- 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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- AN IMPROVED AND PRACTICAL SYNTHESIS OF 4-FLUOROBENZALDEHYDE BY HALOGEN-EXCHANGE FLUORINATION REACTION
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A process which can afford a large quantity of 4-fluorobenzaldehyde was developed from halogen-exchange of 4-chlorobenzaldehyde with potassium fluoride in aromatic hydrocarbon solvents in the presence of tetraphenylphosphonium bromide plus polyethylene glycol dimethyl ether.The features of the reaction are discussed.
- Yoshida, Yasuo,Kimura, Yoshikazu
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- Synthesis, characterization, crystal structure, and catalytic activity of an end-on azido-bridged polymeric copper(Ii) complex derived from 4-methyl-2- [(3-methylaminopropylimino)methyl]phenol
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An end-on azido-bridged polymeric copper(II) complex, [CuL(μ1,1-N3)]n (HL D 4-methyl-2- [(3-methylaminopropylimino)methyl]phenol), was synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-r
- Liu, Li-Jun
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- Synthesis of an amino-functionalized metal-organic framework at a nanoscale level for gold nanoparticle deposition and catalysis
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In this study, highly dispersed Au nanoparticles have been immobilized on amino-functionalized metal-organic frameworks (MOFs) via a novel absorption/reduction method in solution. The amino functionality of the MOF rapidly coordinated with HAuCl4/su
- Luan, Yi,Qi, Yue,Gao, Hongyi,Zheng, Nannan,Wang, Ge
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- Cobalt(II) supported on ethylenediamine-functionalized nanocellulose as an efficient catalyst for room temperature aerobic oxidation of alcohols
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Ethylenediamine-functionalized nanocellulose complexed with cobalt(II) was found to be a highly efficient heterogeneous catalyst for the room temperature aerobic oxidation of various types of primary and secondary benzylic alcohols into their correspondin
- Shaabani, Ahmad,Keshipour, Sajjad,Hamidzad, Mona,Seyyedhamzeh, Mozhdeh
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- 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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- Highly atom efficient synthesis of 2,2,4,5-tetrasubstituted 3(2H)-furanones having both hydroxyl and amino substituents
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We have developed a highly atom efficient synthesis of tetrasubstituted 3(2H)-furanones from easily accessible starting materials such as C,N-diarylaldonitrones and dibenzoylacetylene. Control experiments revealed that reaction of aldonitrones having electron-withdrawing groups on the C-aryl substituent in polar aprotic solvents exhibited high product selectivity while reaction temperature has only a negligible effect on product yield and selectivity.
- Antony, Jesna,Mathai, Sindhu,Natarajan, Rakesh,P. Musthafa, Sumi,Rappai, John P.,S. Devaky, Karakkattu
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supporting information
(2022/02/25)
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- Functionalized-1,3,4-oxadiazole ligands for the ruthenium-catalyzed Lemieux-Johnson type oxidation of olefins and alkynes in water
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Three arene-ruthenium(II) complexes bearing alkyloxy(5-phenyl-1,3,4-oxadiazol-2-ylamino)(4-trifluoromethylphenyl)methyl ligands were quantitatively obtained through the reaction of (E)-1-(4-trifluoromethylphenyl)-N-(5-phenyl-1,3,4-oxadiazol-2-yl)-methanimine with the ruthenium precursor [RuCl2(η6-p-cymene)]2 in a mixture of the corresponding alcohol and CH2Cl2 at 50 °C. The obtained complexes were fully characterized by elemental analysis, infrared, NMR and mass spectrometry. Solid-state structures confirmed the coordination of the 1,3,4-oxadiazole moiety to the ruthenium center via their electronically enriched nitrogen atom at position 3 in the aromatic ring. These complexes were evaluated as precatalysts in the Lemieux-Johnson type oxidative cleavage of olefins and alkynes in water at room temperature with NaIO4 as oxidizing agent. Good to full conversions of olefins into the corresponding aldehydes were measured, but low catalytic activity was observed in the case of alkynes. In order to get more insight into the mechanism, three analogue arene-ruthenium complexes were synthesized and tested in the oxidative cleavage of styrene. The latter tests clearly demonstrated the importance of the hemilabile alkyloxy groups, which may form more stable (N,O)-chelate intermediates and increase the efficiency of the cis-dioxo-ruthenium(VI) catalyst.
