- Effect of solvent in the hydrogenation of acetophenone catalyzed by Pd/S-DVB
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A solvent effect was found in the hydrogenation of acetophenone catalyzed by a new Pd/S-DVB catalyst, immobilized on a styrene (S)/divinylbenzene (DVB) copolymer containing phosphinic groups. The porous structure of the catalyst was characterized by a specific surface area of 94.7 m2g?1. The presence of Pd(ii) and Pd(0) in Pd/S-DVB was evidenced by XPS and TEM. Pd/S-DVB catalyzes the hydrogenation of acetophenone (APh) to 1-phenylethanol (PhE) and ethylbenzene (EtB). The highest conversion of APh was obtained in methanol (MeOH) and in 2-propanol (2-PrOH), while in water it was lower. The conversion of APh correlates well with the hydrogen-bond-acceptance (HBA) capacity of the solvent. However, in all binary mixtures of alcohol and water the APh conversion and the yield of products significantly decreased. The observed inhibiting effect can be explained by the microheterogeneity of these mixtures and the blocking of the catalyst surface restricting access of the substrates to the Pd centers.
- Bereta, Tomasz,Mieczyńska, Ewa,Ronka, Sylwia,Tylus, W?odzimierz,Trzeciak, Anna M.
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p. 5023 - 5028
(2021/03/26)
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- Highly selective hydrogenation of aromatic ketones to alcohols in water: effect of PdO and ZrO2
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Pd/ZrO2and PdO/ZrO2composites, containing Pd or PdO nanoparticles, were prepared using an original one-step methodology. These nanocomposites catalyze the hydrogenation of acetophenone (AP) at 1 bar and 10 bar of H2in an aqueous solution. Compared to unsupported Pd or PdO nanoparticles, a remarkable increase in their activity was achieved as a result of interaction with zirconia. An unsupported PdO hydrogenated AP mainly to ethylbenzene (EB), while excellent regioselectivity towards 1-phenylethanol (PE) was obtained with PdO/ZrO2and it was preserved during recycling. Similarly, regioselectivity to PE was higher with Pd/ZrO2compared to unsupported Pd NPs. PdO and zirconia resulted in high selectivity to alcohols in the hydrogenation of substituted acetophenones.
- Alsalahi, W.,Trzeciak, A. M.,Tylus, W.
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p. 10386 - 10393
(2021/08/09)
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- Dynamic Kinetic Resolution of Alcohols by Enantioselective Silylation Enabled by Two Orthogonal Transition-Metal Catalysts
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A nonenzymatic dynamic kinetic resolution of acyclic and cyclic benzylic alcohols is reported. The approach merges rapid transition-metal-catalyzed alcohol racemization and enantioselective Cu-H-catalyzed dehydrogenative Si-O coupling of alcohols and hydrosilanes. The catalytic processes are orthogonal, and the racemization catalyst does not promote any background reactions such as the racemization of the silyl ether and its unselective formation. Often-used ruthenium half-sandwich complexes are not suitable but a bifunctional ruthenium pincer complex perfectly fulfills this purpose. By this, enantioselective silylation of racemic alcohol mixtures is achieved in high yields and with good levels of enantioselection.
- Oestreich, Martin,Seliger, Jan
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supporting information
p. 247 - 251
(2020/10/29)
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- Application of nitrogen-containing heterocyclic mercaptan cuprous compound in photocatalytic reaction of carbonyl compound
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The invention discloses an application of a nitrogen-containing heterocyclic mercaptan cuprous compound in a photocatalytic reaction of a carbonyl compound, relates to the technical field of application of photocatalysts; in particular, photocatalytic reduction reaction is carried out on the carbonyl compound by adopting the nitrogen-containing heterocyclic mercaptan cuprous compound as a photocatalyst to prepare an alcohol compound. The nitrogen-containing heterocyclic mercaptan cuprous compound is used as the photocatalyst for the photocatalytic reduction reaction of the carbonyl compound, visible light is successfully catalyzed to induce reduction of the carbonyl compound into the alcohol compound, the catalyst is low in price and good in catalytic effect, and the production cost can be reduced.
- -
-
Paragraph 0013; 0035-0036
(2021/06/06)
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- Pincerlike molybdenum complex and preparation method thereof, catalytic composition and application thereof, and alcohol preparation method
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The invention discloses a clamp-type molybdenum complex, a preparation method, a corresponding catalyst composition and application. The method comprises the steps: obtaining 9 molybdenum complexes with different structures through coordination reaction of 2-(substituent ethyl)-(5, 6, 7, 8-tetrahydroquinolyl) amine and a corresponding carbonyl molybdenum metal precursor; and catalyzing a ketone compound transfer hydrogenation reaction through a molybdenum complex to generate 40 alcohol compounds. The preparation method of the molybdenum complex is simple, high in yield and good in stability. For a transfer hydrogenation reaction of ketone, the molybdenum-based catalytic system has high catalytic activity and small molybdenum loading capacity, is used for production of aromatic and aliphatic alcohols, and has the advantages of simple method, small environmental pollution and high yield.
- -
-
Paragraph 0125-0130
(2021/08/11)
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- The solvent determines the product in the hydrogenation of aromatic ketones using unligated RhCl3as catalyst precursor
-
Alkyl cyclohexanes were synthesized in high selectivity via a combined hydrogenation/hydrodeoxygenation of aromatic ketones using ligand-free RhCl3 as pre-catalyst in trifluoroethanol as solvent. The true catalyst consists of rhodium nanoparticles (Rh NPs), generated in situ during the reaction. A range of conjugated as well as non-conjugated aromatic ketones were directly hydrodeoxygenated to the corresponding saturated cyclohexane derivatives at relatively mild conditions. The solvent was found to be the determining factor to switch the selectivity of the ketone hydrogenation. Cyclohexyl alkyl-alcohols were the products using water as a solvent.
