- Hydrothermal self - sacrificing growth of polymorphous MnO2 on magnetic porous - carbon (Fe3O4@Cg/MnO2): A sustainable nanostructured catalyst for activation of molecular oxygen
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Novel core-shell carbon coated-magnetic (Fe3O4@Cg) nanoparticles supported MnO2 nanosheets (with α- and β-type structure) (Fe3O4@Cg/MnO2) are synthesized through a self-sacrificing templet method. The new hybrid material was fully characterized with Fourier transformed infrared spectroscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, X-ray diffraction analysis (XRD), N2 adsorption/desorption analysis, and transmission electron microscopy; XRD and SEM results affirmed that α- and β-MnO2 nanosheets polymorphs onto the Fe3O4@Cg. The catalytic activity of the as-prepared nanostructured catalyst Fe3O4@Cg/MnO2 has been evaluated in O2 activation for the selective oxidation of benzyl alcohol to benzaldehyde with high conversion; it stability being confirmed by the recycling of the nanostructured catalyst with no obvious loss even after six repeated runs.
- Bakhtiarzadeh, Zohreh,Jang, Ho Won,Karimi, Ziba,Kim, Dokyoon,Msagati, Titus A. M.,Ramakrishna, Seeram,Rostamnia, Sadegh,Rouhani, Shamila,Shokouhimehr, Mohammadreza,Varma, Rajender S.
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Read Online
- Boosted photocatalytic performance of uniform hetero-nanostructures of Bi2WO6/CdS and Bi2WO6/ZnS for aerobic selective alcohol oxidation
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A two-dimensional hierarchical structural photocatalyst based on Bi2WO6 was obtained via a hydrothermal method and modified using ZnS and CdS and characterized by physico-chemical techniques XRD, FTIR, SEM, EDAX, and DRS. Their photo
- Safaei, Elham,Mohebbi, Sajjad
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Read Online
- Controlled reduction of activated primary and secondary amides into aldehydes with diisobutylaluminum hydride
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A practical method is disclosed for the reduction of activated primary and secondary amides into aldehydes using diisobutylaluminum hydride (DIBAL-H) in toluene. A wide range of aryl and alkyl N-Boc, N,N-diBoc and N-tosyl amides were converted into the corresponding aldehydes in good to excellent yields. Reduction susceptible functional groups such as nitro, cyano, alkene and alkyne groups were found to be stable. Broad substrate scope, functional group compatibility and quick conversions are the salient features of this methodology.
- Azeez, Sadaf,Kandasamy, Jeyakumar,Sabiah, Shahulhameed,Sureshbabu, Popuri
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supporting information
p. 2048 - 2053
(2022/03/31)
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- SBA-15 Supported Silver Catalyst for the Efficient Aerobic Oxidation of Toluene Under Solvent-Free Conditions
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The efficient SBA-15 supported silver catalysts(Ag/SBA-15) were prepared and characterized by ICP-OES, XRD, TEM, SEM, XPS and N2 adsorption–desorption techniques. The catalysts exhibited an excellent catalytic activity for the aerobic oxidation of toluene to benzaldehyde under solvent-free conditions. Conversion of toluene and selectivity of benzaldehyde were 50% and 89% respectively over catalyst with 9.1 wt% Ag loading (10Ag/SBA-15). A wide range of substrates were tolerated under the selected reaction conditions. The kinetic study shows that the oxidation of toluene over 10Ag/SBA-15 is pseudo-first-order reaction and the activation energy Ea is 45.1?kJ/mol. A plausible mechanism involving oxygen free radicals was proposed for the aerobic oxidation reaction. Compared with the traditional method, the newly designed heterogeneous catalytic system shows better economic applicability, environmental friendliness and broader application prospects. Graphical abstract: [Figure not available: see fulltext.]
- Chen, Lei,Chen, Yanjiao,Dai, Xuan,Guo, Jiaming,Peng, Xinhua
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- Rapid, chemoselective and mild oxidation protocol for alcohols and ethers with recyclable N-chloro-N-(phenylsulfonyl)benzenesulfonamide
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Chlorine is the 20th most abundant element on the earth compared to bromine, iodine, and fluorine, a sulfonimide reagent, N-chloro-N-(phenylsulfonyl)benzenesulfonamide (NCBSI) was identified as a mild and selective oxidant. Without activation, the reagent was proved to oxidize primary and secondary alcohols as well as their symmetrical and mixed ethers to corresponding aldehydes and ketones. With recoverable PS-TEMPO catalyst, selective oxidation over chlorination of primary and secondary alcohols and their ethers with electron-donating substituents was achieved. The reagent precursor of NCBSI was recovered quantitatively and can be reused for synthesizing NCBSI.
- Badani, Purav,Chaturbhuj, Ganesh,Ganwir, Prerna,Misal, Balu,Palav, Amey
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supporting information
(2021/06/03)
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- A new porous Co(ii)-metal-organic framework for high sorption selectivity and affinity to CO2and efficient catalytic oxidation of benzyl alcohols to benzaldehydes
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Herein, we report a new 3D porous Co(ii)-based metal-organic framework catalyst (Me2NH2)2[Co3(L)2(H2O)2]·2DMF (MOF I), which has been successfully prepared by using Co(ii) ions and rigid V-shaped 3,5-di(2,4-dicarboxylphenyl)pyridine (H4L) via the solvothermal reaction. Structural analysis reveals that I displays a porous structure with the pore size of 16.2 × 7.2 ?2 based on the trinuclear [Co3(COO)4(H2O)2N2] secondary building units (SBUs). Gas sorption experiments on the guest free sample I′ reveals a high capacity and selectivity to CO2 over CH4. And further, the catalytic explorations of the I′-catalyzed system (I′: 3 mol%; proline: 40 mol%; CH3CN: 2 mL) reveal that benzyl alcohols with different structures can be efficiently transformed into benzyl alcohols without by-products under mild conditions.
