2,582 results on '"Noyori asymmetric hydrogenation"'
Search Results
52. Efficient alkylation of ketones with primary alcohols catalyzed by ruthenium(II)/P,N ligand complexes
- Author
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Chun-Yu Liu, Lin-Yan Xu, Zhi-Gang Ren, Shi-Yuan Liu, David J. Young, and Jian-Ping Lang
- Subjects
chemistry.chemical_classification ,Ketone ,010405 organic chemistry ,Stereochemistry ,Organic Chemistry ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,Alkylation ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,Biochemistry ,Medicinal chemistry ,0104 chemical sciences ,Ruthenium ,Catalysis ,chemistry.chemical_compound ,chemistry ,Benzyl alcohol ,Drug Discovery ,Dehydrogenation - Abstract
An efficient catalytic system containing [RuCl2(η6-p-cymene)]2 and one P,N ligand, N-diphenylphosphino-2-aminopyridine (L1) was loaded in catalyzing the alkylation of ketones with primary alcohols for a diverse array of substrates. Other five P,N ligands based on pyridin-2-amine and pyrimidin-2-amine were also examined in this reaction to explore the influence of steric hindrance and electronic effects. Monitoring by 1H NMR and ESI-MS reveals a stable cationic L1-coordinated ruthenium hydride intermediate, identified as [Ru(η6-p-cymene)(κ2-L1)H]+. Organic intermediates consistent with a three-step dehydrogenation, alkylation and hydrogenation pathway were also observed. The final step in this reaction, the ruthenium-catalysed transfer hydrogenation reduction of α,β-unsaturated ketone with benzyl alcohol was performed separately.
- Published
- 2017
53. Microkinetic analysis of C3–C5 ketone hydrogenation over supported Ru catalysts
- Author
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Jesse Q. Bond, Andreas Heyden, and Omar A. Abdelrahman
- Subjects
chemistry.chemical_classification ,Order of reaction ,Ketone ,Hydrogen ,Chemistry ,Inorganic chemistry ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,02 engineering and technology ,Partial pressure ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Chemical kinetics ,chemistry.chemical_compound ,Acetone ,Physical and Theoretical Chemistry ,0210 nano-technology - Abstract
Rates of C3-C5 ketone hydrogenation are measured in the vapor phase over Ru/SiO2. Reaction kinetics are considered through a range of ketone partial pressures (0.3–30 Torr), hydrogen partial pressures (90–900 Torr), and reaction temperatures (322–456 K). Ketone hydrogenation is observed to be facile, with site time yields ranging from 0.14 s−1 for 2-pentanone to 0.37 s−1 for acetone at 322 K and 1.2 bar H2. At low temperatures, apparent reaction orders and kinetic barriers are similar for all ketones. During acetone hydrogenation at higher temperatures, (422 K), the ketone order increases from 0 to 0.4, while the hydrogen order increases from 0.5 to 0.9. Furthermore, the apparent barrier decreases from ≈50 kJ mol−1 at 322 K to ≈18 kJ mol−1. Apparent trends in hydrogenation rates are interpreted at an elementary level using a microkinetic analysis that is based on a Horiuti-Polanyi mechanism involving two distinct surface sites.
- Published
- 2017
54. Enantioselective Transfer Hydrogenation of Ketones Catalyzed by a Manganese Complex Containing an Unsymmetrical Chiral PNP′ Tridentate Ligand
- Author
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Berthold Stöger, Afrooz Zirakzadeh, Michael Widhalm, Karl Kirchner, and Sara R. M. M. de Aguiar
- Subjects
010405 organic chemistry ,Stereochemistry ,Organic Chemistry ,Absolute configuration ,Enantioselective synthesis ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,Manganese ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,Medicinal chemistry ,Catalysis ,0104 chemical sciences ,Inorganic Chemistry ,chemistry.chemical_compound ,chemistry ,Ferrocene ,Physical and Theoretical Chemistry ,Selectivity - Abstract
Manganese complexes of the types [Mn(PNP′)(Br)(CO)2] and [Mn(PNP′)(H)(CO)2] containing a tridentate ligand with a planar chiral ferrocene and a centro chiral aliphatic unit were synthesized, characterized, and tested in the enantioselective transfer hydrogenations of 13 ketones. The catalytic reactions proceeded with conversions up to 96 % and ee values up to 86 %. The absolute configuration of all products was determined to be (S). Notably, the presence of dihydrogen (up to 20 bar) did not affect the reduction. On the basis of DFT calculations, preliminary mechanistic details including the origin of the (S) selectivity are presented. The molecular structure of [Mn(PNP′)(Br)(CO)2] was studied by X-ray diffraction.
- Published
- 2017
55. A comparative study of the performance of Pt/MgF2, Ir/MgF2 and Ru/MgF2 catalysts in hydrogenation reactions
- Author
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Monika Kot, Angelika Kiderys, Michał Zieliński, Emilia Alwin, and Mariusz Pietrowski
- Subjects
Magnesium fluoride ,Catalyst support ,Organic Chemistry ,Inorganic chemistry ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Biochemistry ,0104 chemical sciences ,Catalysis ,Ruthenium ,Inorganic Chemistry ,chemistry.chemical_compound ,chemistry ,Chemisorption ,Environmental Chemistry ,Iridium ,Physical and Theoretical Chemistry ,0210 nano-technology ,Platinum - Abstract
This paper reports results of a comparative study of the structure and activity of MgF 2 -supported metal (Me) catalysts containing 1 wt.% of platinum, iridium or ruthenium. Their activities for hydrogenation of toluene and selective hydrogenation of ortho-chloronitrobenzene to ortho-chloroaniline were compared with the hydrogenation performance of metal catalysts prepared by impregnation of a alumina which is one of the most widely used supports. The catalysts were characterized by using low-temperature nitrogen adsorption, TPR-H 2 and H 2 -chemisorption techniques. The nature of metal and support appeared to have a clear influence on metallic phase dispersion and it was reflected by the activity of Me/MgF 2 catalysts. The application of magnesium fluoride as a support has enabled to obtain catalysts showing high activities for hydrogenation of toluene at 323–498 K and selective hydrogenation of ortho-chloronitrobenzene (o-CNB) to ortho-chloroaniline (o-CAN) in the liquid-phase at 353 K under hydrogen pressure of 4 MPa. From among the catalysts studied, the highest activity for the both aforementioned reactions has been found in the case of MgF 2 -supported platinum catalyst and the highest selectivity (100%) in that of ruthenium-containing catalyst. The activity of magnesium fluoride-supported catalysts was several times higher than that of alumina-supported ones.
- Published
- 2017
56. Chiral terpene auxiliaries IV: new monoterpene PHOX ligands and their application in the catalytic asymmetric transfer hydrogenation of ketones
- Author
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Anna Kmieciak and Marek P. Krzemiński
- Subjects
010405 organic chemistry ,Chemistry ,Monoterpene ,Organic Chemistry ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Ruthenium ,Inorganic Chemistry ,Terpene ,Organic chemistry ,Physical and Theoretical Chemistry - Abstract
New PHOX ligands, derived in three steps from (1R,2S,3R,5R)-3-amino-apopinan-2-ol 1 and (1R,2R,3S,5R)-3-amino-pinan-2-ol 2 were applied as chiral ligands for the formation of ruthenium catalysts. The catalysts were used in asymmetric transfer hydrogenations of prochiral ketones producing the corresponding alcohols in moderate to high yields and enantioselectivity.
- Published
- 2017
57. Asymmetric hydrogenation of pro-chiral ketones catalyzed by chiral Ru(II)-benzene organometallic compounds containing amino acid based aroylthiourea ligands
- Author
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M. Muthu Tamizh, Ramasamy Karvembu, M. Mary Sheeba, and Louis J. Farrugia
- Subjects
chemistry.chemical_classification ,010405 organic chemistry ,Organic Chemistry ,Asymmetric hydrogenation ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Medicinal chemistry ,0104 chemical sciences ,Ruthenium ,Catalysis ,Amino acid ,Inorganic Chemistry ,chemistry.chemical_compound ,chemistry ,Materials Chemistry ,Organic chemistry ,Physical and Theoretical Chemistry ,Enantiomer ,Benzene ,Group 2 organometallic chemistry - Abstract
A series of Ru(II)-benzene organometallic compounds (1–6) constructed from [RuCl2(η6-benzene)]2 and chiral aroylthiourea ligands (L1-L6) obtained from D/L-phenylalanine, was fully characterized. The chiral complexes along with 2-propanol and NaOH effected the asymmetric hydrogenation of aromatic ketones at 82 °C within 8–10 h. The reduction reactions proceeded with excellent conversions and enantiomeric excesses (up to 99%).