- Bartling, Stephan,Chakrabortty, Soumyadeep,De Vries, Johannes G.,Kamer, Paul C. J.,Lund, Henrik,Müller, Bernd H.,Rockstroh, Nils
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p. 7608 - 7616
(2021/12/13)
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- Manganese-catalyzed homogeneous hydrogenation of ketones and conjugate reduction of α,β-unsaturated carboxylic acid derivatives: A chemoselective, robust, and phosphine-free in situ-protocol
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We communicate a user-friendly and glove-box-free catalytic protocol for the manganese-catalyzed hydrogenation of ketones and conjugated C[dbnd]C[sbnd]bonds of esters and nitriles. The respective catalyst is readily assembled in situ from the privileged [Mn(CO)5Br] precursor and cheap 2-picolylamine. The catalytic transformations were performed in the presence of t-BuOK whereby the corresponding hydrogenation products were obtained in good to excellent yields. The described system offers a brisk and atom-efficient access to both secondary alcohols and saturated esters avoiding the use of oxygen-sensitive and expensive phosphine-based ligands.
- Topf, Christoph,Vielhaber, Thomas
-
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- Ruthenium-p-cymene Complex Side-Wall Covalently Bonded to Carbon Nanotubes as Efficient Hybrid Transfer Hydrogenation Catalyst
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A half-sandwich ruthenium-p-cymene organometallic complex has been immobilized at Single Walled Carbon Nanotubes (SWNT) sidewalls through a stepwise covalent chemistry protocol. The introduction of amino groups by means of diazonium-chemistry protocols leads the grafting at the outer walls of the nanotubes. This hybrid material is active in the transfer hydrogenation of ketones to yield alcohols, using as hydrogen source 2-propanol. SWNT?NH2?Ru presents a broad scope, performing the reaction under aerobic conditions and can be recycled over 9 consecutive reaction runs without losing activity or leaching ruthenium out. Comparison of the activity with related homogeneous catalysts reveals an improved performance due to the covalent bond between the metal and the material, achieving turnover frequencies as high as 192774 h?1.
- Blanco, Matías,Cembellín, Sara,Agnoli, Stefano,Alemán, José
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p. 5156 - 5165
(2021/11/05)
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- Synthesis, Structure, and Catalytic Hydrogenation Activity of [NO]-Chelate Half-Sandwich Iridium Complexes with Schiff Base Ligands
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A series of N,O-coordinate iridium(III) complexes with a half-sandwich motif bearing Schiff base ligands for catalytic hydrogenation of nitro and carbonyl substrates have been synthesized. All iridium complexes showed efficient catalytic activity for the hydrogenation of ketones, aldehydes, and nitro-containing compounds using clean H2 as reducing reagent. The iridium catalyst displayed the highest TON values of 960 and 950 in the hydrogenation of carbonyl and nitro substrates, respectively. Various types of substrates with different substituted groups afforded corresponding products in excellent yields. All N,O-coordinate iridium(III) complexes 1-4 were well characterized by IR, NMR, HRMS, and elemental analysis. The molecular structure of complex 1 was further characterized by single-crystal X-ray determination.
- Lv, Wen-Rui,Li, Rong-Jian,Liu, Zhen-Jiang,Jin, Yan,Yao, Zi-Jian
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p. 8181 - 8188
(2021/05/26)
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- Selective C-alkylation Between Alcohols Catalyzed by N-Heterocyclic Carbene Molybdenum
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The first implementation of a molybdenum complex with an easily accessible bis-N-heterocyclic carbene ligand to catalyze β-alkylation of secondary alcohols via borrowing-hydrogen (BH) strategy using alcohols as alkylating agents is reported. Remarkably high activity, excellent selectivity, and broad substrate scope compatibility with advantages of catalyst usage low to 0.5 mol%, a catalytic amount of NaOH as the base, and H2O as the by-product are demonstrated in this green and step-economical protocol. Mechanistic studies indicate a plausible outer-sphere mechanism in which the alcohol dehydrogenation is the rate-determining step.
- Liu, Jiahao,Li, Weikang,Li, Yinwu,Liu, Yan,Ke, Zhuofeng
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supporting information
p. 3124 - 3128
(2021/09/20)
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- Cationic ruthenium(II)–NHC pincer complexes: Synthesis, characterisation and catalytic activity for transfer hydrogenation of ketones
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Cationic ruthenium pincer complexes, [Ru(CNC)(CO)(PPh3)Cl]X (CNC = 2,6-bis(1-methylimidazol-2-ylidene)-pyridine, X = Cl? [1a], PF6? [1b]), [Ru(CNC)(PPh3)2Cl]X (X = Cl? [2a], PF6? [2b]) and [Ru(CNC)(PPh3)2(H)]X (X = Cl? [3a], PF6? [3b]) with triphenylphosphine, CO and halides as coligands have been synthesised and characterised by 1H, 13C, 31P NMR, mass and single-crystal X-ray crystallography. The application of Ru complexes in the transfer hydrogenation of a wide range of ketones with 2-propanol as the hydrogen source is explored. The in situ transformations observed during the synthesis help understand and suggest a plausible mechanism via the hydride complex 3b. All complexes appear to be efficient catalyst precursors for transfer hydrogenation of ketones.
- Yadav, Dibya,Misra, Shilpi,Kumar, Dheeraj,Singh, Suryabhan,Singh, Amrendra K.
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- Postsynthetic Modification of Half-Sandwich Ruthenium Complexes by Mechanochemical Synthesis
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A mild and environmentally friendly method to synthesize half-sandwich ruthenium complexes through the Wittig reaction between an aldehyde-tagged half-sandwich ruthenium complex and phosphorus ylide mechanochemically is reported herein. The mechanochemical synthesis of valuable half-sandwich ruthenium complexes resulted in a fast reaction, good yield with simple workup, and the avoidance of harsh reaction conditions and organic solvents. The synthesized half-sandwich ruthenium complexes exhibited high catalytic activity for transfer hydrogenation of ketones using 2-propanol as the hydrogen source and solvent. Density functional theory was carried out to propose a mechanism for the transfer hydrogenation process. The modeling suggests the importance of the labile p-cymene ligand in modulating the reactivity of the catalyst.