- Wu, Yun-Long,Yang, Rong-Rong,Yang, Guo-Ping,Yan, Yang-Tian,Su, Xiao-Lei,He, Xin-Hai,Song, Yan-Yan,Ma, Zheng-Sheng,Wang, Yao-Yu
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p. 3717 - 3723
(2021/05/31)
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- Fe(III) superoxide radicals in halloysite nanotubes for visible-light-assisted benzyl alcohol oxidation and oxidative C[sbnd]C coupling of 2-naphthol
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Selective oxidation of benzyl alcohols to aldehydes and 2-naphthol to BINOL was achieved by activation of molecular oxygen (O2) and hydrogen peroxide (H2O2) over an iron-oxide catalyst embedded in halloysite nanotube. Electron spin resonance spectroscopy (ESR), Raman and in situ FTIR spectroscopic analysis provided direct evidence for the involvement of superoxide radical bound FeIII species in the oxidation reaction. Both the analysis suggested the end-on binding of superoxide radical with FeIII-centre. The stability of such radical bound FeIII-species in halloysite nanotube was analyzed through density functional theory (DFT) calculations. Results suggested that end-on (η1) binding was favourable by 13.5 kcal/ mol than the side-on (η2) binding mode. The formation of such reactive species was believed to play the crucial role in bringing the high selectivity in the catalytic oxidation of benzyl alcohol and oxidative C[sbnd]C coupling of 2-naphthol. UV–Vis spectroscopic studies on the oxidation of benzyl alcohol suggested for the initial adsorption of substrate molecule on the catalyst surface followed by its interaction with FeIII -superoxide/hydroperoxide species generated upon photoirradiation with visible light in presence of O2. The presence of a suitable band gap ~2.14 eV enabled the catalyst to catalyze the reaction under visible light irradiation. Both the reactions (benzyl alcohol and 2-naphthol oxidation) were tested in presence of both O2 and H2O2 as oxidants at ambient temperature. The influence of different parameters like rate of oxygen flow, amount of peroxide, nature of solvent, and catalyst amount on the conversion and selectivity of the reactions were studied to understand their role in the catalytic reactions. Successful oxidation of 2-naphthol with H2O2 as oxidant was a real success to overcome the limitations associated with this reaction using H2O2 as oxidant.
- Bania, Kusum K.,Baruah, Manash J.,Bora, Tonmoy J.,Dutta, Rupjyoti,Guha, Ankur Kanti,Roy, Subhasish
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- α-MnO2 modified exfoliated porous g-C3N4 nanosheet (2D) for enhanced photocatalytic oxidation efficiency of aromatic alcohols
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Porous graphitic carbon nitride (g-C3N4) was synthesized by taking melamine and ammonium bicarbonate through single-step calcination method followed by ultrasonication to obtain exfoliated porous g-C3N4 (2D) nanosheets. Further enhancement of photocatalytic performance, g-C3N4 nanosheet (2D) was further modified with different weight percentage of (1, 3, 5, and 7) of MnO2. The introduction of α-MnO2 onto the g-C3N4 nanosheet establishes an interlayer channels to promote the migration of charge carriers through the valence band and conduction band of the prepared composite MnO2@g-C3N4. The transformation of photo induced charge carriers adopt the Z-scheme mechanism rather band-transfer mechanism. The accumulated photo generated electrons in conduction band of g-C3N4 is more electro negative than the potential of (O2/O2–.) and able to reduce oxygen to superoxide (O2–.) radical. At the same time, the holes in valence band of α-MnO2 are more electro positive than the potential of (OH–/OH.) and help in oxidate OH– to hydroxyl (OH.) radical. Among all the composites, 3 wt% MnO2 modified g-C3N4 shows the best photocatalytic oxidation efficiency towards all the aromatic alcohols. In presence of visible light, heterojuction formation, and formation of active charged species (OH. and O2–.) were mostly responsible for photocatalytic oxidation of aromatic alcohols through free radical mechanism.
- Nanda, Binita,Nanda, Braja B.,Pradhan, Manas Ranjan,Rath, Dharitri,Sethi, Ratikanta
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- Synthesis, characterization, reactivity, and catalytic studies of heterobimetallic vanadium(V) complexes containing hydrazone ligands
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Six heterobimetallic alkali metal dioxidovanadium(V) coordination polymer complexes {[M6{VO(μ-O)}2(μ-OH)4(μ4-slox/nph)].n DMF}∞ where M = Na, K, and Cs; n = 1 for (1), 0 for (2)-(6) of two dihydrazone ligands, disalicylaldehydeoxaloyldihydrazone (H4slox) and bis(2-hydroxy-1-naphthaldehyde)oxaloyldihydrazone (H4nph) are reported. All the complexes have been characterized by various physicochemical techniques such as elemental analyses, molar conductance, IR, NMR, UV–vis, and cyclic voltammetry. The IR, 1HNMR, and 13CNMR spectral data suggest that the dihydrazones are coordinated through phenolate/naphtholate oxygen, enolate oxygen, and azine nitrogen atoms to the metal centres. The structure of complex {[Na6{VO(μ-O)}2(μ-OH)4(μ4-slox)].DMF}∞ (1) is also determined by single-crystal X-ray data, which revealed that the H4slox coordinated via all possible dative sites to metal centres as tetrabasic octadentate ligand. The vanadium metal centres adopted distorted square-pyramidal coordination geometries, and the sodium atoms are also in five coordination atmospheres. The electronic spectra of the complexes showed LMCT bands in addition to intra-ligand π → π* and n → π* transitions. As evident from the cyclic voltammetry, the complexes showed two metal-centred electron transfer reactions {[(VVVV(slox)2?/VVVIV(slox)3?] and [(VVVIV(slox)3?/VVVIV(slox)4?]}, in addition to the ligand centred electron transfer reactions. Further, bovine serum albumin (BSA interaction studies of the complexes {[Na6{VO(μ-O)}2(μ-OH)4(μ4-slox)].DMF}∞ (1) and [Na6{VO(μ-O)}2(μ-OH)4(μ4-nph)]∞ (4) revealed strong binding affinity. Moreover, the catalytic studies of the complexes (1) and (4) were found to be effective for the oxidation of alcohols into their corresponding aldehydes and ketones and bromination of some organic substrates in the presence of H2O2 as an oxidizing agent.
- Borthakur, Rosmita,Dhanpat, Shobha A.,Kumar, Arvind,Kurbah, Sunshine D.,Lal, Ram A.,Syiemlieh, Ibanphylla
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- An expeditious and efficient method for the oxidation of benzyl alcohols by homogeneous electrolysis
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A greener and inexpensive electrochemical method has been developed for the oxidation of benzyl alcohols by homogeneous electrolysis. The electrochemical reaction was carried out in an undivided cell equipped with carbon and stainless steel electrodes at room temperature. The homogeneous solution made up of acetonitrile/water containing substrate and ammonium bromide with a catalytic amount of H2SO4 as supporting electrolyte. The reaction condition was optimized with various electrochemical experimental parameters and evaluated with various substituted benzyl alcohols to result in excellent yield of aldehydes (>83%).