- Published
- 2017
58. Hydrogenation of ketones with a manganese PN3P pincer pre-catalyst
- Author
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Antoine Bruneau-Voisine, Ding Wang, Jean-Baptiste Sortais, Christophe Darcel, Thierry Roisnel, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique, Université de Rennes 1, Fonds Européens de développement économique régional (FEDER founds), FR-CNRS 3707, INCREASE, la Fondation Rennes 1, JCJC ANR-15-CE07-0001, Agence National de la Recherche, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-15-CE07-0001,Ferracycles,Synthèse et application en catalyse de complexes cyclométalés du fer obtenus par activation C-H(2015)
- Subjects
010405 organic chemistry ,Chemistry ,Ligand ,Process Chemistry and Technology ,Cationic polymerization ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,General Chemistry ,Manganese ,010402 general chemistry ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Pincer movement ,Yield (chemistry) ,Polymer chemistry ,[CHIM]Chemical Sciences ,Organic chemistry ,Dehydrogenation - Abstract
International audience; A catalytic hydrogenation of carbonyl derivs. with a manganese pre-catalyst has been developed. The key feature is the use of an air stable cationic manganese pre-catalyst bearing a tridendate ligand with a 2,6-(diaminopyridinyl)diphosphine scaffold. Under 50 bar of H2, at 130°, various ketones were reduced to the corresponding alcs. with moderate to good yield.
- Published
- 2017
59. Counter Anion Controlled Reactivity Switch in Transfer Hydrogenation: A Case Study between Ketones and Nitroarenes
- Author
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Sabuj Kundu, Bhaskar Paul, and Sujan Shee
- Subjects
010405 organic chemistry ,Chemistry ,Phenanthroline ,Noyori asymmetric hydrogenation ,General Chemistry ,010402 general chemistry ,Transfer hydrogenation ,Photochemistry ,01 natural sciences ,Medicinal chemistry ,0104 chemical sciences ,Ion ,Pincer movement ,chemistry.chemical_compound ,Pyridine ,Reactivity (chemistry) - Abstract
A series of phenanthroline based NHC and pyridine containing NNC and NNN pincer Ru(II) complexes were synthesized and fully characterized by various spectroscopic techniques. Comparative studies revealed that Ru(II)-NHC complexes were much more active than the Ru(II)-NNN complexes in both transfer hydrogenation (TH) of ketones and nitroarenes. Wingtip groups and counter anions modulated the impact of NHC complexes in both the reactions. The complexes with PF6- counter anion were found to be more active in TH of ketones while complexes with Cl- counter anion were superior towards the nitroarenes reduction. To the best of our knowledge this is the first example of counter anion controlled reactivity alteration between TH of ketones and nitroarenes.
- Published
- 2017
60. Half-sandwich ruthenium(II) complexes with water-soluble Schiff base ligands: Synthesis and catalytic activity in transfer hydrogenation of carbonyl compounds
- Author
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Gholamhossein Grivani, Victorio Cadierno, Pascale Crochet, and Somayeh Azizi Talouki
- Subjects
Aqueous solution ,Schiff base ,010405 organic chemistry ,Chemistry ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,Chloride ,0104 chemical sciences ,Catalysis ,Ruthenium ,Inorganic Chemistry ,chemistry.chemical_compound ,Hexafluorophosphate ,Polymer chemistry ,Materials Chemistry ,medicine ,Organic chemistry ,Physical and Theoretical Chemistry ,medicine.drug - Abstract
New ionic Schiff-base ligands have been synthesized by condensation of (3-formyl-4-hydroxybenzyl)triphenylphosphonium and 3-(3-formyl-4-hydroxybenzyl)-1-methyl-1H-imidazol-3-ium chloride and hexafluorophosphate salts with N,N-dimethylethylenediamine. Treatment of the dimeric derivative [{RuCl(μ-Cl)(η6-p-cymene)}2] with two equivalents of these ligands allowed the preparation of novel mononuclear water-soluble Ru(II) complexes, which proved to be catalytically active in the transfer hydrogenation of ketones and aldehydes under aqueous conditions.
- Published
- 2017
61. Low-Pressure Hydrogenation of Nitriles to Primary Amines Catalyzed by Ruthenium Pincer Complexes. Scope and mechanism
- Author
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Arup Mukherjee, Yehoshoa Ben-David, Dipankar Srimani, and David Milstein
- Subjects
Primary (chemistry) ,010405 organic chemistry ,Organic Chemistry ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Ruthenium ,Pincer movement ,Inorganic Chemistry ,chemistry ,Organic chemistry ,Physical and Theoretical Chemistry ,Catalytic hydrogenation - Abstract
The catalytic hydrogenation of nitriles to primary amines constitutes an environmentally benign and atom-economical methodology in synthetic organic chemistry. However, selective hydrogenation can be challenging, and usually elevated pressure and the use of various additives is requited. Herein the hydrogenation of aromatic and aliphatic nitriles to form primary amines catalyzed by ruthenium pincer complexes is described. The reactions are conducted at low H2 pressure, low catalytic loadings and, in case of a variety of benzonitriles, under neutral conditions and without any additives. Mechanistic insight is provided.
- Published
- 2017
62. Long-chain α–ω diols from renewable fatty acids via tandem olefin metathesis–ester hydrogenation
- Author
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Mike Schmitkamp, Piotr Gajewski, Angela Gonzalez-de-Castro, Mae Joanne B. Aguila, Laurent Lefort, Elena Cosimi, and Johannes G. de Vries
- Subjects
inorganic chemicals ,chemistry.chemical_classification ,Tandem ,010405 organic chemistry ,Ligand ,organic chemicals ,Diol ,Noyori asymmetric hydrogenation ,Fatty acid ,010402 general chemistry ,Metathesis ,01 natural sciences ,Pollution ,0104 chemical sciences ,Catalysis ,chemistry.chemical_compound ,chemistry ,Environmental Chemistry ,Organic chemistry ,heterocyclic compounds ,Selectivity - Abstract
Long chain α–ω diols were readily accessed from renewable fatty acid methyl esters following an orthogonal tandem self-metathesis–ester hydrogenation protocol. By adding a base and a bidentate ligand, the metathesis catalysts were transformed in situ into efficient ester hydrogenation catalysts. The selectivity of the hydrogenation reaction was tuned towards the exclusive formation of either the unsaturated or the saturated diol by modifying the ligand/catalyst ratio. An orthogonal tandem cross-metathesis–ester hydrogenation reaction was also applied for the synthesis of a fragrance compound.
- Published
- 2017
63. Asymmetric hydrogenation of α-hydroxy ketones with an iridium/f-amphox catalyst: efficient access to chiral 1,2-diols
- Author
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Yun Xie, Xumu Zhang, Xiuxiu Li, Xiu-Qin Dong, Pan Li, Yuanhua Liu, and Weilong Wu
- Subjects
inorganic chemicals ,010405 organic chemistry ,organic chemicals ,Organic Chemistry ,Asymmetric hydrogenation ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Turnover number ,Catalysis ,chemistry ,Yield (chemistry) ,polycyclic compounds ,Organic chemistry ,High activity ,heterocyclic compounds ,Iridium - Abstract
We successfully applied tridentate f-amphox ligands to the iridium-catalytic asymmetric hydrogenation of various α-hydroxy ketones to afford the corresponding chiral 1,2-diols with excellent results (almost all products up to 99% yield and >99% ee). The resulting chiral 1,2-diols and their derivatives are important synthetic and pharmaceutical intermediates. Our catalytic system displayed extremely high activity, achieving up to 1 000 000 turnover number (TON). The great performance of this asymmetric hydrogenation makes the preparation of various chiral 1,2-diols highly practical with great potential.