- Hkiri, Shaima,Touil, Soufiane,Samarat, Ali,Sémeril, David
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- Method for efficiently synthesizing fluorine-containing compound
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The invention discloses a method for efficiently synthesizing a fluorine-containing compound, and relates to the field of fluorine-containing compound synthesis. The method is a method for generating a corresponding fluorine atom substituted fluorine-containing compound by reacting aromatic chloride or activated chloride serving as a raw material with potassium fluoride under the action of a novel catalyst. The method disclosed by the invention has the advantages of good product selectivity, high efficiency, mild reaction conditions, simplicity and convenience in operation, convenience in application and the like.
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Paragraph 0058-0061
(2021/06/26)
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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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- La(OH)3nanoparticles immobilized on Fe3O4@chitosan composites as novel magnetic nanocatalysts for sonochemical oxidation of benzyl alcohol to benzaldehyde
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This work introduces an eco-friendly method for immobilization of La(OH)3 nanoparticles on modified Fe3O4 nanoparticles. The structural and morphological characteristics of the nanocatalyst were determined by various analytical techniques including, FT-IR, EDS, FESEM, VSM and XRD. The catalytic efficiency of the Fe3O4@Cs/La(OH)3 composite as a heterogeneous nanocatalyst was evaluated by selective oxidation of benzylic alcohols to aldehydes. The optimum reaction conditions including time, temperature, nanocatalyst dosage, and solvent were investigated for ultrasound-assisted oxidation processes. Furthermore, the magnetic nanocatalyst was recovered up to seven times without considerable activity loss. Furthermore, the proposed nanocomposite had a remarkable effect on reducing the reaction time and enhancing the yield. This journal is
- Fadaeian, Manoochehr,Ghomi, Javad Safaei,Javidfar, Fereshteh
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p. 35988 - 35993
(2021/12/02)
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- Homogeneous CuCl2/TMEDA/TEMPO-Catalyzed chemoselective base- and halogen- free aerobic oxidation of primary alcohols in mild conditions
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This article describes the developing of a base- and halogen- free homogeneous system aiming to chemoselectively oxidize allyl, furyl, aryl and heteroaryl primary alcohols. The current easy-to-handle aerobic system uses few amounts of CuCl2/TMEDA/TEMPO system under mild reaction conditions to produce aldehydes in high yields. Moreover, the CuCl2/TMEDA cyclic voltammetry was measured for the first time, disclosing that TMEDA as ligand substantially affects the redox potential (E1/2) of the couple E1/2Cu2+/Cu+ to E1/2Cu2+/Cu+-TMEDA by 454 mV in the redox system.
- Alves, Otávio A. L.,Chagas, Rafael C. R.,Princival, Jefferson L.,Ribeiro, RogérioT.,Silva, Emmanuel D.,Villar, José A. F. P.
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- Synthesis of TEMPO radical decorated hollow porous aromatic frameworks for selective oxidation of alcohols
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A bottom-up approach was developed to prepare TEMPO radical decorated hollow aromatic frameworks (HPAF-TEMPO) by using TEMPO radical functionalized monomers and SiO2nanospheres as templates. The accessible inner layer, high density of TEMPO sites, and hybrid micro-/mesopores of the HPAF-TEMPO enable the aerobic oxidation of a broad range of alcohols with high efficiency and excellent selectivity.
- Shen, Yan-Ming,Xue, Yun,Yan, Mi,Mao, Hui-Ling,Cheng, Hu,Chen, Zhuo,Sui, Zhi-Wei,Zhu, Shao-Bin,Yu, Xiu-Jun,Zhuang, Jin-Liang
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supporting information
p. 907 - 910
(2021/02/06)
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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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- Method for preparing carbonyl compound by oxidizing alcohol
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The invention provides a method for preparing aldehyde or ketone by alcohol oxidation. Iron nitrate hydrate (Fe (NO) is used as a solvent. 3 )3 · 992 O). 4 - Hydroxyl -2, 2, 6, 6 - tetramethylpiperidine oxide (4 - OH-TEMPO) and carboxylic acid are catalysts, and the alcohol is oxidized to aldehydes or ketones with oxygen or air as an oxidizing agent. Compared with the prior art, water serves as a solvent, so that the pollution-free halogenated hydrocarbon or strong carcinogenic sodium nitrite (NaNO) is avoided. 2 The method is green and environment-friendly, the cost is greatly reduced, and the method is a method suitable for industrial production.