- Jagatheesan, Rathinavel,Shanmugavelan, Poovan,Sambathkumar, Subramaniyan,Ramesh, Pugalenthi
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supporting information
p. 3013 - 3022
(2021/08/12)
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- Dioxido-vanadium(V) complex catalyzed oxidation of alcohols and tandem synthesis of oximes: a simple catalytic protocol for C–N bond formation
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We report the synthesis of a vanadium(V) complex characterized by FT-IR and 1H NMR spectroscopy. The structure of the complex was established by single crystal X-ray crystallography. We also carried out the catalytic oxidation of benzyl alcohol, hetero-aryl alcohols and propargylic alcohols. Tandem synthesis of oximes from alcohols were also carried out using our vanadium(V) complex. The newly synthesized complex acts as a catalyst for oxidation reactions and tandem synthesis of oxime from alcohols.
- Kurbah, Sunshine Dominic
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p. 905 - 918
(2021/02/03)
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- A porphyrin-conjugated TiO2/CoFe2O4nanostructure photocatalyst for the selective production of aldehydes under visible light
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We investigated the photocatalytic performance of a magnetic nanohybrid of CoFe2O4 and TiO2 hetero-nanostructures (TiO2/CoFe2O4) conjugated with zinc tetrakis carboxyphenyl porphyrin (ZnTCPP) for controlled oxidation of alcohols to aldehydes under visible
- Ghobadifard, Mahdieh,Safaei, Elham,Radovanovic, Pavle V.,Mohebbi, Sajjad
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p. 8032 - 8044
(2021/05/21)
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- Aerobic epoxidation of styrene over Zr-based metal-organic framework encapsulated transition metal substituted phosphomolybdic acid
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Catalytic epoxidation of styrene with molecular oxygen is regarded as an eco-friendly alternative to producing industrially important chemical of styrene oxide (STO). Recent efforts have been focused on developing highly active and stable heterogeneous catalysts with high STO selectivity for the aerobic epoxidation of styrene. Herein, a series of transition metal monosubstituted heteropolyacid compounds (TM-HPAs), such as Fe, Co, Ni or Cu-monosubstituted HPA, were encapsulated in UiO-66 frameworks (denoted as TM-HPA@UiO-66) by direct solvothermal method, and their catalytic properties were investigated for the aerobic epoxidation of styrene with aldehydes as co-reductants. Among them, Co-HPA@UiO-66 showed relatively high catalytic activity, stability and epoxidation selectivity at very mild conditions (313 K, ambient pressure), that can achieve 82 % selectivity to STO under a styrene conversion of 96 % with air as oxidant and pivalaldehyde (PIA) as co-reductant. In addition, the hybrid composite catalyst can also efficiently catalyze the aerobic epoxidation of a variety of styrene derivatives. The monosubstituted Co atoms in Co-HPA@UiO-66 are the main active sites for the aerobic epoxidation of styrene with O2/PIA, which can efficiently converting styrene to the corresponding epoxide through the activation of the in-situ generated acylperoxy radical intermediate.
- Hu, Dianwen,Song, Xiaojing,Zhang, Hao,Chang, Xinyu,Zhao, Chen,Jia, Mingjun
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- C70Fullerene Catalyzed Photoinduced Aerobic Oxidation of Benzylamines to Imines and Aldehydes
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C70 fullerene catalyzed photoinduced oxidation of benzylic amines at ambient conditions has been explored here. The developed strategy's main feature includes the additive/oxidant-free conversion of benzylic amine to corresponding imine and aldehydes. The reaction manifests broad substrate scope with excellent function group leniency and is applicable up to the gram scale. Further, symmetrical secondary amines can also be synthesized from benzylic amine in a one-pot two-step process. Various experiments and density functional theory studies revealed that the current reaction involves the generation of reactive oxygen species, single electron transfer reaction, and benzyl radical formation as key steps under photocatalytic conditions.
- Kumar, Inder,Kumar, Rakesh,Gupta, Shiv Shankar,Sharma, Upendra
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supporting information
p. 6449 - 6457
(2021/05/29)
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- One-Pot Direct Oxidation of Primary Amines to Carboxylic Acids through Tandem ortho-Naphthoquinone-Catalyzed and TBHP-Promoted Oxidation Sequence
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Biomimetic oxidation of primary amines to carboxylic acids has been developed where the copper-containing amine oxidase (CuAO)-like o-NQ-catalyzed aerobic oxidation was combined with the aldehyde dehydrogenase (ALDH)-like TBHP-mediated imine oxidation protocol. Notably, the current tandem oxidation strategy provides a new mechanistic insight into the imine intermediate and the seemingly simple TBHP-mediated oxidation pathways of imines. The developed metal-free amine oxidation protocol allows the use of molecular oxygen and TBHP, safe forms of oxidant that may appeal to the industrial application.
- Kim, Hun Young,Oh, Kyungsoo,Si, Tengda
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supporting information
p. 18150 - 18155
(2021/12/09)
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- Selective oxidation of alkenes to carbonyls under mild conditions
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Herein, a practical and sustainable method for the synthesis of aldehydes, ketones, and carboxylic acids from an inexpensive olefinic feedstock is described. This transformation features very sustainable and mild conditions and utilizes commercially available and inexpensive tetrahydrofuran as the additive, molecular oxygen as the sole oxidant and water as the solvent. A wide range of substituted alkenes were found to be compatible, providing the corresponding carbonyl compounds in moderate-to-good yields. The control experiments demonstrated that a radical mechanism is responsible for the oxidation reaction.
- Huo, Jie,Xiong, Daokai,Xu, Jun,Yue, Xiaoguang,Zhang, Pengfei,Zhang, Yilan
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supporting information
p. 5549 - 5555
(2021/08/16)
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- Hydroxyl radical-mediated oxidative cleavage of CC bonds and further esterification reaction by heterogeneous semiconductor photocatalysis
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A hydroxyl radical-mediated aerobic cleavage of alkenes and further sequence esterification reaction for the preparation of carbonyl compounds have been developed by using tubular carbon nitride (TCN) as a general heterogeneous photocatalyst under an oxygen atmosphere with visible light irradiation. This protocol has an excellent substrate scope and gives the desired aldehydes, ketones and esters in moderate to high yields. Importantly, this metal-free procedure employed photogenerated hydroxyl radicals in situ as green oxidation active species, avoiding the present additional initiators. The reaction could be carried out under solar light irradiation and was applicable to large-scale reactions. Furthermore, the recyclable TCN catalyst could be used several times without a significant loss of activities.