- Published
- 2017
64. Novel chiral multidentate P 3 N 4 -type ligand for asymmetric transfer hydrogenation of aromatic ketones
- Author
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Jing-Xing Gao, Fang Wu, Meng Tao, Yan-Yun Li, and Teng Li
- Subjects
Denticity ,010405 organic chemistry ,Chemistry ,Ligand ,Chiral ligand ,Enantioselective synthesis ,Noyori asymmetric hydrogenation ,General Chemistry ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,0104 chemical sciences ,Catalysis ,Solvent ,Polymer chemistry ,Organic chemistry - Abstract
Novel chiral multidentate P3N4-type ligand has been synthesized and characterized by NMR and HRMS. Using i-PrOH as solvent and hydrogen source, asymmetric transfer hydrogenation of various ketones was investigated. The catalyst generated in situ from chiral multidentate aminophosphine ligand (R,R,R,R)-3 and IrCl(CO)(PPh3)2 exhibited highly catalytic activity and excellent enantioselectivity under mild conditions, achieving the corresponding chiral alcohols with up to 99% yield and 99% ee.
- Published
- 2017
65. 3D charged grid induces a high performance catalyst: ruthenium clusters enclosed in X-zeolite for hydrogenation of phenol to cyclohexanone
- Author
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Yanle Li, Weiping Ding, Liping Ding, Jing Gu, Zhiyang Zhang, Nianhua Xue, Yan Zhu, and Luming Peng
- Subjects
Catalyst support ,chemistry.chemical_element ,Cyclohexanone ,Noyori asymmetric hydrogenation ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Photochemistry ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Ruthenium ,chemistry.chemical_compound ,chemistry ,Phenol ,0210 nano-technology ,Zeolite ,Palladium - Abstract
The hydrogenation of phenol to cyclohexanone is an important industrial reaction and supported palladium catalysts are the most popular catalysts applied nowadays. Hitherto, there has been no success in using ruthenium catalysts for this reaction because of their poor catalytic performance, in spite of the fact that ruthenium is a frequently used metallic component in hydrogenation catalysts. Herein, we report our effort in creating a meso-structured catalyst composed of ruthenium clusters enclosed in the super cages of X-zeolite, which is prepared by mixing precursors of ruthenium and X-zeolite at the beginning stage of preparation, i.e., before the crystallization of the zeolite. This well-defined Ru catalyst exhibits excellent catalytic performance for the selective hydrogenation of phenol, similar to palladium catalysts. The results demonstrate that the joint effects of the 3D negatively charged grid of X-zeolite and the enclosed electron-deficient ruthenium clusters enhance the activity of metallic ruthenium and suppress the further hydrogenation of the valuable product cyclohexanone, which is not possible with traditional Ru catalysts. This investigation reveals the fact that although catalytic reactions are always initiated on the active centers of the catalyst at dimensions on the atomic scale, the effect of the neighboring environment surrounding the active species might extend it to the meso-scale, which should not be ignored as it might induce electronic and structural changes in the active species as well as possibly dramatic changes in the performance of the catalyst. The meso-structured catalyst integrated active species and the neighboring environment as a whole should be considered in discussing the performance of catalysts.
- Published
- 2017
66. Ir/BiphPHOX-catalyzed asymmetric hydrogenation of 3-substituted 2,5-dihydropyrroles and 2,5-dihydrothiophene 1,1-dioxides
- Author
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Xinghua Zhang, Yanzhao Wang, Ke Meng, Wanbin Zhang, Jingzhao Xia, and Guoqiang Yang
- Subjects
010405 organic chemistry ,Chemistry ,Ligand ,Organic Chemistry ,Asymmetric hydrogenation ,Chiral ligand ,Noyori asymmetric hydrogenation ,Organic chemistry ,010402 general chemistry ,01 natural sciences ,Combinatorial chemistry ,0104 chemical sciences ,Catalysis - Abstract
An efficient asymmetric hydrogenation of 3-substituted 2,5-dihydropyrroles using an Ir catalyst with an axially flexible chiral phosphine-oxazoline ligand was developed and chiral 3-substituted pyrrolidines could be prepared with excellent ee. 3-Substituted 2,5-dihydrothiophene 1,1-dioxides could also be hydrogenated by our catalyst, giving the desired products with moderate to high enantioselectivities.
- Published
- 2017
67. Selective hydrogenation of conjugated unsaturated ketones containing a hydroxyaryl substituent in the β-position
- Author
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A. S. Pratsko and V. N. Kovalenko
- Subjects
chemistry.chemical_compound ,010405 organic chemistry ,Chemistry ,Organic Chemistry ,Substituent ,Organic chemistry ,Noyori asymmetric hydrogenation ,Conjugated system ,010402 general chemistry ,Selectivity ,01 natural sciences ,0104 chemical sciences - Abstract
A high selectivity was achieved in the Ni2B-catalyzed hydrogenation of α,β-unsaturated ketones containing a hydroxyaryl (phenolic) substituent in the β-position. The developed hydrogenation procedure was used to synthesize natural compounds of the phenylpropane series and their structural analogs.
- Published
- 2017
68. Iridium-catalyzed asymmetric hydrogenation of cyclic iminium salts
- Author
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Haifeng Du, Yong-Gui Zhou, Lei Shi, Guang-Shou Feng, Yue Ji, and Mu-Wang Chen
- Subjects
010405 organic chemistry ,Chemistry ,Organic Chemistry ,Asymmetric hydrogenation ,Enantioselective synthesis ,Noyori asymmetric hydrogenation ,Iminium ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Catalysis ,Organic chemistry ,Reactivity (chemistry) ,Iridium ,Anion binding - Abstract
An enantioselective hydrogenation of cyclic iminium salts has been successfully realized by employing [Ir(COD)Cl]2 and chiral diphosphine ligands as catalyst, furnishing chiral N-alkyl tetrahydroisoquinolines and N-alkyl tetrahydro-β-carbolines with up to 96% ee and 88% ee, respectively. The hydrogenation provides a direct, simple and efficient protocol toward chiral tertiary amines. Meanwhile, asymmetric hydrogenation at the gram scale was also conducted smoothly without loss of reactivity and enantioselectivity.
- Published
- 2017
69. Theoretical understanding on the selectivity of acrolein hydrogenation over silver surfaces: the non-Horiuti–Polanyi mechanism is the key
- Author
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Bo Yang and Kaili Wang
- Subjects
chemistry.chemical_classification ,Hydrogen ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Photochemistry ,Heterogeneous catalysis ,01 natural sciences ,Aldehyde ,Enol ,Catalysis ,Transition state ,0104 chemical sciences ,chemistry.chemical_compound ,chemistry ,0210 nano-technology ,Selectivity - Abstract
Chemoselective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols is not only an important reaction in the chemical industry but also a good model system to understand the catalytic selectivity in heterogeneous catalysis. In the current work, the selectivity of partial hydrogenation of acrolein (C3H4O), the simplest α,β-unsaturated aldehyde, is investigated employing density functional theory (DFT) calculations. Two hydrogenation mechanisms, namely the Horiuti–Polanyi mechanism and the non-Horiuti–Polanyi mechanism, are employed to study the partial hydrogenation of acrolein over Ag(111), Ag(100), Ag(211) and Ag(111)-mono surfaces. It is found that the hydrogenation of C3H4O to C3H5O at the terminal carbon and oxygen atoms follows the non-Horiuti–Polanyi mechanism in which C3H4O reacts with hydrogen molecules directly over all the silver surfaces studied, whilst atomic hydrogen is the active hydrogen species for the hydrogenation of C3H5O to C3H6O. Subsequently, the selectivities between partial hydrogenation products, i.e. propenol, propanal and enol, over silver surfaces with different morphologies are compared by calculating the energy difference between the rate-determining transition states. We find that the selectivity of propenol formation increases with the coordination number of surface silver atoms, which is in good agreement with the trend of selectivities obtained experimentally. It is also interesting to find that the selectivity trend obtained based solely upon the Horiuti–Polanyi mechanism for the hydrogenation of C3H4O to C3H5O and C3H5O to C3H6O cannot explain the experimental results. In other words, the non-Horiuti–Polanyi mechanism is able to give a more reasonable explanation for the selectivity trend observed experimentally than the normally used Horiuti–Polanyi mechanism in heterogeneous catalysis. Our work highlights the significance of the non-Horiuti–Polanyi mechanism in understanding heterogeneous catalytic hydrogenation reactions.
