- Photoredox-Catalyzed Simultaneous Olefin Hydrogenation and Alcohol Oxidation over Crystalline Porous Polymeric Carbon Nitride
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Booming of photocatalytic water splitting technology (PWST) opens a new avenue for the sustainable synthesis of high-value-added hydrogenated and oxidized fine chemicals, in which the design of efficient semiconductors for the in-situ and synergistic utilization of photogenerated redox centers are key roles. Herein, a porous polymeric carbon nitride (PPCN) with a crystalline backbone was constructed for visible light-induced photocatalytic hydrogen generation by photoexcited electrons, followed by in-situ utilization for olefin hydrogenation. Simultaneously, various alcohols were selectively transformed to valuable aldehydes or ketones by photoexcited holes. The porosity of PPCN provided it with a large surface area and a short transfer path for photogenerated carriers from the bulk to the surface, and the crystalline structure facilitated photogenerated charge transfer and separation, thus enhancing the overall photocatalytic performance. High reactivity and selectivity, good functionality tolerance, and broad reaction scope were achieved by this concerted photocatalysis system. The results contribute to the development of highly efficient semiconductor photocatalysts and synergistic redox reaction systems based on PWST for high-value-added fine chemical production.
- Qiu, Chuntian,Sun, Yangyang,Xu, Yangsen,Zhang, Bing,Zhang, Xu,Yu, Lei,Su, Chenliang
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p. 3344 - 3350
(2021/07/26)
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- Hydrogenation reaction method
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The invention relates to a hydrogenation reaction method, and belongs to the technical field of organic synthesis. The hydrogenation reaction method provided by the invention comprises the following steps: carrying out a hydrogen transfer reaction on a hydrogen acceptor compound, pinacol borane and a catalyst in a solvent in the presence of proton hydrogen, so that the hydrogen acceptor compound is subjected to a hydrogenation reaction; the catalyst is one or more than two of a palladium catalyst, an iridium catalyst and a rhodium catalyst; the hydrogen acceptor compound comprises one or morethan two functional groups of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-nitrogen double bonds, nitrogen-nitrogen double bonds, nitryl, carbon-nitrogentriple bonds and epoxy. The method is mild in reaction condition, easy to operate, high in yield, short in reaction time, wide in substrate application range, suitable for carbon-carbon double bonds,carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-nitrogen double bonds, nitrogen-nitrogen double bonds, nitryl, carbon-nitrogen triple bonds and epoxy functional groups, good in selectivity and high in reaction specificity.
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Paragraph 0034; 0069-0072
(2020/05/14)
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- Catalytic Oxidative Deamination by Water with H2Liberation
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Selective oxidative deamination has long been considered to be an important but challenging transformation, although it is a common critical process in the metabolism of bioactive amino compounds. Most of the synthetic methods developed so far rely on the use of stoichiometric amounts of strong and toxic oxidants. Here we present a green and efficient method for oxidative deamination, using water as the oxidant, catalyzed by a ruthenium pincer complex. This unprecedented reaction protocol liberates hydrogen gas and avoids the use of sacrificial oxidants. A wide variety of primary amines are selectively transformed to carboxylates or ketones in good to high yields. It is noteworthy that mechanistic experiments and DFT calculations indicate that in addition to serving as the oxidant, water also plays an important role in assisting the hydrogen liberation steps involved in amine dehydrogenation.
- Tang, Shan,Rauch, Michael,Montag, Michael,Diskin-Posner, Yael,Ben-David, Yehoshoa,Milstein, David
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supporting information
p. 20875 - 20882
(2020/12/23)
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- NOVEL COMPOUND, RADIATION-SENSITIVE COMPOSITION, CURED FILM AND METHOD FOR FORMING THE SAME
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The invention relates to a novel compound, a radioactive ray sensitivity composition, a solidified film and a forming method thereof. The invention aims to provide a compound, which has a high radiation susceptibility, good dissolvability in a radiation sensitivity composition and good transparency of solidified film when the compound is used as a photo polymerized initiator. A radiation sensitivity compound can obtain the solidified film with good transparency and surface hardness. The invention is a compound expressed in the following formula (1), where R4 is alicyclic alkyl with one part of or the whole hydrogen atoms being replaced by alkyl with 1-12 carbon atoms. The invention is the radiation sensitivity composition having the compound (A) as the photo polymerized initiator and the polymerized compound (B) having ethylene unsaturated double bonds. The radiation sensitivity composition preferably includes alkali soluble resin (C).