- Hong, Mei,Jia, Rui,Miao, Hongyan,Ni, Bangqing,Niu, Tengfei,Wang, Hui
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p. 6591 - 6597
(2021/09/10)
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- METHOD FOR OXIDATIVE CLEAVAGE OF COMPOUNDS WITH UNSATURATED DOUBLE BOND
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A method for oxidative cleavage of a compound with an unsaturated double bond is provided. The method includes the steps of: (A) providing a compound (I) with an unsaturated double bond, a trifluoromethyl-containing reagent, and a catalyst; wherein, the catalyst is represented by Formula (II): M(O)mL1yL2z??(II);wherein, M, L1, L2, m, y, z, R1, R2 and R3 are defined in the specification; and(B) mixing the compound with an unsaturated double bond and the trifluoromethyl-containing reagent to perform an oxidative cleavage of the compound with the unsaturated double bond by using the catalyst in air or under oxygen atmosphere condition to obtain a compound represented by Formula (III):
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Paragraph 0071; 0077
(2021/07/10)
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- Method for oxidative cracking of compound containing unsaturated double bonds
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The invention relates to a method for oxidative cracking of a compound containing unsaturated double bonds. The method comprises the following steps: (A) providing a compound (I) containing unsaturated double bonds, a trifluoromethyl-containing reagent and a catalyst, wherein the catalyst is shown as a formula (II): M(O)mL1yL2z (II), M, L1, L2, m, y, z, R1, R2 and R3 being defined in the specification; and (B) mixing the compound containing the unsaturated double bonds and the trifluoromethyl-containing reagent, and performing an oxidative cracking reaction on the compound containing the unsaturated double bonds in the presence of air or oxygen by using the catalyst to obtain a compound represented by formula (III),.
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Paragraph 0108-0114; 0115-0120; 0127-0132; 0185-0187
(2021/07/09)
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- METHOD FOR OXIDATIVE CLEAVAGE OF COMPOUNDS WITH UNSATURATED DOUBLE BOND
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A method for oxidative cleavage of a compound with an unsaturated double bond is provided. The method comprises the following step: (A) providing a compound (I) with an unsaturated double bond, a reagent with trifluoromethyl, and a catalyst; wherein the catalyst is represented by the following formula (II): M(O)mL1yL2z (II); wherein, M, L1, L2, m, y, z, R1, R2 and R3 are defined in the specification; and (B) mixing the compound with an unsaturated double bond and the reagent with a trifluoromethyl to perform an oxidation of the compound with the unsaturated double bond by using the catalyst at air or an oxygen condition to get a compound presented as formula (III):
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Paragraph 0053-0054; 0062-0063
(2021/03/19)
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- Samarium-based Grignard-type addition of organohalides to carbonyl compounds under catalysis of CuI
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Grignard-type additions were readily achieved under the mediation of CuI (10 mol%) and samarium (2 equiv.) by employing various organohalides,e.g.benzyl, aryl, heterocyclic and aliphatic halides (Cl, Br or I), and diverse carbonyl compounds (e.g.carbonic esters, carboxylic esters, acid anhydrides, acyl chlorides, ketones, aldehydes, propylene epoxides and formamides) to afford alcohols, ketones and aldehydes, respectively, with high efficiency and chemoselectivity, in which the organosamarium intermediate might be involved.
- Liu, Chen,Liu, Yongjun,Qi, Yan,Song, Bin,Wang, Liang,Xiao, Shuhuan
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supporting information
p. 6169 - 6172
(2021/06/30)
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- PhIO-Mediated oxidative dethioacetalization/dethioketalization under water-free conditions
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Treatment of thioacetals and thioketals with iodosobenzene in anhydrous DCM conveniently afforded the corresponding carbonyl compounds in high yields under water-free conditions. The mechanistic studies indicate that this dethioacetalization/dethioketalization process does not need water and the oxygen of the carbonyl products comes from the hypervalent iodine reagent.
- Du, Yunfei,Ouyang, Yaxin,Wang, Xi,Wang, Xiaofan,Yu, Zhenyang,Zhao, Bingyue,Zhao, Kang
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- A Magnetically Recyclable Palladium-Catalyzed Formylation of Aryl Iodides with Formic Acid as CO Source: A Practical Access to Aromatic Aldehydes
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A magnetically recyclable palladium-catalyzed formylation of aryl iodides under CO gas-free conditions has been developed by using a bidentate phosphine ligand-modified magnetic nanoparticles-anchored- palladium(II) complex [2P-Fe 3O 4@SiO 2-Pd(OAc) 2] as catalyst, yielding a wide variety of aromatic aldehydes in moderate to excellent yields. Here, formic acid was employed as both the CO source and the hydrogen donor with iodine and PPh 3as the activators. This immobilized palladium catalyst can be obtained via a simple preparative procedure and can be facilely recovered simply by using an external magnetic field, and reused at least 9 times without any apparent loss of catalytic activity.
- You, Shengyong,Zhang, Rongli,Cai, Mingzhong
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p. 1962 - 1970
(2021/01/25)
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- Merging N-Hydroxyphthalimide into Metal-Organic Frameworks for Highly Efficient and Environmentally Benign Aerobic Oxidation
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Two highly efficient metal-organic framework catalysts TJU-68-NHPI and TJU-68-NDHPI have been successfully synthesized through solvothermal reactions of which the frameworks are merged with N-hydroxyphthalimide (NHPI) units, resulting in the decoration of pore surfaces with highly active nitroxyl catalytic sites. When t-butyl nitrite (TBN) is used as co-catalyst, the as-synthesized MOFs are demonstrated to be highly efficient and recyclable catalysts for a novel three-phase heterogeneous oxidation of activated C?H bond of primary and secondary alcohols, and benzyl compounds under mild conditions. Based on the high efficiency and selectivity, an environmentally benign system with good sustainability, mild conditions, simple work-up procedure has been established for practical oxidation of a wide range of substrates.