- Published
- 2017
70. Hydrogenation of o-cresol on platinum catalyst: Catalytic experiments and first-principles calculations
- Author
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Friederike C. Jentoft, Sanwu Wang, Yaping Li, Zhimin Liu, Wenhua Xue, and Steven P. Crossley
- Subjects
Chemistry ,Ab initio ,General Physics and Astronomy ,Noyori asymmetric hydrogenation ,02 engineering and technology ,Surfaces and Interfaces ,General Chemistry ,Cresol ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,Hydrogen atom abstraction ,Ring (chemistry) ,Photochemistry ,01 natural sciences ,Intermediate product ,0104 chemical sciences ,Surfaces, Coatings and Films ,Catalysis ,Ab initio quantum chemistry methods ,medicine ,0210 nano-technology ,medicine.drug - Abstract
Catalytic experiments were performed for the hydrogenation of o-cresol in n-dodecane over a platinum catalyst. Batch reactions analyzed with an in-situ ATR IR probe suggest that the hydrogenation results in the formation of the final product, 2-methyl-cyclohexanol, with 2-methyl-cyclohexanone as the intermediate product. Ab initio density-functional theory was employed to investigate the atomic-scale mechanism of o-cresol hydrogenation on the Pt(111) surface. The formation of 2-methyl-cyclohexanone was found to involve two steps. The first step is a hydrogen abstraction, that is, the H atom in the hydroxyl group migrates to the Pt surface. The second step is hydrogenation, that is, the pre-existing H atoms on Pt react with the carbon atoms in the aromatic ring. On the other hand, 2-methyl-cyclohexanonol may be produced through two paths, with activation energies slightly greater than that for the formation of 2-methyl-cyclohexanone. One path involves direct hydrogenation of the aromatic ring. Another path involves three steps, with the partial hydrogenation of the ring as the first step, hydrogen abstraction of the OH group as the second, and hydrogenation of remaining C atoms and the O atom the last.
- Published
- 2017
71. Asymmetric synthesis of 4-aryl-1,2,5-thiadiazolidin-3-one 1,1-dioxides via Pd-catalyzed hydrogenation of cyclic ketimines
- Author
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Zhou-Hao Zhu, Meng-Lin Chen, and Guo-Fang Jiang
- Subjects
010405 organic chemistry ,Aryl ,Organic Chemistry ,Asymmetric hydrogenation ,Enantioselective synthesis ,Noyori asymmetric hydrogenation ,Nanotechnology ,Optically active ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Combinatorial chemistry ,0104 chemical sciences ,Catalysis ,chemistry.chemical_compound ,chemistry ,Physical and Theoretical Chemistry - Abstract
An efficient access to optically active sulfahydantoins, 4-aryl-1,2,5-thiadiazolidin-3-one 1,1-dioxides, was developed through palladium-catalyzed asymmetric hydrogenation of the corresponding cyclic N-sulfonylketimines with up to 98% ee.
- Published
- 2017
72. Rh-Catalyzed Asymmetric Hydrogenation of 1,2-Dicyanoalkenes
- Author
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Guohua Hou, Meina Li, Guofu Zi, and Duanyang Kong
- Subjects
010405 organic chemistry ,Chemistry ,Organic Chemistry ,Asymmetric hydrogenation ,Enantioselective synthesis ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,010402 general chemistry ,01 natural sciences ,Combinatorial chemistry ,0104 chemical sciences ,Rhodium ,Catalysis - Abstract
A highly efficient enantioselective hydrogenation of 1,2-dicyanoalkenes catalyzed by the complex of rhodium and f-spiroPhos has been developed. A series of 1,2-dicyanoalkenes were successfully hydrogenated to the corresponding chiral 1,2-dicyanoalkanes under mild conditions with excellent enantioselectivities (up to 98% ee). This methodology provides efficient access to the asymmetric synthesis of chiral diamines.
- Published
- 2016
73. Catalytic Transfer Hydrogenation of Furfural into Furfuryl Alcohol over Magnetic γ-Fe2O3@HAP Catalyst
- Author
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Fan Wang and Zehui Zhang
- Subjects
Green chemistry ,integumentary system ,Hydrogen ,010405 organic chemistry ,Renewable Energy, Sustainability and the Environment ,General Chemical Engineering ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,Alcohol ,General Chemistry ,010402 general chemistry ,Transfer hydrogenation ,Furfural ,01 natural sciences ,0104 chemical sciences ,Furfuryl alcohol ,Catalysis ,chemistry.chemical_compound ,chemistry ,Environmental Chemistry ,Organic chemistry - Abstract
Catalytic transfer hydrogenation of the C═O bond has been considered to be one of the most important processes for the synthesis of fuels and chemicals. In this study, we have developed a metal-free transfer hydrogenation of furfural into furfuryl alcohol and some other valuable carbonyl compounds into alcohols as the hydrogen donors. Hydroxyapatite-encapsulated magnetic γ-Fe2O3 (γ-Fe2O3@HAP) acted as a magnetic base to promote this transfer hydrogenation with iso-propanol as the hydrogen donor. The catalytic performance of the γ-Fe2O3@HAP catalyst was greatly affected by the structure of alcohol. iso-Propanol was the best hydrogen donor for the transfer hydrogenation. In addition, the reaction temperature and the catalyst loading also affected this reaction. The highest yield of furfuryl alcohol reached 91.7% at a furfural conversion of 96.2%. Furthermore, this method was also useful for the transfer hydrogenation of other important carbonyl compounds into value-added chemicals and fuels. After the react...
- Published
- 2016
74. Ketone Asymmetric Hydrogenation Catalyzed by P-NH-P′ Pincer Iron Catalysts: An Experimental and Computational Study
- Author
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Robert H. Morris, Peter E. Sues, Jessica F. Sonnenberg, and Kai Y. Wan
- Subjects
chemistry.chemical_classification ,Ketone ,010405 organic chemistry ,Hydride ,Asymmetric hydrogenation ,Noyori asymmetric hydrogenation ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,Catalysis ,0104 chemical sciences ,3. Good health ,chemistry.chemical_compound ,chemistry ,Amide ,Alkoxide ,Organic chemistry ,Acetophenone - Abstract
Our group previously reported the development of iron carbonyl catalysts bearing chiral tridentate P–N–P′ ligands for the asymmetric hydrogenation of prochiral ketones in THF. An NMR study into the activation process identified the amine hydride alkoxide complexes Fe(P-NH-P′)(CO)(H)(OR1) with R1 = Me, tBu, or tAmyl and P-NH-P′ = PPh2CH2CH2NHCH2CH2PiPr2 or (S,S)-PPh2CHPhCHMeNHCH2CH2PCy2. These still required treatment with excess KOtBu and H2(g) to be catalytically active in THF. Both experimental methods and density functional theory (DFT) calculations were used to show that this treatment leads to the formation of a hydride amide complex Fe(P–N–P′)(CO)(H), which reacts with dihydrogen to form cis and trans dihydride complexes Fe(P-NH-P′)(CO)(H)2, identified by NMR spectroscopy. In the presence of KOtBu, NaOtBu, or KOtBu/2,2,2-cryptand and H2(g), these species are active for the catalytic hydrogenation of acetophenone, whereas in the absence of H2(g), inactive Fe(0) complexes are formed. Ketone hydrogenat...
- Published
- 2016
75. Third-Generation Amino Acid Furanoside-Based Ligands from <scp>d</scp> -Mannose for the Asymmetric Transfer Hydrogenation of Ketones: Catalysts with an Exceptionally Wide Substrate Scope
- Author
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Jèssica Margalef, Hans Adolfsson, Fredrik Tinnis, Montserrat Diéguez, Oscar Pàmies, and Tove Slagbrand
- Subjects
chemistry.chemical_classification ,010405 organic chemistry ,Ligand ,Substrate (chemistry) ,Noyori asymmetric hydrogenation ,Mannose ,chemistry.chemical_element ,General Chemistry ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,0104 chemical sciences ,Amino acid ,Catalysis ,Rhodium ,chemistry.chemical_compound ,chemistry ,Organic chemistry - Abstract
A modular ligand library of -amino acid hydroxyamides and thioamides was prepared from 10 different N-tert-butyloxycarbonyl-protected -amino acids and three different amino alcohols derived from 2, ...