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Paragraph 0026
(2021/09/08)
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- V2O5@TiO2 Catalyzed Green and Selective Oxidation of Alcohols, Alkylbenzenes and Styrenes to Carbonyls
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The versatile application of different functional groups such as alcohols (1° and 2°), alkyl arenes, and (aryl)olefins to construct carbon-oxygen bond via oxidation is an area of intense research. Here, we report a reusable heterogeneous V2O5@TiO2 catalyzed selective oxidation of various functionalities utilizing different mild and eco-compatible oxidants under greener reaction conditions. The method was successfully applied for the alcohol oxidation, oxidative scission of styrenes, and benzylic C?H oxidation to their corresponding aldehydes and ketones. The utilization of mild and eco-friendly oxidizing reagents such as K2S2O8, H2O2 (30 % aq.), TBHP (70 % aq.), broad substrate scope, gram-scale synthesis, and catalyst recyclability are notable features of the developed protocol.
- Upadhyay, Rahul,Kumar, Shashi,Maurya, Sushil K.
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p. 3594 - 3600
(2021/07/02)
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- Selective aerobic oxidation of benzylic and allylic alcohols catalyzed by Cu(OAc)2/TEMPO/Et2NH
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Selective oxidation of benzylic and allylic alcohols to their corresponding aldehyde/ketone derivative without affecting saturated alcohols is still a challenging endeavor in organic synthesis. Various metal complexes, especially the copper complexes in the presence of TEMPO are being used very often for such transformations under aerobic conditions, but they are not selective to allylic and benzylic alcohols. The use of copper salt for oxidation of alcohols in the absence of a ligand are very scarcely studied except for the one catalyzed by CuCl/TEMPO where chloride inhibition and lack of selective oxidation have been noted upon use of CuCl2. Herein we report a Cu(OAc)2 catalyzed and TEMPO mediated selective aerobic oxidation of benzylic and allylic alcohols to aldehyde/ketone in the presence of Et2NH. The method avoids pre-synthesis of the catalyst as in the case of Cu(II)/(I) complexes/TEMPO catalyzed oxidation reactions, requires low catalyst loading, employs cheaper copper salt, and gives excellent selectivity for oxidation of benzylic and allylic alcohols.
- Bez, Ghanashyam,Gogoi, Achinta,Pasupuleti, Bala Gangadhar
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p. 589 - 597
(2021/09/28)
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- Mild oxidation of benzyl alcohols to benzyl aldehydes or ketones catalyzed by visible light
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Induced by visible light, mild oxidation condition to prepare benzyl aldehydes or ketones have been developed by using bromotrichloromethane as photochemical oxidant. This method avoids high temperature, pressure and peroxidation with only visible light as the green driving force.
- Cheng, Dongping,Li, Xiaonian,Ren, Shujian,Xu, Xiaoliang
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supporting information
(2021/07/02)
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- A highly effective green catalyst Ni/Cu bimetallic nanoparticles supported by dendritic ligand for chemoselective oxidation and reduction reaction
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The highly active Ni/Cu bimetallic nanoparticles (NPs) of the different molar ratios of Ni and Cu (1:1, 1:3, 3:1) assisted by dendritic ligand 2,4,6-Tris (di-4-chlorobenzamido)-1,3-diazine were synthesized successfully confirmed by Scanning Electron Microscopy (SEM), Electron Diffraction X-ray (EDX), X-ray fluorescence spectroscopy (XRF), X-ray diffraction (XRD), and Transmission Electron Microscopy (TEM) analysis. These NPs were studied as a heterogeneous catalyst for the chemoselective oxidation of alcohol to the corresponding aldehyde at 30?min and chemoselective reduction of aromatic nitro substituents to the corresponding amino substituents at 20?min, while the Ni/Cu (3:1) NPs were found to be the most effective among other Ni/Cu?(1:1)?and Ni/Cu?(1:3)?NPs at room temperature under mild conditions. The Ni/Cu (3:1) NPs can be recycled for at least five successive runs with no perceptible decrease in catalytic activity. Graphic abstract: [Figure not available: see fulltext.]