- Jia, Wei-Guo,Zhi, Xue-Ting,Li, Xiao-Dong,Zhou, Jun-Peng,Zhong, Rui,Yu, Haibo,Lee, Richmond
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p. 4313 - 4321
(2021/05/04)
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- Half-sandwich ruthenium(II) complexes containing 4-substituted aniline derivatives: structural characterizations and catalytic properties in transfer hydrogenation of ketones
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Four half-sandwich Ru(II) complexes (1)–(4) with the general formulae [Ru(η6-p-cymene)(L)Cl2] were synthesized by the reaction of one equivalent of the Ru(II) p-cymene dimer with two equivalents of a p-substituted aniline derivative L (where L is p-methyl, p-isopropyl, p-methoxy, or p-hydroxy aniline). The structures of complexes (2)–(4) were determined by single-crystal X-ray diffraction studies. The structural analysis revealed piano-stool geometry at the Ru(II) ions which are coordinated to the η6-p-cymene, two chloride anions and the amine group of the aniline ligand. In the structure of (2)–(4), the coordinated chloride ions make intermolecular hydrogen bonding with the –NH2 group of an adjacent molecules (NH–Cl) resulting in hydrogen bond networks. The catalytic activities of the complexes in transfer hydrogenation of acetophenone were studied. Complex [Ru(η6-p-cymene)(p-methylaniline)Cl2] (1) showed the best catalytic performance in the transfer hydrogenation of acetophenone. The presence and positions of methyl and bromide groups on the acetophenone have an impact on the catalytic activity in transfer hydrogenation properties of the complex (1). Moreover, catalytic activity of the complex (1) is significantly higher in the transfers hydrogenation of cyclohexanone than 2-hexanone.
- Sad?k, Mean,Karabork, Muharrem,Sahin, Irfan,Kose, Muhammet
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p. 457 - 464
(2021/05/21)
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- Low-valence anionic α-diimine iron complexes: Synthesis, characterization, and catalytic hydroboration studies
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The synthesis of rare anionic heteroleptic and homoleptic α-diimine iron complexes is described. Heteroleptic BIAN (bis(aryl)iminoacenaphthene) complexes 1-[K([18]c-6)-(thf)0.5] and 2-[K([18]c-6)(thf)2] were synthesized by reduction of the [(BIAN)FeBr2] precursor complex using stoichiometric amounts of potassium graphite in the presence of the corresponding olefin. The electronic structure of these paramagnetic species was investigated by numerous spectroscopic analyses (NMR, EPR, 57Fe M?ssbauer, UV-vis), magnetic measurements (Evans NMR method, SQUID), and theoretical techniques (DFT, CASSCF). Whereas anion 1 is a low-spin complex, anion 2 consists of an intermediate-spin Fe(III) center. Both complexes are efficient precatalysts for the hydroboration of carbonyl compounds under mild reaction conditions. The reaction of bis(anthracene) ferrate(1-) gave the homoleptic BIAN complex 3-[K([18]c-6)(thf)], which is less catalytically active. The electronic structure was elucidated with the same techniques as described for complexes 1-[K([18]c-6)(thf)0.5] and 2-[K([18]c-6)(thf)2] and revealed an Fe(II) species in a quartet ground state.
- Bodensteiner, Michael,Coburger, Peter,Demeshko, Serhiy,Gawron, Martin,Maier, Thomas M.,Meyer, Franc,Wolf, Robert,de Bruin, Bas,van Leest, Nicolaas P.
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p. 16035 - 16052
(2020/11/20)
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- Capturing the Monomeric (L)CuH in NHC-Capped Cyclodextrin: Cavity-Controlled Chemoselective Hydrosilylation of α,β-Unsaturated Ketones
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The encapsulation of copper inside a cyclodextrin capped with an N-heterocyclic carbene (ICyD) allowed both to catch the elusive monomeric (L)CuH and a cavity-controlled chemoselective copper-catalyzed hydrosilylation of α,β-unsaturated ketones. Remarkably, (α-ICyD)CuCl promoted the 1,2-addition exclusively, while (β-ICyD)CuCl produced the fully reduced product. The chemoselectivity is controlled by the size of the cavity and weak interactions between the substrate and internal C?H bonds of the cyclodextrin.
- Bistri-Aslanoff, Olivia,Derat, Etienne,Leloux, Sébastien,Leyssens, Tom,Ménand, Micka?l,Meijide Suárez, Jorge,Riant, Olivier,Roland, Sylvain,Sollogoub, Matthieu,Xu, Guangcan,Zhang, Pinglu,Zhang, Yongmin
-
supporting information
p. 7591 - 7597
(2020/03/23)
-
- Efficient Transfer Hydrogenation of Ketones Catalyzed by a Phosphine-Free Cobalt-NHC Complex
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A simple phosphine-free cobalt-NHC pincer complex has been synthesized and utilized for the transfer hydrogenation of ketones with 2-propanol as hydrogen donor. A broad range of ketones varying from aromatic, aliphatic and heterocyclic were effectively reduced to their corresponding alcohols in moderate to excellent yields with good tolerance of functional groups.
- Ibrahim, Jessica Juweriah,Reddy, C. Bal,Fang, Xiaolong,Yang, Yong
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p. 4429 - 4432
(2020/07/04)
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- Palladium-Catalyzed Alkoxycarbonylation of sec-Benzylic Ethers
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Herein, we report the palladium-catalyzed synthesis of 3-arylpropionate esters starting from secondary benzylic ethers. With this investigation it could be shown that ethers are suitable starting materials in addition to the established carbonylation reactions of olefins, alcohols, or aryl halides.
- Beller, Matthias,Jackstell, Ralf,Maes, Bert U. W.,Schneider, Carolin
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supporting information
(2020/02/25)
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- Transfer Hydrogenation of Ketones and Imines with Methanol under Base-Free Conditions Catalyzed by an Anionic Metal-Ligand Bifunctional Iridium Catalyst
-
An anionic iridium complex [Cp*Ir(2,2′-bpyO)(OH)][Na] was found to be a general and highly efficient catalyst for transfer hydrogenation of ketones and imines with methanol under base-free conditions. Readily reducible or labile substituents, such as nitro, cyano, and ester groups, were tolerated under present reaction conditions. Notably, this study exhibits the unique potential of anionic metal-ligand bifunctional iridium catalysts for transfer hydrogenation with methanol as a hydrogen source.