- Wang, Man,Liang, Gan,Wang, Yunhao,Fan, Tao,Yuan, Baoling,Liu, Mingxian,Yin, Ying,Li, Liangchun
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supporting information
p. 9674 - 9685
(2021/06/09)
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- DIBALH: From known fundamental to an unusual reaction; Chemoselective partial reduction of tertiary amides in the presence of esters
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This study presents a quick and reliable approach to the chemoselective partial reduction of tertiary amides to aldehydes in the presence of readily reducible ester groups using commercial DIBALH reagent. Moreover, the developed method was also extended to multi-functional molecules bearing ester moieties, which were successfully chemoselectively reduced to the corresponding aldehydes. This journal is
- An, Duk Keun,Heo, Yu Jin,Jaladi, Ashok Kumar,Kim, Hyun Tae
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p. 33809 - 33813
(2021/12/09)
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- Atomically Dispersed Pt-N3C1Sites Enabling Efficient and Selective Electrocatalytic C-C Bond Cleavage in Lignin Models under Ambient Conditions
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Selective cleavage of C-C linkages is the key and a challenge for lignin degradation to harvest value-added aromatic compounds. To this end, electrocatalytic oxidation presents a promising technique by virtue of mild reaction conditions and strong sustainability. However, the existing electrocatalysts (traditional bulk metal and metal oxides) for C-C bond oxidative cleavage suffer from poor selectivity and low product yields. We show for the first time that atomically dispersed Pt-N3C1sites planted on nitrogen-doped carbon nanotubes (Pt1/N-CNTs), constructed via a stepwise polymerization-carbonization-electrostatic adsorption strategy, are highly active and selective toward Cα-Cβbond cleavage in β-O-4 model compounds under ambient conditions. Pt1/N-CNTs exhibits 99% substrate conversion with 81% yield of benzaldehyde, which is exceptional and unprecedented compared with previously reported electrocatalysts. Moreover, Pt1/N-CNTs using only 0.41 wt % Pt achieved a much higher benzaldehyde yield than those of the state-of-the-art bulk Pt electrode (100 wt % Pt) and commercial Pt/C catalyst (20 wt % Pt). Systematic experimental investigation together with density functional theory (DFT) calculation suggests that the superior performance of Pt1/N-CNTs arises from the atomically dispersed Pt-N3C1sites facilitating the formation of a key Cβradical intermediate, further inducing a radical/radical cross-coupling path to break the Cα-Cβbond. This work opens up opportunities in lignin valorization via a green and sustainable electrochemical route with ultralow noble metal usage.
- Cui, Tingting,Ma, Lina,Wang, Shibin,Ye, Chenliang,Liang, Xiao,Zhang, Zedong,Meng, Ge,Zheng, Lirong,Hu, Han-Shi,Zhang, Jiangwei,Duan, Haohong,Wang, Dingsheng,Li, Yadong
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supporting information
p. 9429 - 9439
(2021/07/19)
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- A Remote ‘Imidazole’-Based Ruthenium(II) Para-Cymene Pre-catalyst for the Selective Oxidation Reaction of Alkyl Arenes and Alcohols
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Herein we disclosed the use of a remote ‘imidazole’-based precatalyst [(para-cymene)RuII(L)Cl]+, C-1 where L=2-(4-substituted-phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline) for the selective oxidation of a variety of alkyl arenes/heteroarenes and alcohols to their corresponding aldehydes or ketones in presence of tert-butyl hydroperoxide (TBHP). The remote ‘imidazole’ moiety present in the complex facilitates the activation of oxidant and subsequent generation of active species via the release of para-cymene from C-1, which in-turn was less effective without the ‘imidazole’ moiety. The mechanistic features of C-1 promoted oxidation of alkyl arenes were also assessed from spectroscopic, kinetic, and few control experiments. The substrate scope for C-1 promoted oxidation reaction was assessed based on the selective oxidation of 27-different alkyl arenes/heteroarenes and 25 different alcohols to their corresponding aldehydes/ketones in moderate to good yields.
- Dutta, Manali,Bania, Kusum K.,Pratihar, Sanjay
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p. 926 - 932
(2020/03/05)
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- Selective oxidation of alcohols by using CoFe2O4/Ag2MoO4 as a visible-light-driven heterogeneous photocatalyst
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A new magnetic photocatalyst, CoFe2O4/Ag2MoO4, was fabricated by a facile in situ coprecipitation method and characterized by FT-IR, XRD, SEM, TEM, EDX, VSM, DRS, and PL analysis. The photocatalytic performance
- Ghobadifard, Mahdieh,Mohebbi, Sajjad,Radovanovic, Pavle V.
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p. 2858 - 2867
(2020/03/03)
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- Solvent-free, microwave assisted oxidation of alcohols with 4-hydroxypyridinium chlorochromate functionalized silica gel
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4-Hydroxypyridinium chlorochromate functionalized silica gel was found to be an efficient and reusable oxidant for the very fast oxidation of primary and secondary alcohols to the corresponding carbonyl compounds under solventfree conditions and microwave irradiation in excellent yields.
- AHMADI, Sayed Ali,GHALEHBANDI, Shermineh Sadat,GHAZANFARI, Dadkhoda,SHEIKHHOSSEINI, Enayatollah
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p. 283 - 289
(2020/10/06)
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- Metal-bipyridinium photocatalyst as well as preparation method and application thereof
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The invention belongs to the field of photocatalysis, and particularly relates to a metal onium salt photocatalyst, a preparation method and an application thereof. The catalyst is a compound composedof bipyridinium salt and metal salt; the bipyridinium s
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Paragraph 0056-0059; 0061-0064
(2020/07/21)
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- ALK5 INHIBITORS
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The present disclosure provides inhibitors of activin receptor-like kinase 5 (ALK5). Also disclosed are methods to modulate the activity of ALK5 and methods of treatment of disorders mediated by ALK5.
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- Synthesis and structure activity relationships of cyanopyridone based anti-tuberculosis agents
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Mycobacterium tuberculosis, the causative agent of tuberculosis, relies on thymidylate kinase (MtbTMPK) for the synthesis of thymidine triphosphates and thus also DNA synthesis. Therefore, this enzyme constitutes a potential Achilles heel of the pathogen. Based on a previously reported MtbTMPK 6-aryl-substituted pyridone inhibitor and guided by two co-crystal structures of MtbTMPK with pyridone- and thymine-based inhibitors, we report the synthesis of a series of aryl-shifted cyanopyridone analogues. These compounds generally lacked significant MtbTMPK inhibitory potency, but some analogues did exhibit promising antitubercular activity. Analogue 11i demonstrated a 10-fold increased antitubercular activity (MIC H37Rv, 1.2 μM) compared to literature compound 5. Many analogues with whole-cell antimycobacterial activity were devoid of significant cytotoxicity.