- Published
- 2016
76. Coupling Synergetic Effect between Ruthenium and Ruthenium Oxide with Size Effect of Ruthenium Particles on Ketone Catalytic Hydrogenation
- Author
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Binghui Chen, Dan Li, Jinbao Zheng, Yang Zhao, Lei Zhang, and Nuowei Zhang
- Subjects
chemistry.chemical_classification ,Ketone ,Organic Chemistry ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Photochemistry ,01 natural sciences ,Catalysis ,Ruthenium oxide ,0104 chemical sciences ,Ruthenium ,Inorganic Chemistry ,Coupling (electronics) ,chemistry ,Physical and Theoretical Chemistry ,0210 nano-technology ,Catalytic hydrogenation - Published
- 2016
77. Colloidal and nanosized catalysts in organic synthesis: XV. Gas-phase hydrogenation of alkenes catalyzed by supported nickel nanoparticles
- Author
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A. O. Panov, P. M. Shirkhanyan, V. M. Mokhov, Yu. V. Popov, D. N. Nebykov, K. V. Shcherbakova, A. A. Dontsova, and S. E. Latyshova
- Subjects
Diene ,Hydrogen ,010405 organic chemistry ,Silica gel ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,General Chemistry ,010402 general chemistry ,Photochemistry ,01 natural sciences ,0104 chemical sciences ,Catalysis ,chemistry.chemical_compound ,Nickel ,chemistry ,Organic synthesis ,Zeolite - Abstract
Gas-phase hydrogenation of alkenes and their derivatives, catalyzed by nickel nanoparticles supported on zeolite or silica gel support occurs at 150–250°С and an atmospheric hydrogen pressure and results in a high conversion. The selectivity of the hydrogenation depends on the amount of hydrogen: at a low diene (triene)–hydrogen ratio, selective hydrogenation of one multiple bond in the substrate is possible.
- Published
- 2016
78. A Ferrocenyl-Benzo-Fused Imidazolylidene Complex of Ruthenium as Redox-Switchable Catalyst for the Transfer Hydrogenation of Ketones and Imines
- Author
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Macarena Poyatos, Eduardo Peris, and Susana Ibáñez
- Subjects
Tetrafluoroborate ,010405 organic chemistry ,Chemistry ,Organic Chemistry ,Cationic polymerization ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,010402 general chemistry ,Transfer hydrogenation ,Photochemistry ,01 natural sciences ,Redox ,Catalysis ,0104 chemical sciences ,Ruthenium ,Inorganic Chemistry ,chemistry.chemical_compound ,Polymer chemistry ,Cobaltocene ,Physical and Theoretical Chemistry - Abstract
A ferrocenyl-benzo-fused imidazolylidene complex of RuII was prepared and fully characterized. In the presence of acetylferrocenium tetrafluoroborate this complex can be oxidized to generate a complex with a cationic ligand. The neutral complex can be recovered by reducing the oxidized cationic compound with cobaltocene. The activity of the neutral and oxidized complexes was tested in the transfer hydrogenation of ketones and imines, using isopropyl alcohol as the hydrogen source. The neutral complex is very active in the reduction of all tested substrates, whereas the oxidized species shows low activity in the reduction of ketones. The rate of the reduction of hexaphenone could be modulated by addition of subsequent amounts of oxidant and reductant. The addition of acetylferrocenium tetrafluoroborate caused a decrease in the catalytic activity, whereas the addition of cobaltocene restored the activity. The catalytic activity shown by both catalysts in the reduction of N-benzylideneaniline was similar.
- Published
- 2016
79. Heterogeneous Metal-Free Hydrogenation over Defect-Laden Hexagonal Boron Nitride
- Author
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Natalia S. Parra, Omar K. Farha, Rachel A. Penabade, Talat S. Rahman, Richard G. Blair, David J. Nash, James K. Harper, Maral Aminpour, Zhanyong Li, Kyle E. Giesler, Duy Le, and David T. Restrepo
- Subjects
Materials science ,010405 organic chemistry ,General Chemical Engineering ,Inorganic chemistry ,Cyclohexene ,Noyori asymmetric hydrogenation ,Hexagonal boron nitride ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Article ,0104 chemical sciences ,Catalysis ,lcsh:Chemistry ,Propene ,chemistry.chemical_compound ,lcsh:QD1-999 ,chemistry ,Metal free ,Desorption ,Octadecene - Abstract
Catalytic hydrogenation is an important process used for the production of everything from foods to fuels. Current heterogeneous implementations of this process utilize metals as the active species. Until recently, catalytic heterogeneous hydrogenation over a metal-free solid was unknown; implementation of such a system would eliminate the health, environmental, and economic concerns associated with metal-based catalysts. Here, we report good hydrogenation rates and yields for a metal-free heterogeneous hydrogenation catalyst as well as its unique hydrogenation mechanism. Catalytic hydrogenation of olefins was achieved over defect-laden h-BN (dh-BN) in a reactor designed to maximize the defects in h-BN sheets. Good yields (>90%) and turnover frequencies (6 × 10–5–4 × 10–3) were obtained for the hydrogenation of propene, cyclohexene, 1,1-diphenylethene, (E)- and (Z)-1,2-diphenylethene, octadecene, and benzylideneacetophenone. Temperature-programmed desorption of ethene over processed h-BN indicates the formation of a highly defective structure. Solid-state NMR (SSNMR) measurements of dh-BN with high and low propene surface coverages show four different binding modes. The introduction of defects into h-BN creates regions of electronic deficiency and excess. Density functional theory calculations show that both the alkene and hydrogen-bond order are reduced over four specific defects: boron substitution for nitrogen (BN), vacancies (VB and VN), and Stone–Wales defects. SSNMR and binding-energy calculations show that VN are most likely the catalytically active sites. This work shows that catalytic sites can be introduced into a material previously thought to be catalytically inactive through the production of defects.
- Published
- 2016
80. Domino Methylenation/Hydrogenation of Aldehydes and Ketones by Combining Matsubara's Reagent and Wilkinson's Catalyst
- Author
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Kevin Gervais, Alejandro Perez-Luna, Olivier Jackowski, Raoudha Abderrahim, Radhouan Maazaoui, Fabrice Chemla, Franck Ferreira, and María Pin-Nó
- Subjects
010405 organic chemistry ,Chemistry ,Organic Chemistry ,Noyori asymmetric hydrogenation ,010402 general chemistry ,01 natural sciences ,Domino ,Wilkinson's catalyst ,0104 chemical sciences ,chemistry.chemical_compound ,Cascade reaction ,Reagent ,Organic chemistry ,Domino process ,Physical and Theoretical Chemistry ,Chemoselectivity ,Methyl group - Abstract
The methylenation/hydrogenation cascade reaction of aldehydes or ketones through a domino process involving two ensuing steps in a single pot is realized. The compatibility of Matsubara's reagent and Wilkinson's complex give a combination that allows, under dihydrogen, the transformation of a carbonyl function into a methyl group. This new method is suitable to introduce an ethyl motif from aromatic and aliphatic aldehydes with total chemoselectivity and total retention of α-stereochemical purity. The developed procedure is also extended to the introduction of methyl groups from ketones.
- Published
- 2016
81. Low temperature CO2 hydrogenation to alcohols and hydrocarbons over Mo2C supported metal catalysts
- Author
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Saemin Choi, Yuan Chen, and Levi T. Thompson
- Subjects
Inorganic chemistry ,Noyori asymmetric hydrogenation ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Solvent ,chemistry.chemical_compound ,chemistry ,High surface area ,Methanol ,Metal catalyst ,Physical and Theoretical Chemistry ,0210 nano-technology - Abstract
A series of M/Mo2C (M = Cu, Pd, Co and Fe) were synthesized and evaluated for CO2 hydrogenation at 135–200 °C in liquid 1,4-dioxane solvent. The Mo2C served as both a support and a co-catalyst for CO2 hydrogenation, exhibiting turnover frequencies of 0.6 × 10−4 and 20 × 10−4 s−1 at 135 and 200 °C, respectively. Methanol was the major product at 135 °C, while CH3OH, C2H5OH, and C2+ hydrocarbons were produced at 200 °C. The addition of Cu and Pd onto the high surface area Mo2C enhanced the production of CH3OH, while Co and Fe enhanced the production of C2+ hydrocarbons. Results for CO2, CO, and CH3OH hydrogenation experiments suggested that CO2 was the primary source for CH3OH while CO was the intermediate to hydrocarbons during CO2 hydrogenation. Characterization of the spent M/Mo2C catalysts revealed very little change in the surface and bulk chemistries and structures, indicating their stability in the liquid environment.