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Paragraph 0168; 0169; 0171; 0172
(2018/05/03)
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- METAL CATALYSED CARBONYLATION OF UNSATURATED COMPOUNDS
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The invention provides a method for the hydroxycarbonylation, alkoxycarbonylation, aryloxycarbonylation or thiocarbonylation of an unsaturated molecule comprising effecting a hydroxycarbonylation, alkoxycarbonylation, aryloxycarbonylation or thiocarbonylation reaction on the unsaturated molecule in which a complex comprising a ligand comprising a [n,n']cyclophane comprising two non-fused monocyclic aromatic rings bridged by two linear and aliphatic linkages, in which each of the non-fused monocyclic aromatic rings is substituted with a phosphorus atom-containing substituent, is used to catalyse the hydroxycarbonylation, alkoxycarbonylation, aryloxycarbonylation or thiocarbonylation reaction.
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Page/Page column 30-31
(2011/04/18)
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- Partial and full agonists of A1 adenosine receptors
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Disclosed are novel compounds that are partial and full A1 adenosine receptor agonists, useful for treating various disease states, in particular tachycardia and atrial flutter, angina, and myocardial infarction.
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- New spirocyclic oxindole synthesis based on a hetero claisen rearrangement
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(Equation Presented) A new method for preparing spirocyclic oxindoles is presented. Featuring a [3,3]-sigmatropic enolate rearrangement, the three-step process converts carboxylic acid starting materials to oxidnole products in overall yields of 52-76%. The enolate rearrangement step occurs at -78 °C and provides easy access to oxindole products that have previously been difficult to prepare.
- Mao, Zhan,Baldwin, Steven W.
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p. 2425 - 2428
(2007/10/03)
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- Ru-catalyzed hydroamidation of alkenes and cooperative aminocarboxylation procedure with chelating formamide
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(Matrix presented) A strategy of chelation-assisted activation of formamide was employed to achieve hydroamidation of alkenes to generate one-carbon-elongated amides in moderate to good selectivity and yields. Also reported is the two-metal-catalyzed cooperative aminocarboxylation of aryl iodides, in which Ru is presumed to catalyze decarbonylation of formamide to release carbon monoxide and amine for the subsequent Pd-catalyzed aminocarboxylation routes, thus enabling the net transformation to be performed in the absence of external CO pressure.
- Ko, Sangwon,Han, Hoon,Chang, Sukbok
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p. 2687 - 2690
(2007/10/03)
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- Method for producing optically active 3-substituted-2-norbornanones and their intermediates
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The present invention provides a method for producing optically active 3-substituted-2-norbornanones which are useful as starting materials for several kinds of physiologically active materials, and to their intermediates, optically active 2-hydroxy-2-norbornanecarboxylic acid and to a method for producing these intermediates.
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- Bicyclonon-1-ene: Matrix Isolation and Spectroscopic Characterization of a Moderately Strained Bridgehead Olefin
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Bicyclonon-1-ene was generated in low-temperature matrices and in fluid solutions by photodecomposition of bicyclooct-1-yldiazomethane and its photorearrangement product, 3-(bicyclooct-1-yl)diazirine.It was characterized by IR and UV absorption and by 1H and 13C NMR spectroscopy.Further evidence for the proposed structure was provided by self-trapping and by the spectral effects of deuteration on the olefinic carbon.Observed IR spectra and isotopic shifts agree well with the results of semiempirical (MNDO) and ab initio (SCF/6-31G*) calculations.