- Islam, Md. Sayedul,Khan, Md. Wahab
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p. 2353 - 2369
(2021/01/07)
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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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- Preparation method for synthesizing aryl aldehyde compounds by reducing aryl secondary amide or aryl secondary amide derivative through phenylsilane
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The invention provides a preparation method for synthesizing aryl aldehyde compounds by reducing an aryl secondary amide or aryl secondary amide derivative through phenylsilane. In an inert atmosphere, the aryl secondary amide or an aryl secondary amide derivative is used as a raw material, phenylsilane is used as a reducing agent, 1, 4-dioxane or tetrahydrofuran or diethyl ether is used as a solvent, under the action of isopropyl magnesium chloride, a reaction is performed for 12-48 h at 40-70 DEG C, quenching, separating and purification are performed after the reaction is completed, and the aryl aldehyde product is obtained. The whole preparation process realizes one-step conversion from aryl secondary amide to aryl aldehyde, has the advantages of low cost, mild reaction conditions and high reaction yield, and avoids the use of high-temperature harsh conditions and high-cost noble metal catalysts.
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Paragraph 0032-0036
(2021/11/10)
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- Indium Catalyzed Sequential Regioselective Remote C?H Indolylation and Rearrangement Reaction of Peroxyoxindole
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Indium-catalyzed sequential remote C?H functionalization (C-6 position) and C3-indolylation of peroxyoxindole using indole is described for the synthesis of terindolinone derivatives. Whereas, N-substituted 3-phenyl peroxyoxindole derivatives undergoes consecutive skeletal rearrangement to generate transient carbocation, which has been trapped with indole nucleophile to generate 2-(1H-indol-3-yl)-4-alkyl-benzo[b][1,4]oxazin-3(4H)-one derivatives. In contrast with Indium (III) Chloride, FeCl3 ? 6H2O facilitates oxidative cleavage of the peroxyoxindole (Hock cleavage) and further reaction with indole to afford biologically important trisindoline derivatives. A plausible mechanism has been proposed for these reactions with experimental evidences. (Figure presented.).
- Shaikh, Moseen A.,Ubale, Akash S.,Gnanaprakasam, Boopathy
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supporting information
p. 4876 - 4882
(2021/09/14)
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- Photoinduced FeCl3-Catalyzed Alkyl Aromatics Oxidation toward Degradation of Polystyrene at Room Temperature?
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While polystyrene is widely used in daily life as a synthetic plastic, the subsequently selective degradation is still very challenging and highly required. Herein, we disclose a highly practical and selective reaction for the catalytically efficient oxidation of alkyl aromatics (including 1°, 2°, and 3° alkyl aromatics) to carboxylic acids. While dioxygen was used as the sole terminal oxidant, this protocol was catalyzed by the inexpensive and readily available ferric compound (FeCl3) with irradiation of visible light (blue LEDs) under only 1 atmosphere of O2 at room temperature. This system could further facilitate the selective degradation of polystyrene to benzoic acid, providing an important and practical tool to generate high-value chemical from abundant polystyrene wastes.
- Zhang, Guoxiang,Zhang, Zongnan,Zeng, Rong
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supporting information
p. 3225 - 3230
(2021/09/28)
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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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- 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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- 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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- Aerobic oxidative C?C bond cleavage of aromatic alkenes by a high valency iron-containing perovskite catalyst
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High valency iron-containing perovskite catalyst BaFeO3-dcould efficiently promote the additive-free oxidative C?C bond cleavage of various aromatic alkenes to the corresponding aldehydes or ketones using O2as the sole oxidant. This system was applicable to the gram-scale oxidation of 1,1-diphenylethylene, in which 2.71 g (75% yield) of the analytically pure ketone could be isolated.