- Han, Xingyou,Li, Feng,Liu, Peng,Wang, Rongzhou,Xu, Jing
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p. 2242 - 2249
(2020/03/13)
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- Green synthesis of chiral aromatic alcohols with Lactobacillus kefiri P2 as a novel biocatalyst
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Biocatalytic reduction is a very important field of research in synthetic organic chemistry. Herein, three different Lactic Acid Bacteria (LAB) strains were evaluated for their bioreduction potential using acetophenone as a model substrate. Among these strains, Lactobacillus kefiri P2 strain was determined as the best asymmetric reduction biocatalyst. Reaction optimization parameters such as reaction time, temperature, agitation speed and pH were systematically optimized using Lactobacillus kefiri P2 strain and model substrate acetophenone. Under these optimized reaction conditions, secondary chiral alcohols were obtained by bioreduction of various prochiral ketones with results up to 99% enantiomeric excess. In addition, the steric and electronic effects of substituents on enantioselectivity and conversion were evaluated. It has been shown that Lactobacillus kefiri P2 biocatalyst was an effective catalyst for asymmetric reduction. This method provides an environmentally friendly method for the synthesis of optically pure alcohols and an alternative approach to chemical catalysts.
- Bayda?, Yasemin,Dertli, Enes,?ahin, Engin
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p. 1035 - 1045
(2020/03/03)
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- Assembled Multinuclear Ruthenium(II)-NNNN Complexes: Synthesis, Catalytic Properties, and DFT Calculations
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Using a coordinatively unsaturated 16-electron mononuclear ruthenium(II)-pyrazolyl-imidazolyl-pyridine complex [Ru(II)-NNN] as the building block and oligopyridines as the polydentate ligands, pincer-type tri- A nd hexanuclear ruthenium(II) complexes [Ru(II)-NNNN]n were efficiently assembled. These complexes were characterized by elemental analyses, NMR, IR, and MALDI-TOF mass spectroscopies. In refluxing 2-propanol, the multinuclear ruthenium(II)-NNNN complexes exhibited exceptionally high catalytic activity for the transfer hydrogenation of ketones at very low concentrations and reached turnover frequencies (TOFs) up to 7.1 × 106 h-1, featuring a remarkable cooperative effect from the multiple Ru(II)-NNNN functionalities. DFT calculations have revealed the origin of the high catalytic activities of these Ru(II)-NNNN complexes.
- Liu, Tingting,Wu, Kaikai,Wang, Liandi,Fan, Hongjun,Zhou, Yong-Gui,Yu, Zhengkun
-
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- A facile and highly efficient transfer hydrogenation of ketones and aldehydes catalyzed by palladium nanoparticles supported on mesoporous graphitic carbon nitride
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A novel transfer hydrogenation methodology for the reduction of ketones (14 examples) and benzaldehyde derivatives (12 examples) to the corresponding alcohols using Pd nanoparticles supported on mesoporous graphitic carbon nitride (mpg-C3N4/Pd) as a reusable catalyst and ammonia borane as a safe hydrogen source in an aqueous solution MeOH/H2O (v/v = 1/1) is described. The catalytic hydrogenation reactions were conducted in a commercially available high-pressure glass tube at room temperature, and the corresponding alcohols were obtained in high yields in 2–5 min. Moreover, the presented transfer hydrogenation protocol shows partial halogen selectivity with bromo-, fluoro-, and chloro-substituted carbonyl analogs. In addition, the present catalyst can be reused up to five times without losing its efficiency, and scaling-up the reaction enables α-methylbenzyl alcohol to be produced in 90% isolated yield.
- Ni?anc?, Bilal,Da?alan, Ziya
-
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- Group 6 Metal Carbonyl Complexes Supported by a Bidentate PN Ligand: Syntheses, Characterization, and Catalytic Hydrogenation Activity
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We report on the preparation of a series of phosphorus-nitrogen donor ligand complexes [M(CO)4(PN)], where M = Cr, Mo, W and PN is 2-(diphenylphosphino)ethylamine. The organometallic compounds were readily obtained upon reacting the respective metal hexacarbonyls with equimolar amounts of the pertinent ligand in the presence of tetraethylammonium bromide. The PN-ligated metal carbonyls were fully characterized by standard spectroscopic techniques and X-ray crystallography. The ability of the title compounds to function as homogeneous hydrogenation catalysts was probed in the reduction of acetophenone and benzaldehyde derivatives to yield the corresponding alcohols. The reaction setup was easily assembled by simply combining the components in the autoclave on the bench outside an inert-gas-operated glovebox system.
- Faust, Kirill,Topf, Christoph,Vielhaber, Thomas
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p. 4535 - 4543
(2020/12/23)
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- Iron complex containing meta-carborane triazole ligand, preparation and application thereof
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The invention relates to an iron complex containing a meta-carborane triazole ligand, preparation and application thereof. The preparation method of the iron complex includes the steps of: 1) adding an n-BuLi solution into a meta-carborane solution, and then carrying out reaction at room temperature for 30-60min; 2) adding 3-propargyl bromide, carrying out reaction at room temperature for 2-4h, then pumping out the solvent, and carrying out recrystallization to obtain 1, 3-dipropargyl meta-carborane; 3) dissolving 1, 3-dipropargyl meta-carborane, aryl azide and a catalyst in an organic solvent, and then carrying out reaction at room temperature for 3-6h; and 4) adding FeCl2, carrying out reaction at room temperature for 5-8h, and then performing separation. The iron complex is used for catalytic oxidation of aromatic hydrocarbon to synthesize aromatic alcohol. Compared with the prior art, the invention adopts one-pot method to obtain the iron complex containing the meta-carborane triazole ligand, the synthesis process is simple and green, and the iron complex can achieve efficient catalytic oxidation of aromatic hydrocarbon to prepare an aromatic alcohol compound under the condition that hydrogen peroxide serves as an oxidizing agent.
- -
-
Paragraph 0077-0080
(2020/01/12)
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- In Situ Generated Gold Nanoparticles on Active Carbon as Reusable Highly Efficient Catalysts for a Csp3 ?Csp3 Stille Coupling
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Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional Csp2-Csp2 cross-coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form Csp3-Csp3 bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross-coupling reaction of an organic halide and an organometallic reagent.
