycles. These rings can be heated to undergo ring-opening polymerization and produce a polymer network or they can be added to a polycondensation reaction to prepare poly(ether ether ketones) with variable degrees of cross-linking. Photochemical cross-linking of PEK rings and ring opening polymerization (n: 2,6). (a) h,, iPrOH, DCM; (b) CsF, 260,°C (polymer 3); (c) 4,4,,difluorobenzophenone, hydroquinone, diphenylsulphone, K2CO3, 260,°C (2% polymer 4; 6% polymer 5). [source]

Substrate binding induces structural changes in cytochrome P450cam

Keisuke Sakurai
The binding of (+)-camphor to cytochrome P450cam (P450cam) expels a cluster of waters at the active site, raising the redox potential of the haem to an extent that allows reduction by the electron-transfer system. This binding was reported to involve no significant structural changes in the protein. Here, two ferric P450cam structures partially complexed with (+)-camphor were determined by X-ray crystallography at 1.30,1.35,Ĺ resolution, revealing the structures of the substrate-free and substrate-bound forms. (+)-Camphor binding induces rotation of Thr101 to form a hydrogen bond that acts as a hydrogen donor to a peripheral haem propionate. This bonding contributes to the redox-potential change. [source]

Synthetic Scope and Mechanistic Studies of Ru(OH)x/Al2O3 -Catalyzed Heterogeneous Hydrogen-Transfer Reactions

Kazuya Yamaguchi Dr.
Abstract Three kinds of hydrogen-transfer reactions, namely racemization of chiral secondary alcohols, reduction of carbonyl compounds to alcohols using 2-propanol as a hydrogen donor, and isomerization of allylic alcohols to saturated ketones, are efficiently promoted by the easily prepared and inexpensive supported ruthenium catalyst Ru(OH)x/Al2O3. A wide variety of substrates, such as aromatic, aliphatic, and heterocyclic alcohols or carbonyl compounds, can be converted into the desired products, under anaerobic conditions, in moderate to excellent yields and without the need for additives such as bases. A larger scale, solvent-free reaction is also demonstrated: the isomerization of 1-octen-3-ol with a substrate/catalyst ratio of 20,000/1 shows a very high turnover frequency (TOF) of 18,400 h,1, with a turnover number (TON) that reaches 17,200. The catalysis for these reactions is intrinsically heterogeneous in nature, and the Ru(OH)x/Al2O3 recovered after the reactions can be reused without appreciable loss of catalytic performance. The reaction mechanism of the present Ru(OH)x/Al2O3 -catalyzed hydrogen-transfer reactions were examined with monodeuterated substrates. After the racemization of (S)-1-deuterio-1-phenylethanol in the presence of acetophenone was complete, the deuterium content at the ,-position of the corresponding racemic alcohol was 91,%, whereas no deuterium was incorporated into the ,-position during the racemization of (S)-1-phenylethanol-OD. These results show that direct carbon-to-carbon hydrogen transfer occurs via a metal monohydride for the racemization of chiral secondary alcohols and reduction of carbonyl compounds to alcohols. For the isomerization, the ,-deuterium of 3-deuterio-1-octen-3-ol was selectively relocated at the ,-position of the corresponding ketones (99,% D at the ,-position), suggesting the involvement of a 1,4-addition of ruthenium monohydride species to the ,,,-unsaturated ketone intermediate. The ruthenium monohydride species and the ,,,-unsaturated ketone would be formed through alcoholate formation/,-elimination. Kinetic studies and kinetic isotope effects show that the RuH bond cleavage (hydride transfer) is included in the rate-determining step. [source]

The asymmetric synthesis of (R,R)-formoterol via transfer hydrogenation with polyethylene glycol bound Rh catalyst in PEG2000 and water

CHIRALITY, Issue 2 2010
Ling Huang
Abstract (R,R)-formoterol was synthesized in seven steps with 4-hydroxyl-3-nitro-acetophenone as the starting material. The key intermediate, the chiral secondary alcohol 4, was prepared via Rh-catalyzed asymmetric transfer hydrogenation with (S,S)-PEGBsDPEN as the ligand and sodium formate as the hydrogen donor under mild conditions. With a mixture of PEG 2000 and water as the reaction media, the catalyst system could be recycled four times. Chirality, 2010. © 2009 Wiley-Liss, Inc. [source]

The Tris(trimethylsilyl)silane/Thiol Reducing System: A Tool for Measuring Rate Constants for Reactions of Carbon-Centered Radicals with Thiols

Chryssostomos Chatgilialoglu
Abstract An extension of the well-known ,free-radical-clock' methodology is described that allows one to determine the rate constants of carbon-centered radicals with a variety of thiols by using the tris(trimethylsilyl)silane/thiol couple as a reducing system. A total of 20 rate constants for the hydrogen abstraction from a variety of alkyl-, silyl-, and aryl-substituted thiols by the primary-alkyl radical 2 in toluene at 80° were determined with the aid of the 5- exo-trig cyclization as a timing device. Further, seven rate constants for the hydrogen abstraction from a variety of alkyl- and silyl-substituted thiols by the acyl radical 9 in benzene at 80° were measured using the decarbonylation process as a timing device. The rate constants varied over two orders of magnitude from 106 to 108,M,1 s,1. Substituent effects were rationalized. The radical-trapping abilities of these reducing systems and those of other common hydrogen donors were compared. [source]

Hydrogen-bonded supramolecular motifs in pyrimethaminium 4-methylbenzoate, pyrimethaminium 3-hydroxypicolinate and pyrimethaminium 2,4-dichlorobenzoate

Kaliyaperumal Thanigaimani
In 2,4-diamino-5-(4-chlorophenyl)-6-ethylpyrimidin-1-ium (pyrimethaminium, PMNH) 4-methylbenzoate, C12H14ClN4+·C8H7O2,, (I), pyrimethaminium 3-hydroxypicolinate, C12H14ClN4+·C6H4NO3,, (II), and pyrimethaminium 2,4-dichlorobenzoate, C12H14ClN4+·C7H3Cl2O2,, (III), the PMNH cations interact with the carboxylate groups of the corresponding anion via nearly parallel N,H...O hydrogen bonds, forming R22(8) ring motifs. A description of the observed arrays of quadruple hydrogen bonds in (I) and (II) in terms of hydrogen donors and acceptors (the DA model), their graph-set motifs and the resulting supramolecular ladder is given. In (III), supramolecular chains along the b axis and helical chains along the a axis are formed via N,H...O hydrogen bonds involving the 2-amino and 4-amino groups of the PMNH cation, respectively. Weak Cl...Cl interactions are also found in (III). [source]

Transition metal complexes with ­thiosemicarbazide-based ligands.

In the title compound, [ZnCl(C2H7N3S)2]Cl, the ZnII ion is five-coordinated in a distorted trigonal,bipyramidal arrangement, with the hydrazine N atoms located in the apical positions. The structure is stabilized by N,H,Cl hydrogen bonds, which involve both the Cl atoms and all the hydrogen donors, except for one of the two thio­amide N atoms. A comparison of the geometry of thio­semicarbazide and S -­methyl­iso­thio­semicarbazide complexes with ZnII, CuII and NiII shows the pronounced influence of the hydrogen-bond network on the coordination geometry of ZnII compounds. [source]