- Published
- 2016
82. Hydrogenation of Carbonyl Derivatives with a Well-Defined Rhenium Precatalyst
- Author
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Thierry Roisnel, Jean-Baptiste Sortais, Duo Wei, Christophe Darcel, Eric Clot, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), We thank the Centre National de la Recherche Scientifique(CNRS),the Universit8 de Rennes 1, and Fonds Europ8ens de D8-veloppementEconomique R8gion al (FEDER) for fundin g., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
- Subjects
Reaction mechanism ,ketones ,010405 organic chemistry ,Ligand ,[SDV]Life Sciences [q-bio] ,Organic Chemistry ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,rhenium ,Rhenium ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,Catalysis ,0104 chemical sciences ,Inorganic Chemistry ,reaction mechanisms ,chemistry ,density functional calculations ,Organic chemistry ,Carbonyl derivatives ,hydrogenation ,Physical and Theoretical Chemistry - Abstract
International audience; The first efficient and general rhenium-catalyzed hydrogenation of carbonyl derivatives was developed. The key to the success of the reaction was the use of a well-defined rhenium complex bearing a tridentate diphosphinoamino ligand as the catalyst (0.5 mol %) at 70 °C in the presence of H2 (30 bar). The mechanism of the reaction was investigated by DFT(PBE0-D3) calculations.
- Published
- 2016
83. Attraction versus Repulsion in Rhodium-Catalyzed Asymmetric Hydrogenation
- Author
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Ilya D. Gridnev
- Subjects
chemistry.chemical_classification ,010405 organic chemistry ,Organic Chemistry ,Asymmetric hydrogenation ,Enantioselective synthesis ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,010402 general chemistry ,01 natural sciences ,Attraction ,Catalysis ,0104 chemical sciences ,Rhodium ,Inorganic Chemistry ,chemistry ,Computational chemistry ,Non-covalent interactions ,Organic chemistry ,Physical and Theoretical Chemistry - Published
- 2016
84. Molecularly Defined Manganese Pincer Complexes for Selective Transfer Hydrogenation of Ketones
- Author
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Matthias Beller, Kathrin Junge, Saravanakumar Elangovan, Anke Spannenberg, and Marc Perez
- Subjects
Manganese ,Hydrogen ,010405 organic chemistry ,General Chemical Engineering ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,Homogeneous catalysis ,Ketones ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Pincer movement ,General Energy ,chemistry ,Organometallic Compounds ,Environmental Chemistry ,Organic chemistry ,General Materials Science ,Hydrogenation ,Group 2 organometallic chemistry - Abstract
For the first time an easily accessible and well-defined manganese N,N,N-pincer complex catalyzes the transfer hydrogenation of a broad range of ketones with good to excellent yields. This cheap earth abundant-metal based catalyst provides access to useful secondary alcohols without the need of hydrogen gas. Preliminary investigations to explore the mechanism of this transformation are also reported.
- Published
- 2016
85. Catalytic Properties of a Novel Raney-Nickel Foam in the Hydrogenation of Benzene
- Author
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Andreas S. Wirth, Christoph Dörfelt, Matthias Albert, Robin Kolvenbach, and Klaus Köhler
- Subjects
inorganic chemicals ,010405 organic chemistry ,organic chemicals ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,Homogeneous catalysis ,General Chemistry ,010402 general chemistry ,Heterogeneous catalysis ,01 natural sciences ,Catalysis ,Raney nickel ,0104 chemical sciences ,chemistry.chemical_compound ,Nickel ,chemistry ,otorhinolaryngologic diseases ,Organic chemistry ,heterocyclic compounds ,Benzene ,Organometallic chemistry - Abstract
The catalytic properties of a novel Raney-Nickel mold were investigated in the liquid-phase hydrogenation of benzene and compared to commercially available Raney-Nickel. The novel Raney-Nickel catalyst showed similar activity as the commercial catalyst but facile product/catalyst separation. Furthermore, the novel Raney-Nickel catalyst is recyclable without loss in activity unlike the commercial nickel sponge.
- Published
- 2016
86. N,N-Dimethylformamide as Hydride Source in Nickel-Catalyzed Asymmetric Hydrogenation of α,β-Unsaturated Esters
- Author
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Siyu Guo and Jianrong Steve Zhou
- Subjects
010405 organic chemistry ,Hydride ,Organic Chemistry ,Asymmetric hydrogenation ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,Biochemistry ,0104 chemical sciences ,Catalysis ,Nickel ,chemistry ,Organic chemistry ,N dimethylformamide ,Physical and Theoretical Chemistry - Abstract
Asymmetric transfer hydrogenation of α,β-unsaturated esters is realized by using a nickel/bisphosphine catalyst and N,N-dimethylformamide (DMF) as the hydride source.
- Published
- 2016
87. Designing Vasicine-Derived Ligands and Their Application for Ruthenium-Catalyzed Transfer Hydrogenation Reactions in Water: Synthesis of Amines and Alcohols
- Author
-
Bikram Singh, Upendra Sharma, Sushila Sharma, Maheshwar S. Thakur, Vinod Bhatt, Onkar S. Nayal, Manoranjan Kumar, and Neeraj Kumar
- Subjects
010405 organic chemistry ,Chemistry ,Organic Chemistry ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,Reductive amination ,Vasicine ,0104 chemical sciences ,Ruthenium ,Catalysis ,chemistry.chemical_compound ,Organic chemistry ,Amine gas treating ,Vasicinone - Abstract
Six quinazoline ligands (i.e., 3–8) were synthesized by starting from vasicine and vasicinone, and their applications towards ruthenium-catalyzed transfer hydrogenation reactions were evaluated. The 3/[RuCl2(p-cymene)]2 catalytic system was assessed for its use in the ruthenium-catalyzed transfer hydrogenation reaction of aldehydes, ketones, and imines to give the corresponding alcohols and amines and also assessed for its use in the direct reductive amination of carbonyl compounds with anilines. The 3/[RuCl2(p-cymene)]2 catalytic system demonstrated good to excellent activity in water with sodium formate as the hydrogen source. Current studies have revealed that among all of the synthesized ligands, those that have secondary amine groups and a rigid backbone are more active towards transfer hydrogenation reactions of unsaturated compounds.
- Published
- 2016
88. Transition-Metal-Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation: Sustainable Chemistry to Access Bioactive Molecules
- Author
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Virginie Ratovelomanana-Vidal, Tahar Ayad, and Phannarath Phansavath
- Subjects
Green chemistry ,Biological Products ,010405 organic chemistry ,Chemistry ,General Chemical Engineering ,Asymmetric hydrogenation ,Enantioselective synthesis ,Total synthesis ,Noyori asymmetric hydrogenation ,Stereoisomerism ,General Chemistry ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,Biochemistry ,Catalysis ,0104 chemical sciences ,Transition metal ,Metals, Heavy ,Transition Elements ,Materials Chemistry ,Organic chemistry ,Hydrogenation - Abstract
Over the last few decades, the development of new and highly efficient synthetic methods to obtain chiral compounds has become an increasingly important and challenging research area in modern synthetic organic chemistry. In this account, we review recent work from our laboratory toward the synthesis of valuable chiral building blocks through transition-metal-catalyzed asymmetric hydrogenation and transfer hydrogenation of C=O, C=N and C=C bonds. Application to the synthesis of biologically relevant products is also described.
- Published
- 2016
89. Selective N-cycle hydrogenation of quinolines with sodium borohydride in aqueous media catalyzed by hectorite-supported ruthenium nanoparticles
- Author
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Georg Süss-Fink, Diego Carnevale, and Bing Sun
- Subjects
010405 organic chemistry ,Hydride ,Organic Chemistry ,Quinoline ,Inorganic chemistry ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,Biochemistry ,0104 chemical sciences ,Catalysis ,Ruthenium ,Inorganic Chemistry ,chemistry.chemical_compound ,Sodium borohydride ,chemistry ,Polymer chemistry ,Materials Chemistry ,Hectorite ,Physical and Theoretical Chemistry ,Isoquinoline - Abstract
A new catalyst containing metallic ruthenium nanoparticles intercalated in hectorite (nanoRu′@hectorite) was found to catalyze the reduction of quinoline and quinoline derivatives by NaBH4 in aqueous solution to give selectively the corresponding 1,2,3,4-tetrahydroquinolines (N-cycle hydrogenation). In most cases the reaction can be done under mild conditions (25–60 °C) without pressure equipment, conversion and selectivity being superior to 99%. In the case of sterically hindered derivatives, the reaction can be done in a pressure vessel under self-generated pressure (up to 9 bar). Isoquinoline and quinoxalines also undergo selective N-cycle hydrogenation, but 2-phenyl-quinoline is hydrogenated to give 2-phenyl-5,6,7,8-tetrahydroquinoline (C-cycle hydrogenation). Isotope labeling experiments combined with semi-empirical calculations of the electrostatic potentials support a heterolytic hydrogenation mechanism involving a hydride from NaBH4 and a proton from H2O. The catalyst nanoRu′@hectorite can be recycled and reused.