- Holz, Julia,Pfeffer, Camilla,Zuo, Hualiang,Beierlein, Dennis,Richter, Gunther,Klemm, Elias,Peters, René
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supporting information
p. 10330 - 10334
(2019/06/27)
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- Transfer hydrogenation of ketones catalyzed by 2,6‐bis(triazinyl)pyridine ruthenium complexes: The influence of alkyl arms
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The transfer hydrogenation of ketones catalyzed by transition metal complexes has attracted much attention. A series of ruthenium(II) complexes bearing 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine ligands (R-BTPs) were synthesized and characterized by NMR analysis and X-ray diffraction. These ruthenium(II) complexes were applied in the transfer hydrogenation of ketones. Their different catalytic activity were attributed to the alkyl arms on the 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine. As the length of the alkyl arms rising, the catalytic activities of the complex catalysts decreased. By means of 0.4 mol % catalyst RuCl2(PPh3)(3-methylbutyl-BTP) in refluxing 2-propanol, a variety of ketones were reduced to their corresponding alcohols with >95% conversion over a period of 3 h.
- Wang, Liandi,Liu, Tingting
-
supporting information
(2019/08/12)
-
- Method for synthesizing secondary alcohol
-
The invention discloses a method for synthesizing secondary alcohol, which utilizes transition metal catalysis and uses isopropanol as a hydrogen source to synthesize the secondary alcohol. The reaction not only uses inexpensive and environmentally friendly isopropanol as the hydrogen source and a solvent, but also has the advantages of high yield, environmental protection, and the like, and therefore the reaction has broad development prospects.
- -
-
Paragraph 0030; 0031; 0032; 0033
(2019/03/15)
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- Ambient-pressure hydrogenation of ketones and aldehydes by a metal-ligand bifunctional catalyst [Cp*Ir(2,2′-bpyO)(H2O)] without using base
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An efficient catalytic system for hydrogenation of ketones and aldehydes using a Cp*Ir complex [Cp*Ir(2,2′-bpyO)(H2O)] bearing a bipyridine-based functional ligand as catalyst has been developed. A wide variety of secondary and primary alcohols were synthesized by the catalyzed hydrogenation of ketones and aldehydes under facile atmospheric-pressure without a base. The catalyst also displays an excellent chemoselectivity towards other carbonyl functionalities and unsaturated motifs. This catalytic system exhibits high activity for hydrogenation of ketones and aldehydes with H2 gas.
- Wang, Rongzhou,Qi, Jipeng,Yue, Yuancheng,Lian, Zhe,Xiao, Haibin,Zhuo, Shuping,Xing, Lingbao
-
-
- Synthesis, characterization of novel Nickel(II) complexes with PxNy-Type ligands and their application in reduction of ketones
-
Novel nickel(II) complexes 1 and 2 could be conveniently prepared using PxNy-type ligands and easily available NiCl2·6H2O as a starting material. Furthermore, we obtained the single crystals suitable for X-ray diffraction to confirm the structure of these two nickel(II) complexes. With the well-designed nickel(II) complex, the hydrogenation of a wide range of ketones proceeded smoothly under relative mild reaction conditions, affording the corresponding alcohols with high isolated yields.
- Wang, Zhe,Yu, Shen-Luan,Wei, Zan-Bin,An, Dong-Li,Li, Yan-Yun,Gao, Jing-Xing
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supporting information
(2019/08/12)
-
- Catalytic hydrogenation of carbonyl and nitro compounds using an [: N, O] -chelate half-sandwich ruthenium catalyst
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A series of N,O-chelate half-sandwich ruthenium complexes for both carbonyl and nitro compound hydrogenation have been synthesized based on β-ketoamino ligands. All complexes exhibited high activity for the catalytic hydrogenation of a series of ketones and nitroarenes with molecular H2 as the reducing reagent in aqueous medium. Consequently, the catalytic system showed the catalytic TON values of 950 for 1-phenylethanol in acetophenone hydrogenation and 1960 for 1-chloro-4-nitrobenzene in p-chloroaniline hydrogenation. Good catalytic activity was displayed for various kinds of substrates with either electron-donating or electron-withdrawing groups. The neutral ruthenium complexes 1-4 were fully characterized using NMR, IR, and elemental analysis. Molecular structures of complexes 2 and 4 were further confirmed using single-crystal X-ray diffraction analysis.
- Yao, Zi-Jian,Zhu, Jing-Wei,Lin, Nan,Qiao, Xin-Chao,Deng, Wei
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p. 7158 - 7166
(2019/06/13)
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- Transfer Hydrogenation of Carbonyl Groups, Imines and N-Heterocycles Catalyzed by Simple, Bipyridine-Based MnI Complexes
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Utilization of hydroxy-substituted bipyridine ligands in transition metal catalysis mimicking [Fe]-hydrogenase has been shown to be a promising approach in developing new catalysts for hydrogenation. For example, MnI complexes with 6,6′-dihydroxy-2,2′-bipyridine ligand have been previously shown to be active catalysts for CO2 hydrogenation. In this work, simple bipyridine-based Mn catalysts were developed that act as active catalysts for transfer hydrogenation of ketones, aldehydes and imines. For the first time, Mn-catalyzed transfer hydrogenation of N-heterocycles was reported. The highest catalytic activity among complexes with variously substituted ligands was observed for the complex bearing two OH groups in bipyridine. Deuterium labeling experiments suggest a monohydride pathway.
- Dubey, Abhishek,Rahaman, S. M. Wahidur,Fayzullin, Robert R.,Khusnutdinova, Julia R.
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p. 3844 - 3852
(2019/04/08)
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- Manganese(I)-Catalyzed Transfer Hydrogenation and Acceptorless Dehydrogenative Condensation: Promotional Influence of the Uncoordinated N-Heterocycle
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The four bidentate manganese(I) complexes [(C5H4N-C5H3N-OH)Mn(CO)3Br] (1), [(C9H6N-C5H3N-OH)Mn(CO)3Br] (2), [(C8H5N2-C5H3N-OH)Mn(CO)3Br] (3), and [(C8H5N2-C5H3N-OCH3)Mn(CO)3Br] (4) were synthesized. These complexes were tested as catalysts for the transfer hydrogenation of ketones, and 3 showed the highest activity. The reactions proceeded well with 0.5 mol % of catalyst loading and 20 mol % of t-BuOK at 85 °C for 24 h. Furthermore, 3 was also used as a catalyst for the synthesis of primary alcohols via transfer hydrogenation of aldehydes and the synthesis of 1,2-disubstituted benzimidazoles and quinolines via acceptorless dehydrogenative condensations.