- Boshoff, Helena I. M.,Caljon, Guy,Forbes, He Eun,Hulpia, Fabian,Jian, Yanlin,Munier-Lehmann, Héle?ne,Risseeuw, Martijn D. P.,Van Calenbergh, Serge
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- 9,10-Dihydroanthracene auto-photooxidation efficiently triggered photo-catalytic oxidation of organic compounds by molecular oxygen under visible light
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The development of mild and efficient process for the selective oxidation of organic compounds by molecular oxygen (O2) can be one of the key technologies for synthesizing oxygenates. This paper discloses an efficient and mild synthesis protocol for the O2-involved ethylbenzene (EB) photooxidation triggered by 910-dihydroanthracene (DHA) auto- photooxidation in acetone under visible light illumination, which can achieve 87.7 percent EB conversion and 99.5 percent acetylacetone (ACP) selectivity under ambient conditions. Also, 62.9 percent EB conversion and 96.3 percent ACP selectivity is obtained in air atmosphere. Furthermore, this protocol has a good adaptability for the photooxidation of other organic substrates such as tetrahydronaphthalene, diphenylmethane, toluene, cyclohexane, cyclohexene, alcohol, methylfuran and thioether to their corresponding oxygenates. A series of control and quenching tests, combined with EPR spectra, suggest that the photo-excited DHA can transfer its photo-electron to O2 to yield a superoxide radical anion (O2??), then DHA is preferentially oxidized to anthraquinone (AQ) by the active O2?? owing to its high reactivity. Finally, the in situ generated AQ as an active photo-catalyst can achieve the photooxidation of EB and other organic compounds by O2. The present photo-autoxidation protocol gives a good example for the O2-based selective oxidation of inert hydrocarbons under mild conditions.
- Chen, Mengke,Deng, Youer,Fu, Zaihui,Hu, Wenwei,Jiang, Dabo,Liu, Yachun,Mao, Feng,Su, Anqun,Yang, Bo,Zhang, Chao
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- Visible-light mediated facile dithiane deprotection under metal free conditions
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Visible light mediated facile and selective dithiane deprotection under metal free conditions is developed. Eosin Y (1 mol%) proved to be an effective catalyst for the dithiane deprotection under the ambient photoredox conditions. The standard household compact fluorescent light source (CFL bulb) proved to be effective under open-air conditions in aqueous acetonitrile at room temperature. The protocol that exhibits a broad substrate scope and functional group tolerance has been shown to expand to a range of transformations for the electron-rich and -deficient thioacetals and thioketals. The synthetic utility of this protocol has also been demonstrated by gram-scale application.
- Dharpure, Pankaj D.,Bhowmick, Anindita,Warghude, Prakash K.,Bhat, Ramakrishna G.
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- Spinel Structured Copper Ferrite Nano Catalyst with Magnetic Recyclability for Oxidative Decarboxylation of Phenyl Acetic Acids
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Abstract: A simple, efficient and environmentally benign method has been discussed for the synthesis of aldehydes and ketones by the oxidative decarboxylation of phenylacetic acid under ligand free condition using simple, efficient, preparatively easy, magnetically recoverable and low cost spinel CuFe2O4 nanoparticles. The catalyst was characterised using powder-XRD, FTIR, FE-SEM, EDX, VSM and HRTEM. The recyclability was examined and the results showed that the catalyst remained almost equally active up to five consecutive cycles. Graphic Abstract: Spinel Structured Copper Ferrite is a very efficient nano catalyst for Oxidative decarboxylation of Phenyl acetic acids and can be reused up to five cycles without significant loss in catalytic activity.[Figure not available: see fulltext.].
- Rahman, Taskia,Borah, Geetika,Gogoi, Pradip K.
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p. 2267 - 2272
(2020/02/18)
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- Cerium(IV) Carboxylate Photocatalyst for Catalytic Radical Formation from Carboxylic Acids: Decarboxylative Oxygenation of Aliphatic Carboxylic Acids and Lactonization of Aromatic Carboxylic Acids
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We found that in situ generated cerium(IV) carboxylate generated by mixing the precursor Ce(OtBu)4 with the corresponding carboxylic acids served as efficient photocatalysts for the direct formation of carboxyl radicals from carboxylic acids under blue light-emitting diodes (blue LEDs) irradiation and air, resulting in catalytic decarboxylative oxygenation of aliphatic carboxylic acids to give C-O bond-forming products such as aldehydes and ketones. Control experiments revealed that hexanuclear Ce(IV) carboxylate clusters initially formed in the reaction mixture and the ligand-to-metal charge transfer nature of the Ce(IV) carboxylate clusters was responsible for the high catalytic performance to transform the carboxylate ligands to the carboxyl radical. In addition, the Ce(IV) carboxylate cluster catalyzed direct lactonization of 2-isopropylbenzoic acid to produce the corresponding peroxy lactone and ?3-lactone via intramolecular 1,5-hydrogen atom transfer (1,5-HAT).
- Hirosawa, Keishi,Mashima, Kazushi,Satoh, Tetsuya,Shinohara, Koichi,Shirase, Satoru,Tamaki, Sota,Tsurugi, Hayato
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supporting information
(2020/03/25)
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- Selective Solvent-Free and Additive-Free Oxidation of Primary Benzylic C–H Bonds with O2 Catalyzed by the Combination of Metalloporphyrin with N-Hydroxyphthalimide
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Abstract: A protocol for solvent-free and additive-free oxidation of primary benzylic C–H bonds with O2 was presented through adjusting the combination of metalloporphyrins and NHPI as binary catalysts to overcome the deficiencies encountered in current oxidation systems. The effects of reaction temperature, porphyrin structure, central metal, catalyst loading and O2 pressure were investigated systematically. For the optimized combination of T(2-OCH3)PPCo and NHPI, all the primary benzylic C–H bonds could be functionalized efficiently and selectively at 120 °C and 1.0?MPa O2 with aromatic acids as the primary products. The selectivity towards aromatic acids could reach up to 70–95% in the conversion of more than 30% for most of the substrates possessing primary benzylic C–H bonds in the metalloporphyrin loading of 0.012% (mol/mol). And the superior performance of T(2-OCH3)PPCo among the metalloporphyrins investigated was mainly attributed to its high efficiency in charge transfer and fewer positive charges around central metal Co (II) which favored the adduction of O2 to cobalt (II) forming the high-valence metal-oxo complex followed by the production of phthalimide N-oxyl radical (PINO) and the initiation of the catalytic oxidation cycle. This work would provide not only an efficient protocol in utilization of hydrocarbons containing primary benzylic C–H bonds, but also a significant reference in the construction of more efficient C–H bonds oxidation systems. Graphic Abstract: The solvent-free and additive-free oxidation of primary benzylic C–H bonds with O2 was presented through adjusting the combination of metalloporphyrins and NHPI as binary catalysts, and the highest selectivity towards aromatic acid reached up to 95.1% with the conversion of 88.5% in the optimized combination of T(2-OCH3)PPCo and NHPI.[Figure not available: see fulltext.].