- Shibata, Satomi,Kamata, Keigo,Hara, Michikazu
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p. 2369 - 2373
(2021/04/22)
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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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- 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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- 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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- 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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- Method for preparing carbonyl compound through oxidative cleavage of visible light excitation aqueous solution quantum dot catalytic olefin compound
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The invention provides a method for preparing carbonyl compounds through oxidative cleavage of a visible light excitation aqueous solution quantum dot catalytic olefin compound. Belong to photocatalysis synthesis technical field. To the method, an aqueous solution quantum dot is used as a photocatalyst, and an aqueous solution quantum dot activated molecular oxygen catalytic oxidation aromatic alkene compound is excited by visible light to be cracked to prepare a carbonyl compound. Low-loading capacity is used, a simple aqueous solution quantum dot is used as a catalyst, the yield of the carbonyl compound is high, TON more than ten millions are obtained. The reaction conditions are mild, water serves as a main solvent for the reaction, and the carbonyl compound can be obtained by catalytic olefin compound oxidation cracking without addition of a cocatalyst or the like. The method is simple to operate, wide in substrate range and low in cost.
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Paragraph 0044
(2021/11/10)
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- Method for generating benzaldehyde by catalyzing alpha-monosubstituted styrene to be oxidized by N-hydroxyphthalimide
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The invention discloses a method for generating benzaldehyde by catalyzing alpha-mono-substituted styrene to be oxidized through N-hydroxyphthalimide. According to the method, N-hydroxyphthalimide isused as a catalyst, oxygen is used as an oxidizing agent, and an alpha mono-substituted styrene compound is oxidized in an organic solvent to obtain the benzaldehyde derivative. The method has the advantages of simple reaction operation, low cost, mild conditions, high yield, no heavy metal pollution and the like.
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Paragraph 0042-0044
(2021/01/24)
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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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- Thiol-initiated photocatalytic oxidative cleavage of the C=C bond in olefins and its extension to direct production of acetals from olefins
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The oxidative cleavage of olefins to produce aldehydes/ketones is an important reaction in organic syntheses. In this manuscript, a mild and operationally simple protocol for the aerobic oxidation of olefins to produce carbonyl compounds was realized over ZnIn2S4under visible light, using air as the oxidant and a thiol as the initiator. It was proposed that the photogenerated holes over ZnIn2S4attack the thiol to produce thiyl radicals, which initiate the oxidative cleavage of the C=C bond in olefins to produce aldehydes/ketones. By further coupling with the condensation between the as-obtained aldehydes/ketones and alcohols, this strategy can also be applied to the production of different acetals directly from the olefins. This study demonstrates a new pathway to realize the oxidative cleavage of olefins to produce aldehydes/ketones, and also provides a new protocol for the production of acetals directly from the olefins.
- Wang, Xinglin,Li, Yuanyuan,Li, Zhaohui
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p. 1000 - 1006
(2021/02/26)
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- A highly stable metal-organic framework with cubane-like clusters for the selective oxidation of aryl alkenes to aldehydes or ketones
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Triazine derivatives, a class of electron-deficient π-conjugated molecules with high photochemical activity and excellent luminescent characteristics, have been utilized as a kind of electron-acceptor for the construction of molecular cages, luminescent and photochromic materials. In this paper, a novel and highly stable MOF with cubane-like clusters, [Co4(SO4)3(F)3(tpt)2(tatb)] (1) (tpt = 2,4,6-tris-(4-pyridyl)-1,3,5-triazine, H3tatb = 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)tribenzoic acid), has been successfully synthesized based on a triazine derivative, and possesses unprecedented sulfate- and fluoride-bridged cubane-type tetranuclear cobalt clusters and a 3D + 3D → 3D open framework. Compound1shows a rather high BET surface area and exhibits excellent thermal stability and high chemical stability in common solvents and even in acidic or basic solutions (in a pH range from 4 to 12). Moreover, catalytic measurements show that compound1is an excellent heterogeneous catalyst for the selective oxidation of aryl alkenes to aldehydes or ketones with conversions of 97%.
- He, Chixian,Liu, Jiaming,Liu, Jian-Jun,Liu, Teng,Shen, Xianfu,Shen, Xiang
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p. 4667 - 4673
(2021/07/11)
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- Method for preparing aldehyde compounds by oxidative cleavage of carbon-carbon bonds of terminal alkene compounds
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The invention discloses a method for preparing aldehyde compounds by oxidizing and breaking carbon-carbon bonds of terminal alkene compounds. The method comprises the following steps: adding an alkene-terminated compound, an additive and a nitrogen-doped mesoporous carbon-loaded monatomic catalyst into a fatty primary alcohol solvent, putting into a pressure container, sealing, introducing oxygen source gas with a certain pressure, controlling the pressure of the oxygen source gas to be 0.1-1MPa and the reaction temperature to be 80-150 DEG C, and obtaining a reaction product, namely the aldehyde compound. The nitrogen-doped mesoporous carbon-loaded monatomic catalyst adopted by the invention is high in activity, the highest separation yield of the aldehyde compound as a reaction product reaches 99%, the method is wide in application range, the reaction conditions are easy to control, the catalyst can be recycled, the post-treatment is simple, and the method is suitable for industrial production.