- Gudipati, Murthy S.,Radziszewski, Juliusz G.,Kaszynski, Piotr,Michl, Josef
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p. 3668 - 3674
(2007/10/02)
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- Electrochemical incorporation of carbon dioxide into alkenes by nickel complexes
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Electrogenerated Ni(0) complexes from stable Ni(II) compounds are the catalysts for the electrochemical incorporation of carbon dioxide into carbon-carbon double bonds. Different kind of olefin derivatives have been carboxylated to afford mono- or dicarboxylic acid derivatives depending on the alkene structure. The electrolyses are carried out in one compartment cells fitted with a magnesium anode under mild conditions.
- Derien, Sylvie,Clinet, Jean-Claude,Dunach, Elisabet,Perichon, Jacques
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p. 5235 - 5248
(2007/10/02)
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- Process for improving the coefficient of traction and traction drive fluid
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A process for improving the coefficient of traction at high temperatures in a traction drive, and a tranction drive fluid for use therein. This traction drive fluid comprises the hydrogenated product of a dimer, a trimer or a tetramer of norbornanes and/or norbornenes, and exhibits excellent traction performance over a wide temperature range from low temperature to high temperature.
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- cis-Diazenes. Pressure Effects on Their Thermal Deazatization and Isomerization Reactions
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Effects of pressure on solution-phase rates of overall thermal decomposition, deazatization, and isomerization of several symmetric cis-diazenes (cis-azoalkanes) have been determined in hexane and in ethanol.Increasing pressure decreases all the rates.The large positive activation volumes for deazatization (e.g., +16 to +22 cm3/mol) have been interpreted in terms of a one-bond scission mechanism and an intermediate diazenyl radical.The smaller positive activation volumes for isomerization (e.g., +5 to +7 cm3/mol) are consistent with a nonradical inversion mechanism.Dramatic differences in rates between polar and nonpolar solvents are consistent with these mechanisms.
- Neuman, Robert C.,Berge, Charles T.,Binegar, Glen Al.,Adam, Waldemar,Nishizawa, Yoshinori
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p. 4564 - 4568
(2007/10/02)
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- NICKEL(0)-INDUZIERTE C-C-VERKNUEPFUNG ZWISCHEN ALKENEN UND KOHLENDIOXID
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The oxanickelacyclopentanone-derivate (I) can easily be prepared from norbornene (bicycloheptene), CO2 and nickel(0) compounds.
- Hoberg, Heinz,Schaefer, Dietmar
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p. C28 - C30
(2007/10/02)
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- KINETIC RESOLUTION OF RACEMIC GRIGNARD REAGENTS BY NICKEL-CATALYZED ASYMMETRIC GRIGNARD CROSS-COUPLING
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Racemic Grignard reagents, 2-phenylpropylmagnesium chloride and 2-norbornylmagnesium chloride were kinetically resolved by asymmetric cross-coupling with vinyl bromides in the presence of chiral phosphine-nickel catalysts to give optically active coupling products (ca. 37percent ee) and carboxylic acids after carbonation with carbon dioxide.
- Hayashi, Tamio,Kanehira, Koichi,Hioki, Tsuyoshi,Kumada, Makoto
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p. 137 - 140
(2007/10/02)
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- ETUDE DU CARACTERE NUCLEOPHILE DES RADICAUX LORS DE LA REACTION DE TRANSFERT SUR LA LIAISON O-O DES PERACIDES
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Peracids RCO3H yield free radicals R. which react either with the peracid or with solvent giving the alcohol ROH and the hydrocarbon RH.The nucleophilic character of the free radicals was modified either by substitution of the carbon bearing the odd electron by inductive groups or by changing the free radical hybridation by the means of blocked structures such as cyclic or bicyclic free radicals.For each R., the measurement of the ratio ROH/RH establishes a reactivity scale for R. with the peracid O-O bond.This reactivity does not depend on free radical stability but depends strongly on nucleophilic character.A primary free radical is less reactive than a secondary one, and is much less reactive than a tertiary one.A bridgehead free radical as the bicycloheptyle-1 does not react with the peracid.These results are interpreted to indicate a transition state with charge transfer (polar effect), the peracid being electrophilic and the free radical nucleophilic; PMO theory is discussed.
- Fossey, Jacques,Lefort, Daniel
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p. 1023 - 1036
(2007/10/02)
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