- Shen, Hai-Min,Qi, Bei,Hu, Meng-Yun,Liu, Lei,Ye, Hong-Liang,She, Yuan-Bin
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p. 3096 - 3111
(2020/04/29)
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- Continuous flow synthesis of aryl aldehydes by Pd-catalyzed formylation of phenol-derived aryl fluorosulfonates using syngas
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This communication describes the palladium-catalyzed reductive carbonylation of aryl fluorosulfonates (ArOSO2F) using syngas as an inexpensive and sustainable source of carbon monoxide and hydrogen. The conversion of phenols to aryl fluorosulfonates can be conveniently achieved by employing the inexpensive commodity chemical sulfuryl fluoride (SO2F2) and base. The developed continuous flow formylation protocol requires relatively low loadings for palladium acetate (1.25 mol%) and ligand (2.5 mol%). Good to excellent yields of aryl aldehydes were obtained within 45 min for substrates containing electron withdrawing substituents, and 2 h for substrates containing electron donating substituents. The optimal reaction conditions were identified as 120 °C temperature and 20 bar pressure in dimethyl sulfoxide (DMSO) as solvent. DMSO was crucial in suppressing Pd black formation and enhancing reaction rate and selectivity. This journal is
- Hanselmann, Paul,Hone, Christopher A.,Hu, Guixian,K?ckinger, Manuel,Kappe, C. Oliver
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p. 22449 - 22453
(2020/07/03)
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- Decarboxylative formylation of aryl halides with glyoxylic acid by palladium catalysis under oxygen
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A new free radical/palladium cooperative catalyzed formylation of aryl halides with glyoxylic acid as the formyl source under oxygen conditions has been developed. Various aromatic and heteroaromatic aldehydes were produced in medium to good yields.
- Cao, Hualiang,Pu, Weiwen,Zhang, Jie,Yan, Peijun,Zhang, Jun,Xu, Sheng
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supporting information
p. 1287 - 1290
(2020/08/21)
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- Heterogeneous carbon nitride photocatalyst for C-C bond oxidative cleavage of vicinal diols in aerobic micellar medium
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A green and efficient visible-light promoted aerobic oxidative C-C bond cleavage of vicinal diols in micellar medium has been developed. This protocol used graphitic carbon nitride with nitrogen vacancies (CN620) as a metal-free recyclable photocatalyst and CTAB as surfactant in water. Control experiments and the ESR results indicated that superoxide radicals and valence band holes played an important role in the reaction. Further isotope experiments suggested both a β-scission/HAT pathway and an oxidation/hydrolysis/dehydration pathway for the reaction, which is different from previous reports. The semiconductor/micellar catalyst system can be recycled at least 10 times without a significant reduction in activity. Furthermore, this reaction could be carried out under solar light irradiation and was applicable to large-scale reactions with similar results.
- Chen, Jiayang,Chen, Shengjun,Dong, Xinyu,Hong, Mei,Ni, Bangqing,Niu, Tengfei,Zhang, Tianhao
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supporting information
p. 5042 - 5049
(2020/08/25)
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- KMnO4-catalyzed chemoselective deprotection of acetate and controllable deacetylation-oxidation in one pot
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A novel and efficient protocol for chemoselective deacetylation under ambient conditions was developed using catalytic KMnO4. The stoichiometric use of KMnO4 highlighted the dual role of a heterogeneous oxidant enabling direct access to aromatic aldehydes in one-pot sequential deacetylation-oxidation. The reaction employed an alternative solvent system and allowed the clean transformation of benzyl acetate to sensitive aldehyde in a single step while preventing over-oxidation to acids. Use of inexpensive and readily accessible KMnO4 as an environmentally benign reagent and the ease of the reaction operation were particularly attractive, and enabled the controlled oxidation and facile cleavage of acetate in a preceding step. This journal is
- Gurawa, Aakanksha,Kumar, Manoj,Rao, Dodla S.,Kashyap, Sudhir
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supporting information
p. 16702 - 16707
(2020/10/27)
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- One-pot, oxidative and selective conversion of benzylic silyl and tetrahydropyranyl ethers to gem-dichlorides using trichloroisocyanuric acid and triphenylphosphine as an efficient and neutral system
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A one-pot and oxidative method is described for the first time for the conversion of benzylic trimethylsilyl (TMS) and tetrahydropyranyl (THP) ethers to gem-dichlorides using trichloroisocyanuric acid (TCCA) and triphenylphosphine (PPh3) in neutral media. Various theses substrates containing electron withdrawing or donating groups can be efficiently converted to their corresponding gem-dichlorides in good to excellent yields. The present method shows a high degree of chemoselectivity, and due to its one-pot nature is in accordance with green chemistry.
- Khadem Moghaddam, Roqayeh,Aghapour, Ghasem
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p. 398 - 406
(2020/11/19)
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- Rhodium-catalyzed reductive carbonylation of aryl iodides to arylaldehydes with syngas
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The reductive carbonylation of aryl iodides to aryl aldehydes possesses broad application prospects. We present an efficient and facile Rh-based catalytic system composed of the commercially available Rh salt RhCl3·3H2O, PPh3 as phosphine ligand, and Et3N as the base, for the synthesis of arylaldehydes via the reductive carbonylation of aryl iodides with CO and H2 under relatively mild conditions with a broad substrate range affording the products in good to excellent yields. Systematic investigations were carried out to study the experimental parameters. We explored the optimal ratio of Rh salt and PPh3 ligand, substrate scope, carbonyl source and hydrogen source, and the reaction mechanism. Particularly, a scaled-up experiment indicated that the catalytic method could find valuable applications in industrial productions. The low gas pressure, cheap ligand and low metal dosage could significantly improve the practicability in both chemical researches and industrial applications.
- Chen, Suqing,Liu, Zhenghui,Mu, Tiancheng,Wang, Peng,Yan, Zhenzhong,Yu, Dongkun,Zhao, Xinhui
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p. 645 - 656
(2020/05/14)
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- Cobalt(ii)-catalyzed benzylic oxidations with potassium persulfate in TFA/TFAA
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A cobalt-catalyzed C(sp3)-H oxygenation reaction to furnish aldehyde was herein reported. This transformation demonstrated high chemo-selectivity, and tolerated various methylarenes bearing electron-withdrawing substituents. This reaction provided rapid access to diverse aldehydes form methylarenes. Notably, TFA/TFAA was used for the first time as a mixed solvent in cobalt-catalyzed oxygenation of benzylic methylenes.