- Published
- 2016
90. Enantioselective Hydrogenation of Ketones Catalyzed by Chiral Cobalt Complexes Containing PNNP Ligand
- Author
-
Dong Zhang, Zhi-Wei Lin, Jing-Xing Gao, Zan-Bin Wei, Yan-Yun Li, and En-Ze Zhu
- Subjects
inorganic chemicals ,010405 organic chemistry ,Ligand ,Organic Chemistry ,Asymmetric hydrogenation ,Enantioselective synthesis ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,law.invention ,Catalysis ,chemistry ,law ,Yield (chemistry) ,Polymer chemistry ,Organic chemistry ,Electron paramagnetic resonance ,Cobalt - Abstract
Novel chiral cobalt complexes containing a PNNP-type ligand were synthesized using a straightforward method. The structures of the cobalt complexes have been fully characterized by X-ray crystallography, high resolution mass spectrometry (HRMS), and electron paramagnetic resonance (EPR). Using H2 as the hydrogen source, the cobalt-catalyzed asymmetric hydrogenation of various ketones was investigated, and the corresponding chiral alcohols were afforded with up to 99 % yield and 95 % ee. To the best of our knowledge, this is the first example of a cobalt-catalyzed enantioselective hydrogenation of ketones with molecular hydrogen.
- Published
- 2016
91. Synthesis of aminomethyl quinazoline based ruthenium (II) complex and its application in asymmetric transfer hydrogenation under mild conditions
- Author
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Sabri Ulukanli, Sedat Emir, Ahmet Agac, Irfan Sahin, Semistan Karabuga, and Idris Karakaya
- Subjects
010405 organic chemistry ,Ligand ,Chemistry ,Organic Chemistry ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,Phenylalanine ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,Biochemistry ,Medicinal chemistry ,0104 chemical sciences ,Catalysis ,Ruthenium ,Inorganic Chemistry ,chemistry.chemical_compound ,Materials Chemistry ,Quinazoline ,Organic chemistry ,Reactivity (chemistry) ,Physical and Theoretical Chemistry - Abstract
The new chiral aminomethyl quinazoline (amq) type ligand derived from L-phenylalanine was synthesized and coordinated with [RuCl2(PPh3) dppb] to obtain ruthenium(II) complex. This catalyst displayed considerable reactivity (up to 97% ee and 99% conversion) in the asymmetric transfer hydrogenation of ketones using 2-propanol as a hydrogen source in the presence of NaOiPr. (C) 2016 Elsevier B.V. All rights reserved.
- Published
- 2016
92. Enantioselective transfer hydrogenation of various ketones with novel efficient iridium(III) ferrocenyl-phosphinite catalysts
- Author
-
Murat Aydemir and Nermin Meriç
- Subjects
Hydrogen ,Phosphinite ,010405 organic chemistry ,Chemistry ,Organic Chemistry ,Enantioselective synthesis ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,Homogeneous catalysis ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,Biochemistry ,0104 chemical sciences ,Catalysis ,Inorganic Chemistry ,chemistry.chemical_compound ,Materials Chemistry ,Organic chemistry ,Iridium ,Physical and Theoretical Chemistry - Abstract
The asymmetric reduction of prochiral ketones is a pivotal reaction for the preparation of chiral alcohols which form an extremely important class of intermediates for fine chemicals and pharmaceuticals. Especially, iridium-based asymmetric reduction of ketones to enantiomerically enriched alcohols has recently attracted important attention by a number of research groups and interest in this area is growing. Therefore, a series of novel neutral mononuclear iridium(III) ferrocenyl-phosphinite complexes have been prepared and applied in the iridium(III)-catalyzed asymmetric transfer hydrogenation (ATH) of ketones to give corresponding secondary alcohols with outstanding enantioselectivities and reactivities using 2-propanol as the hydrogen source (up to 99% ee and 99% conversion). It was seen that the substituents on the backbone of the ligands resulted in a significant effect on both the activity and % enantioselectivity. Furthermore, the structural elucidation of the complexes was carried out by elemental analysis, IR and multi-nuclear NMR spectroscopic data.
- Published
- 2016
93. Catalytic hydrogenation of condensation product of furfural with cyclopentanone using molecular hydrogen and formic acid as hydrogen donor
- Author
-
Tibor Liptaj, Katarína Fulajtárová, Tomáš Soták, Naďa Prónayová, and Milan Hronec
- Subjects
inorganic chemicals ,Hydrogen ,010405 organic chemistry ,Formic acid ,General Chemical Engineering ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,General Chemistry ,010402 general chemistry ,Furfural ,Cyclopentanone ,Transfer hydrogenation ,Photochemistry ,01 natural sciences ,0104 chemical sciences ,Catalysis ,chemistry.chemical_compound ,chemistry ,mental disorders ,Organic chemistry ,Palladium - Abstract
In this study we report the catalytic hydrogenation of biomass-derived condensation product of furfural and cyclopentanone (F2C) with molecular hydrogen and formic acid as a source of hydrogen. Supported palladium catalysts have been used for hydrogenation and decomposition of formic acid. Complete conversion of F2C and higher than 90% yield of C15 bis-cyclic ether were achieved over 5% Pd/C catalyst at mild reaction conditions and short reaction time by catalytic hydrogenation with molecular hydrogen. Despite high activity of palladium catalysts in F2C hydrogenation with molecular hydrogen and also decomposition of formic acid to hydrogen these catalysts exhibited significantly lower activity in transfer hydrogenation. A dramatic activity loss in transfer hydrogenation may be caused by a strong adsorption of formic acid on Pd sites which hinders the competitive adsorption of F2C molecules solvated with formic acid.
- Published
- 2016
94. Alkene hydrogenation over palladium supported on a carbon–silica material
- Author
-
E. G. Galkin, P. P. Talipova, V. A. Dokichev, S. A. Grabovskii, N. Z. Baibulatova, and T. I. Akchurin
- Subjects
inorganic chemicals ,chemistry.chemical_classification ,010405 organic chemistry ,Alkene ,Substituent ,chemistry.chemical_element ,Noyori asymmetric hydrogenation ,General Chemistry ,010402 general chemistry ,Heterogeneous catalysis ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Computer Science Applications ,Reaction rate ,chemistry.chemical_compound ,chemistry ,Modeling and Simulation ,Organic chemistry ,Carbon ,Palladium - Abstract
Palladium catalysts supported on a carbon–silica material were synthesized. Hydrogenation by molecular hydrogen was studied in the presence of straight-chain and cyclic olefins. As distinct from what is observed for olefins having a phenyl substituent, for aliphatic alkenes the reaction rate decreases with an increasing conversion due to the accumulation of hydrogenation products. The synthesized palladium catalysts show a higher hydrogenation activity than Pd/C.
- Published
- 2016
95. Transfer hydrogenation reactions catalyzed by chiral half-sandwich Ruthenium complexes derived from Proline
- Author
-
Ashoka G. Samuelson and Arun Kumar
- Subjects
inorganic chemicals ,010405 organic chemistry ,Chemistry ,Hydride ,Diastereomer ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,General Chemistry ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,0104 chemical sciences ,Ruthenium ,chemistry.chemical_compound ,Diamine ,Polymer chemistry ,Benzyl group ,Phenyl group ,Organic chemistry - Abstract
Chiral ruthenium half-sandwich complexes were prepared using a chelating diamine made from proline with a phenyl, ethyl, or benzyl group, instead of hydrogen on one of the coordinating arms. Three of these complexes were obtained as single diastereoisomers and their configuration identified by X-ray crystallography. The complexes are recyclable catalysts for the reduction of ketones to chiral alcohols in water. A ruthenium hydride species is identified as the active species by NMR spectroscopy and isotopic labelling experiments. Maximum enantio-selectivity was attained when a phenyl group was directly attached to the primary amine on the diamine ligand derived from proline.