- Zhang, Chong,Hu, Bowen,Chen, Dafa,Xia, Haiping
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p. 3218 - 3226
(2019/09/13)
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- Photoenzymatic Catalysis Enables Radical-Mediated Ketone Reduction in Ene-Reductases
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Flavin-dependent ene-reductases (EREDs) are known to stereoselectively reduce activated alkenes, but are inactive toward carbonyls. Demonstrated here is that in the presence of photoredox catalysts, these enzymes will reduce aromatic ketones. Mechanistic experiments suggest this reaction proceeds through ketyl radical formation, a reaction pathway that is distinct from the native hydride-transfer mechanism. Furthermore, this reactivity is accessible without modification of either the enzyme or cofactors, allowing both native and non-natural mechanisms to occur simultaneously. Based on control experiments, we hypothesize that binding to the enzyme active site attenuates the reduction potential of the substrate, enabling single-electron reduction. This reactivity highlights opportunities to access new catalytic manifolds by merging photoredox catalysis with biocatalysis.
- Sandoval, Braddock A.,Kurtoic, Sarah I.,Chung, Megan M.,Biegasiewicz, Kyle F.,Hyster, Todd K.
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supporting information
p. 8714 - 8718
(2019/05/28)
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- Oxidative β-Halogenation of Alcohols: A Concise and Diastereoselective Approach to Halohydrins
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β-Halohydrins bearing transformable halo- and hydroxyl groups, are easily converted into various valuable blocks in organic and pharmaceutical synthesis. A diastereoselective β-halogenation of benzylic alcohols was achieved under simple and low-cost conditions, which provided a direct synthesis of β-halohydrins. The simple reaction conditions, easily available reagents, high diastereoselectivities, and additional oxidant-free make this reaction very attractive and practical.
- Ai, Lingsheng,Wang, Weijin,Wei, Jialiang,Li, Qing,Song, Song,Jiao, Ning
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supporting information
p. 437 - 441
(2019/02/26)
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- Mild palladium-catalysed highly efficient hydrogenation of CN, C-NO2, and CO bonds using H2 of 1 atm in H2O
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Here we present the first example of a mild and high-efficiency protocol enabling a process in water using 1 atm of H2 for the efficient and selective hydrogenation of nitriles, nitro compounds, ketones, and aldehydes to yield primary amines and alcohols with satisfactory yields of up to >99%. Several palladium-based nanoparticle catalysts were prepared from K2PdCl4 and ligands, and one of them was found to be the best and most suitable for the hydrogenation of CN, C-NO2, and CO bonds. In addition, the catalyst Pd-NPs can be easily recycled and reused without losing their activity and selectivity. A plausible mechanism for the hydrogenation of a CN bond was also proposed, representing the first example that possesses great potential for sustainable industrial purposes.
- Liu, Yaxu,He, Shaopo,Quan, Ziyi,Cai, Huizhuo,Zhao, Yang,Wang, Bo
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supporting information
p. 830 - 838
(2019/02/27)
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- Design, Synthesis, and Application of NNN Pincer Ligands Possessing a Remote Hydroxyl Group for Ruthenium-Catalyzed Transfer Hydrogenation of Ketones
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A new family of pyridyl-based NNN pincer ligands bearing a remote pendent OH group were developed. Considerable acceleration effects on the activity of Ru-catalyzed transfer hydrogenation of ketones were imparted by the pendent OH group, and importantly, introducing a CH2OH group to the 4′-position of the pyrazolyl moiety is an appropriate choice. The results present a general strategy for exploring bifunctional ligands to construct effective catalysts.
- Cao, Zhengqiang,Qiao, Hong,Zeng, Fanlong
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p. 797 - 804
(2019/03/04)
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- Production of enantiomerically enriched chiral carbinols using Weissella paramesenteroides as a novel whole cell biocatalyst
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In this study, four bacterial strains were tested for their ability to reduce acetophenones to its corresponding alcohol. Among these strains Weissella paramesenteroides N7 was found to be the most successful biocatalyst to reduce the ketones to the corresponding alcohols. The reaction conditions were systematically optimized for W. paramesenteroides N7 that resulted in high enantioselectivity and conversion rates for the bioreduction. The scale-up asymmetric reduction of 1-(4-methoxyphenyl) propan-1-one (1r) by W. paramesenteroides N7 gave (R)-1-(4-methoxyphenyl) propan-1-ol (2r) with 94% yield and >99% enantiomeric excess. This is the first report showing the synthesis of (R)-1-(4-methoxyphenyl) propan-1-ol (2r) in enantiopure form using a biocatalyst on a gram scale. The whole cell catalyzed the reductions of ketone substrates on the preparative scale, demonstrating that W. paramesenteroides N7 would be a valuable biocatalyst for the preparation of chiral aromatic alcohols of pharmaceutical interest as a promising and alternative green approach.
- Tozlu, Caner,?ahin, Engin,Serencam, Hüseyin,Dertli, Enes
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p. 388 - 398
(2019/02/14)
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- Monodisperse CuPt alloy nanoparticles assembled on reduced graphene oxide as catalysts in the transfer hydrogenation of various functional organic groups
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We present herein a new nanocatalyst, namely binary CuPt alloy nanoparticles (NPs) supported on reduced graphene oxide (CuPt-rGO), as a highly active heterogeneous catalyst for the transfer hydrogenation (TH) protocol that is demonstrated to be applicable over the reduction of various unsaturated organic compounds (olefins, aldehydes/ketones and nitroarenes) in aqueous solutions at room temperature. CuPt alloy NPs were synthesized by the co-reduction of metal (II) acetylacetonates by borane-tert-butylamine (BTB) complex in hot oleylamine (OAm) solution and then assembled on reduced graphene oxide (rGO) via ultrasonic-assisted liquid phase self-assembly method. The structure of yielded CuPt NPs and CuPt-rGO nanocatalyst were characterized by TEM, XRD and ICP-MS. The activity of Cu7Pt3-rGO nanocatalysts were then tested for the THs that were conducted in a commercially available high-pressure tube using water as sole solvent and ammonia borane as a hydrogen donor at room temperature. The presented catalytic TH protocol was successfully applied over nitroarenes, olefines and aldehydes/ketones, and all the tested compounds were converted to corresponding reduction products with the yields reaching up to 99% under ambient conditions. Moreover, the Cu7Pt3-rGO nanocatalyst was also reusable in the TH by providing 99% yield after five consecutive runs in TH of nitrobenzene as an example.