- Li, Tianlei,Li, Jishun,Zhu, Zihao,Pan, Weidong,Wu, Song
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p. 20879 - 20883
(2019/07/12)
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- Europium-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones and Photoluminescence Tracking
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Europium is a lanthanide rare-earth metal and is known as a key element in luminophore development. Since europium has two relatively stable oxidation states, Eu2+ and Eu3+, which is exceptional among the various lanthanide elements, we have developed a europium-catalyzed aerobic oxidation with external oxidants utilizing the redox cycle of Eu2+/Eu3+. The reaction was performed under mild conditions with a wide substrate scope. The photoluminescence spectra clearly demonstrate the oxidation state changes that occur during the presented europium-catalyzed aerobic oxidation. (Figure presented.).
- Kim, Seongwoo,Kim, Youngik,Jin, Hyomin,Park, Myung Hwan,Kim, Youngjo,Lee, Kang Mun,Kim, Min
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supporting information
(2019/02/05)
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- Selective Aerobic Oxidation of Benzylic Alcohols Catalyzed by a Dicyclopropenylidene-Ag(I) Complex
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The unprecedented synthesis, single-crystal X-ray structure, and first catalytic application of a dicarbene-Ag(I) complex [Ag(BAC)2][CO2CF3] (BAC = bis(diisopropyl)aminocyclopropenylidene) is reported. This novel complex provides a versatile catalytic platform for selective aerobic oxidation of benzylic alcohols to aldehyde or ketone products in high yields. Ease of experimental execution coupled with the use of abundant atmospheric molecular oxygen as an oxidant and low catalyst loading are inherit strengths of these oxidations.
- Mir, Roya,Rowshanpour, Rozhin,Dempsey, Katie,Pilkington, Melanie,Dudding, Travis
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p. 5726 - 5731
(2019/05/10)
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- Metal-ligand cooperativity in a ruthenium(II) complex of bis-azoaromatic ligand for catalytic dehydrogenation of alcohols
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Herein a new Ru-phosphine complex (1) with molecular formula [RuL(PPh3)Cl2] is reported where L is a redox active pincer ligand 2,6-bis(phenylazo)pyridine. The isolated complex has been characterized by usual spectroscopic techniques including single crystal X-ray crystallographic analysis. Complex 1 efficiently catalyzes aerobic oxidation of a wide range of primary and secondary benzylic, allylic, heterocyclic, alicyclic alcohols under mild conditions and is found to be superior over several other Ru (0, +2 and +3), Ru-H and Ru-PPh3 catalysts. Mechanistic studies indicate that a transient Ru-H intermediate is formed in the catalytic cycle which gets switched into a Ru-hydrazo intermediate via hydrogen-walking mechanism. The catalyst is regenerated by aerial oxidation producing H2O2 as a by-product.
- Saha, Tanushri,Pramanick, Rajib,Sengupta, Debabrata,Goswami, Sreebrata
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p. 160 - 166
(2018/09/29)
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- Efficient acceptorless photo-dehydrogenation of alcohols and: N -heterocycles with binuclear platinum(ii) diphosphite complexes
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Although photoredox catalysis employing Ru(ii) and Ir(iii) complexes as photocatalysts has emerged as a versatile tool for oxidative C-H functionalization under mild conditions, the need for additional reagents acting as electron donor/scavenger for completing the catalytic cycle undermines the practicability of this approach. Herein we demonstrate that photo-induced oxidative C-H functionalization can be catalysed with high product yields under oxygen-free and acceptorless conditions via inner-sphere atom abstraction by binuclear platinum(ii) diphosphite complexes. Both alcohols (51 examples), particularly the aliphatic ones, and saturated N-heterocycles (24 examples) can be efficiently dehydrogenated under light irradiation at room temperature. Regeneration of the photocatalyst by means of reductive elimination of dihydrogen from the in situ formed platinum(iii)-hydride species represents an alternative paradigm to the current approach in photoredox catalysis.
- Zhong, Jian-Ji,To, Wai-Pong,Liu, Yungen,Lu, Wei,Che, Chi-Ming
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p. 4883 - 4889
(2019/05/16)
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- Aerobic alcohol oxidation catalyzed by CuO-rectorite/TEMPO in water
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An environmentally benign CuO-rectorite was prepared by calcining the co-precipitation product of Cu2+ with an acid-activated rectorite at pH 6. It could be well dispersed in water and used as a co-catalyst with TEMPO to selectively aerobically oxidize alcohols to aldehydes. The conversion of most primary benzylic alcohols was very high under optimized conditions. Interestingly, the oxidation protocol also allowed highly selective transformation of benzylic alcohols containing a phenolic hydroxyl group into the corresponding aldehydes. Additionally, very little copper was leached from the catalyst during the catalytic reaction. CuO-rectorite could be reused by centrifugation and washed with acetonitrile and water. At the same time, its catalytic activity remained high.
- Liu, Wanghui,Yang, Jianhong,Cai, Jun
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p. 549 - 561
(2018/10/15)
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- Synthesis, crystal structure and reactivity of homobimetallic vanadium(V) complexes derived from oxaloyldihydrazone ligands
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Treatment of V2O5 with dihydrazone ligands (H4L) (disalicylaldehydeoxaloyldihydrazone (H4L1 = H4slox), bis(2-hydroxy-1-naphthaldehyde)oxaloyldihydrazone (H4L2 = H4nph) and bis(5-bromosalicylaldehyde)oxaloyldihydrazone (H4L3 = H4sloxBr)) in methanol leads to the formation of homobimetallic vanadium(V) complexes of the composition [(CH3)2NH2]2[(VO2)2(L)]·nH2O, where n = 2 (1, 2) and n = 4 (3). The reaction of complexes 1–3 with H2O2 results in the formation of bis(monooxidoperoxidovanadate(V)) complexes[{VO(O2)}2(L)]2? and the reaction with HCl leads to the formation of oxidohydroxido species of the composition [(VO(OH)(L)]2?. The complexes show great potential for the oxidation of alcohols and the oxidative bromination of some organic substrates.
- Syiemlieh, Ibanphylla,Asthana, Mrityunjaya,Kurbah, Sunshine D.,Lal, Ram A.
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p. 202 - 216
(2019/06/19)
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