- Published
- 2016
96. Steric and Electronic Effects of Bidentate Phosphine Ligands on Ruthenium(II)-Catalyzed Hydrogenation of Carbon Dioxide
- Author
-
Li Dang, Pan Zhang, and Shao-Fei Ni
- Subjects
inorganic chemicals ,Steric effects ,Denticity ,010405 organic chemistry ,Chemistry ,Ligand ,Organic Chemistry ,Asymmetric hydrogenation ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,General Chemistry ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Biochemistry ,Medicinal chemistry ,0104 chemical sciences ,Ruthenium ,Electronic effect ,Isomerization - Abstract
The reactivity difference between the hydrogenation of CO2 catalyzed by various ruthenium bidentate phosphine complexes was explored by DFT. In addition to the ligand dmpe (Me2 PCH2 CH2 PMe2 ), which was studied experimentally previously, a more bulky diphosphine ligand, dmpp (Me2 PCH2 CH2 CH2 PMe2 ), together with a more electron-withdrawing diphosphine ligand, PN(Me) P (Me2 PCH2 N(Me) CH2 PMe2 ), have been studied theoretically to analyze the steric and electronic effects on these catalyzed reactions. Results show that all of the most favorable pathways for the hydrogenation of CO2 catalyzed by bidentate phosphine ruthenium dihydride complexes undergo three major steps: cis-trans isomerization of ruthenium dihydride complex, CO2 insertion into the Ru-H bond, and H2 insertion into the ruthenium formate ion. Of these steps, CO2 insertion into the Ru-H bond has the lowest barrier compared with the other two steps in each preferred pathway. For the hydrogenation of CO2 catalyzed by ruthenium complexes of dmpe and dmpp, cis-trans isomerization of ruthenium dihydride complex has a similar barrier to that of H2 insertion into the ruthenium formate ion. However, in the reaction catalyzed by the PN(Me) PRu complex, cis-trans isomerization of the ruthenium dihydride complex has a lower barrier than H2 insertion into the ruthenium formate ion. These results suggest that the steric effect caused by the change of the outer sphere of the diphosphine ligand on the reaction is not clear, although the electronic effect is significant to cis-trans isomerization and H2 insertion. This finding refreshes understanding of the mechanism and provides necessary insights for ligand design in transition-metal-catalyzed CO2 transformation.
- Published
- 2016
97. Advancement in Catalytic Asymmetric Hydrogenation of Ketones and Imines, and Development of Asymmetric Isomerization of Allylic Alcohols
- Author
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Takeshi Ohkuma and Noriyoshi Arai
- Subjects
Allylic rearrangement ,genetic structures ,General Chemical Engineering ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,Biochemistry ,isomerization ,Catalysis ,Materials Chemistry ,Organic chemistry ,heterocyclic compounds ,ruthenium ,010405 organic chemistry ,organic chemicals ,Asymmetric hydrogenation ,Enantioselective synthesis ,asymmetric catalysis ,General Chemistry ,iridium ,0104 chemical sciences ,Ruthenium ,chemistry ,Stereoselectivity ,hydrogenation ,Isomerization - Abstract
Catalytic asymmetric hydrogenation of ketones through the "metal-ligand cooperative mechanism" has been improved in terms of the efficiency, stereoselectivity, and scope of substrates by varying the arrangement of the catalyst structure and reaction conditions. Imino compounds are also smoothly converted to the optically active amines with appropriate catalysts. This type of catalyst exhibits excellent performance on the asymmetric isomerization of primary allylic alcohols into the optically active aldehydes. This personal account describes recent progress on these topics.
- Published
- 2016
98. Iron Group Hydrides in Noyori Bifunctional Catalysis
- Author
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Robert H. Morris
- Subjects
010405 organic chemistry ,Chemistry ,General Chemical Engineering ,Asymmetric hydrogenation ,Enantioselective synthesis ,Noyori asymmetric hydrogenation ,Homogeneous catalysis ,General Chemistry ,010402 general chemistry ,Transfer hydrogenation ,01 natural sciences ,Biochemistry ,Asymmetric induction ,0104 chemical sciences ,Catalysis ,chemistry.chemical_compound ,Materials Chemistry ,Organic chemistry ,Bifunctional - Abstract
This is an overview of the hydride-containing catalysts prepared in the Morris group for the efficient hydrogenation of simple ketones, imines, nitriles and esters and the asymmetric hydrogenation and transfer hydrogenation of prochiral ketones and imines. The work was inspired by and makes use of Noyori metal-ligand bifunctional concepts involving the hydride-ruthenium amine-hydrogen HRuNH design. It describes the synthesis and some catalytic properties of hydridochloro, dihydride and amide complexes of ruthenium and in one case, osmium, with monodentate, bidentate and tetradentate phosphorus and nitrogen donor ligands. The iron hydride that has been identified in a very effective asymmetric transfer hydrogenation process is also mentioned. The link between the HMNH structure and the sense of enantioinduction is demonstrated by use of simple transition state models.
- Published
- 2016
99. N-Heterocyclic Carbenes in Asymmetric Hydrogenation
- Author
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Daniel Paul, Dongbing Zhao, Frank Glorius, and Lisa Candish
- Subjects
010405 organic chemistry ,Chemistry ,Asymmetric hydrogenation ,Enantioselective synthesis ,Noyori asymmetric hydrogenation ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Catalysis ,0104 chemical sciences ,chemistry.chemical_compound ,Transition metal ,Atom economy ,Organic chemistry ,Stereoselectivity ,Carbene - Abstract
N-heterocyclic carbene (NHC)-metal complexes have become known as efficient catalysts for numerous transition metal catalyzed processes. An important application of many NHC-metal complexes is in the field of asymmetric catalysis, and this is achieved through the introduction of chiral information on the NHC ligands. Among the asymmetric transformations catalyzed by NHC-metal complexes is asymmetric hydrogenation, which is an attractive process for the synthesis of optically active compounds due to its high atom economy. However, to date, few chiral NHC-metal catalysts have been reported to be highly stereoselective for asymmetric hydrogenation. Over the past few years our group has made some significant breakthroughs within the field of asymmetric hydrogenation using chiral NHC catalysts. We have reported the NHC-Ru catalyzed asymmetric hydrogenation of a wide range of heterocyclic compounds with high regio- and enantioselectivity. The field of chiral NHC-metal complex catalyzed asymmetric hydrogenation ...
- Published
- 2016
100. Solvent-Regulated Asymmetric Hydrogenation of Quinoline Derivatives in Oligo(Ethylene Glycol)s through Host-Guest Interactions
- Author
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Ya Chen, Tian Li Wang, Guanghui Ouyang, Zhiyan Li, Qing-Hua Fan, and Yan-Mei He
- Subjects
animal structures ,010405 organic chemistry ,Organic Chemistry ,Quinoline ,Asymmetric hydrogenation ,technology, industry, and agriculture ,Enantioselective synthesis ,Noyori asymmetric hydrogenation ,chemistry.chemical_element ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Biochemistry ,0104 chemical sciences ,Catalysis ,Ruthenium ,chemistry.chemical_compound ,chemistry ,Polymer chemistry ,Organic chemistry ,Ethylene glycol ,Triethylene glycol - Abstract
The asymmetric hydrogenation of quinolines in oligo(ethylene glycol)s (OEGs) and poly(ethylene glycol)s (PEGs) with chiral cationic ruthenium diamine complexes has been investigated. Interestingly, in liquid PEGs or long-chain OEGs, the Ru catalysts lost their reactivity. Upon the addition of a little MeOH, the hydrogenation of quinoline was switched "ON". Evidence from mass spectrometry and control experiments revealed that encapsulation of the quinolinium salt by PEG or long-chain OEG molecules through supramolecular interactions is possibly the main reason for such a switchable hydrogenation reaction. Moreover, the asymmetric hydrogenation of 2-substituted quinoline derivatives was achieved in triethylene glycol (3-OEG), thereby affording 1,2,3,4-tetrahydroquinolines with excellent reactivities and enantioselectivities (up to 99 % ee). Furthermore, the Ru catalyst could be readily recycled for both pure 3-OEG and biphasic 3-OEG/n-hexane systems without a clear loss of reactivity and enantioselectivity.
- Published
- 2016
Catalog
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