- Ganjehyan, Khadijeh,Ni?anc?, Bilal,Sevim, Melike,Da?tan, Arif,Metin, ?nder
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- Solvent and substituent effects in hydrogenation of aromatic ketones over Ru/polymer catalyst under very mild conditions
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The paper reports on the solvent and the substituent effects in hydrogenation of aromatic ketones (acetophenone and its derivatives) in the presence of Ru catalyst supported on functionalized gel-type methacrylate-styrene resin under very mild conditions
- Duraczyńska,Serwicka,Drelinkiewicz,Socha,Zimowska,Lityńska-Dobrzyńska,Bukowska
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p. 145 - 151
(2019/04/13)
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- Deoxygenative cross-electrophile coupling of benzyl chloroformates with aryl iodides
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This work describes Ni-catalyzed cross-electrophile coupling of benzyl chloroformate derivatives with aryl iodides that generates a wide range of diaryl methane products. The mild reaction conditions merit the C-O bond radical fragmentation of benzyl chloroformates via halide abstraction or a single electron reduction by a Ni catalyst. This work offers a new substrate type for cross-electrophile couplings.
- Pan, Yingying,Gong, Yuxin,Song, Yanhong,Tong, Weiqi,Gong, Hegui
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supporting information
p. 4230 - 4233
(2019/05/06)
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- Highly dispersed Ni nanoparticles on mesoporous silica nanospheres by melt infiltration for transfer hydrogenation of aryl ketones
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Nickel-based catalysts have been applied to the catalytic reactions for transfer hydrogenation of carbonyl compounds. In the present work, highly dispersed nickel particles located at the pores of mesoporous silica spheres (Ni@mSiO2) were prepared via an optimized melt infiltration route. The nickel nanoparticles of 10 wt% in the Ni@mSiO2 catalyst could be uniformly loaded with high dispersion of 36.3%, resulting excellent performance for catalytic transfer hydrogenation of aryl ketones.
- Kweon, Hyemin,Jang, Sanha,Bereketova, Akerke,Chan Park, Ji,Park, Kang Hyun
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p. 14154 - 14159
(2019/05/21)
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- Phosphine-NHC Manganese Hydrogenation Catalyst Exhibiting a Non-Classical Metal-Ligand Cooperative H2 Activation Mode
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Deprotonation of the MnI NHC-phosphine complex fac-[MnBr(CO)3(κ2P,C-Ph2PCH2NHC)] (2) under a H2 atmosphere readily gives the hydride fac-[MnH(CO)3(κ2P,C-Ph2PCH2NHC)] (3) via the intermediacy of the highly reactive 18-e NHC-phosphinomethanide complex fac-[Mn(CO)3(κ3P,C,C-Ph2PCHNHC)] (6 a). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16-e mangana-substituted phosphonium ylide complex fac-[Mn(CO)3(κ2P,C-Ph2P=CHNHC)] (6 b) as key intermediate able to activate H2 via a non-classical mode of metal-ligand cooperation implying a formal λ5-P–λ3-P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre-catalysts for ketone hydrogenation in the MnI series reported to date (TON up to 6200).
- Buhaibeh, Ruqaya,Filippov, Oleg A.,Bruneau-Voisine, Antoine,Willot, Jérémy,Duhayon, Carine,Valyaev, Dmitry A.,Lugan, No?l,Canac, Yves,Sortais, Jean-Baptiste
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supporting information
p. 6727 - 6731
(2019/04/17)
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- Design, synthesis and structure-based optimization of novel isoxazole-containing benzamide derivatives as FtsZ modulators
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Antibiotic resistance among clinically significant bacterial pathogens is becoming a prevalent threat to public health, and new antibacterial agents with novel mechanisms of action hence are in an urgent need. Utilizing computational docking method and structure-based optimization strategy, we rationally designed and synthesized two series of isoxazol-3-yl- and isoxazol-5-yl-containing benzamide derivatives that targeted the bacterial cell division protein FtsZ. Evaluation of their activity against a panel of Gram-positive and -negative pathogens revealed that compounds B14 and B16 that possessed the isoxazol-5-yl group showed strong antibacterial activity against various testing strains, including methicillin-resistant Staphylococcus aureus and penicillin-resistant S. aureus. Further molecular biological studies and docking analyses proved that the compound functioned as an effective inhibitor to alter the dynamics of FtsZ self-polymerization via a stimulatory mechanism, which finally terminated the cell division and caused cell death. Taken together, these results could suggest a promising chemotype for development of new FtsZ-targeting bactericidal agent.
- Bi, Fangchao,Song, Di,Zhang, Nan,Liu, Zhiyang,Gu, Xinjie,Hu, Chaoyu,Cai, Xiaokang,Venter, Henrietta,Ma, Shutao
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- FLP-Catalyzed Transfer Hydrogenation of Silyl Enol Ethers
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Herein we report the first catalytic transfer hydrogenation of silyl enol ethers. This metal free approach employs tris(pentafluorophenyl)borane and 2,2,6,6-tetramethylpiperidine (TMP) as a commercially available FLP catalyst system and naturally occurring γ-terpinene as a dihydrogen surrogate. A variety of silyl enol ethers undergo efficient hydrogenation, with the reduced products isolated in excellent yields (29 examples, 82 % average yield).
- Khan, Imtiaz,Reed-Berendt, Benjamin G.,Melen, Rebecca L.,Morrill, Louis C.
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p. 12356 - 12359
(2018/09/18)
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- Transfer Hydrogenation of Aldehydes and Ketones with Isopropanol under Neutral Conditions Catalyzed by a Metal-Ligand Bifunctional Catalyst [Cp?Ir(2,2′-bpyO)(H2O)]
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A Cp?Ir complex bearing a functional bipyridonate ligand [Cp?Ir(2,2′-bpyO)(H2O)] was found to be a highly efficient and general catalyst for transfer hydrogenation of aldehydes and chemoselective transfer hydrogenation of unsaturated aldehydes with isopropanol under neutral conditions. It was noteworthy that many readily reducible or labile functional groups such as nitro, cyano, ester, and halide did not undergo any change under the reaction conditions. Furthermore, this catalytic system exhibited high activity for transfer hydrogenation of ketones with isopropanol. Notably, this research exhibited new potential of metal-ligand bifunctional catalysts for transfer hydrogenation.
- Wang, Rongzhou,Tang, Yawen,Xu, Meng,Meng, Chong,Li, Feng
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p. 2274 - 2281
(2018/02/23)
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- Ruthenium NNN complexes with a 2-hydroxypyridylmethylene fragment for transfer hydrogenation of ketones
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Four NNN tridentate ligands L1–L4 containing 2-methoxypyridylmethene or 2-hydroxypyridylmethene fragment were synthesized and introduced to ruthenium centers. When (HOC5H3NCH2C5H3NC5H7N2) (L2) and (HOC5H3NCH2C5H3NC6H6N3) (L4) reacted with RuCl2(PPh3)3, two ruthenium chloride products Ru(L2)(PPh3)Cl2 (1) and Ru(L4)(PPh3)Cl2 (2) were isolated, respectively. Reactions of (MeOC5H3NCH2C5H3NC5H7N2) (L1) and (MeOC5H3NCH2C5H3NC6H6N3) (L3) with RuCl2(PPh3)3 in the presence of NH4PF6 generated two dicationic complexes [Ru(L1)2][PF6]2 (3) and [Ru(L3)2][PF6]2 (4), respectively. Complex 1 reacted with CO to afford product [Ru(L2)(PPh3)(CO)Cl][Cl]. The catalytic activity for transfer hydrogenation of ketones was investigated. Complex 1 showed the highest activity, with a turnover frequency value of 1.44?×?103?h?1 for acetophenone, while complexes 3 and 4 were not active.
- Shi, Jing,Shang, Shu,Hu, Bowen,Chen, Dafa
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- Ruthenium(II) complex catalysts bearing a 2,6-bis(tetrazolyl)pyridine ligand for the transfer hydrogenation of ketones
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Three ruthenium(II) complex catalysts bearing 2,6-bis(tetrazolyl)pyridine were synthesized, structurally characterized, and applied in the transfer hydrogenation of ketones. Their different catalytic activities were attributed to the different phosphine ligands on the 4-chloro-2,6-bis(1-(p-tolyl)- 1H- tetrazol-5-yl)pyridine ruthenium(II) complexes, with that based on 1,4- bis(diphenylphosphino) butane exhibiting better catalytic activity. A variety of ketones were reduced to their corresponding alcohols with >95% conversion.
- Wang, Liandi,Liu, Tingting
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p. 327 - 333
(2018/02/20)
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- 3-Aminoquinazoline–phosphine ligands and their ruthenium(II) complexes: application in catalytic hydrogenation and transfer hydrogenation reactions
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3-Aminoquinazolinone–phosphine proligands (5a–e) and their Ru(II) complexes (6a–e) were prepared and characterized by NMR (1H, 13C, 31P{1H}), FTIR and microanalysis. The 3-aminoquinazolinone–phosphine ligands were found to coordinate with the Ru(II) center via their phosphorus and nitrogen atoms. The Ru(II) complexes were applied as catalysts for the hydrogenation and transfer hydrogenation of prochiral ketones. The results showed that these complexes are efficient transfer hydrogenation catalysts.
- Y?lmaz, Mustafa Kemal,Kele?, Mustafa
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p. 285 - 292
(2018/02/19)
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- Synthesis of C2-symmetric bisphosphines and their application in enantioselective transition metal catalysis
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C2-symmetric bisphosphine ligands (with a dioxolane backbone) have been synthesized by using corresponding chiral bromo-substituted hydrobenzoin derivatives in two steps with moderate yields. The last step for desired bisphosphines defined the electronic
- G?k, Halil Zeki,K?l??arslan, Seda,G?k, Ya?ar
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- The Oxidation of Hydrophobic Aromatic Substrates by Using a Variant of the P450 Monooxygenase CYP101B1
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The cytochrome P450 monooxygenase CYP101B1, from a Novosphingobium bacterium is able to bind and oxidise aromatic substrates but at a lower activity and efficiency than norisoprenoids and monoterpenoid esters. Histidine 85 of CYP101B1 aligns with tyrosine 96 of CYP101A1, which, in the latter enzyme forms the only hydrophilic interaction with its substrate, camphor. The histidine residue of CYP101B1 was mutated to phenylalanine with the aim of improving the activity of the enzyme for hydrophobic substrates. The H85F mutant lowered the binding affinity and activity of the enzyme for β-ionone and altered the oxidation selectivity. This variant also showed enhanced affinity and activity towards alkylbenzenes, styrenes and methylnaphthalenes. For example the rate of product formation for acenaphthene oxidation was improved sixfold to 245 nmol per nmol CYP per min. Certain disubstituted naphthalenes and substrates, such as phenylcyclohexane and biphenyls, were oxidised with lower activity by the H85F variant. Variants at H85 (A and G) designed to introduce additional space into the active site so as to accommodate these larger substrates did not improve the oxidation activity. As the H85F mutant of CYP101B1 improved the oxidation of hydrophobic substrates, this residue is likely to be in the substrate binding pocket or the access channel of the enzyme. The side chain of the histidine might interact with the carbonyl groups of the favoured norisoprenoid substrates of CYP101B1.
- Sarkar, Md. Raihan,Lee, Joel H. Z.,Bell, Stephen G.
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p. 2119 - 2128
(2017/10/12)
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- Cp2TiCl2-catalyzed cycloboration of α-olefins with PhBCl2in the synthesis of 2-alkyl(aryl,benzyl)-1-phenylboriranes
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A one-pot method for the synthesis of 2-alkyl(aryl, benzyl)-1-phenylboriranes has been developed via the reaction of α-olefins with PhBCl2in the presence of Cp2TiCl2as the catalyst. The method implies the formation of boriranes as the result of transmetalation of titanacyclopropane intermediates generated in the reaction of α-olefins with Cp2TiCl2. Individual 1-phenyl-2-substituted boriranes were isolated and their structures confirmed by NMR spectral methods.
- Khusainova, Liliya I.,Khafizova, Leila O.,Tyumkina, Tatyana V.,Ryazanov, Kirill S.,Dzhemilev, Usein M.
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