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Paragraph 0049-0050; 0089-0090
(2021/06/06)
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- Visible-Light-Driven Oxidative Cleavage of Alkenes Using Water-Soluble CdSe Quantum Dots
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The oxidative cleavage of C=C bonds is an important chemical reaction, which is a popular reaction in the photocatalytic field. However, high catalyst-loading and low turnover number (TON) are general shortcomings in reported visible-light-driven reactions. Herein, the direct oxidative cleavage of C=C bonds through water-soluble CdSe quantum dots (QDs) is described under visible-light irradiation at room temperature with high TON (up to 3.7×104). Under the same conditions, water-soluble CdSe QDs could also oxidize sulfides to sulfoxides with 51–84 % yields and TONs up to 3.4×104. The key features of this photocatalytic protocol include high TONs, wide substrates scope, low catalyst loadings, simple and mild reaction conditions, and molecular O2 as the oxidant.
- Li, Jianing,Zhao, Jingnan,Ma, Cunfei,Yu, Zongyi,Zhu, Hongfei,Yun, Lei,Meng, Qingwei
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p. 4985 - 4992
(2021/10/16)
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- A novel selective oxidative cleavage of C–C bond mediated by black nickel oxide in the presence of molecular oxygen
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A selective aerobic oxidative cleavage of C–C bond is developed with black nickel oxide (NiOx) as the catalyst. For the oxidation of 1-phenyl-1, 2-ethanediol, a 97.5% conversion in 96.7% selectivity of benzaldehyde is obtained under 0.3 MPa of O2 at 140 °C for 3 h. The relationship between the catalytic performance of NiOx and structure is discussed. It is concluded that the existence of Ni3+ should be crucial to the activity of catalyst. Moreover, the recycling experiments showed that the catalyst can retain a high activity even after being reused for five times.
- Meng, Lingwu,Li, Wei,Guo, Pengfei,Wang, Shun,Tong, Xinli
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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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- A decatungstate-based ionic liquid exhibiting a very low dielectric constant suitable for acting as a solvent and a catalyst for the oxidation of organic substrates
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In this contribution, a new POM-based ionic liquid, namely (P6,6,6,14)4[W10O32], was fully characterized. Its viscosity and its very low dielectric constant make this hybrid ionic liquid suitable to be used as a solvent for organic transformations. As a proof of concept, this unique ionic liquid having both solvent and catalyst properties was tested for the catalytic oxidation of various alcohols and alkenes in the presence of H2O2.
- Martinetto, Yohan,Pégot, Bruce,Roch-Marchal, Catherine,Haouas, Mohamed,Cottyn-Boitte, Betty,Camerel, Franck,Jeftic, Jelena,Morineau, Denis,Magnier, Emmanuel,Floquet, Sébastien
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supporting information
p. 9751 - 9755
(2021/06/15)
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- Zirconium-based metal-organic framework as an efficiently heterogeneous photocatalyst for oxidation of benzyl halides to aldehydes
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The development of efficient heterogeneous catalysts for fine chemical synthesis is critical for practical applications. Herein, for the first time, the zirconium-based metal-organic framework (UiO-66-NH2) is applied as an efficiently heterogeneous photocatalyst for conversion of benzyl halides to corresponding aldehydes with high selectivity (about 80 %) and conversion (up to 99 %) in the presence of oxygen and DMF as solvent. Through a series of experiments and analysis, the reaction mechanism is proposed to involve nucleophilic attack of the N-oxide. This study provides a general, environmental and high selective method to prepare benzaldehydes and broadens the application fields of UiO-66-NH2.
- Xue, Ping,Huang, Jiming,Lin, Liguang,Li, Rong,Tang, Mi,Wang, Zhengbang
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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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- Ferric ion concentration-controlled aerobic photo-oxidation of benzylic C–H bond with high selectivity and conversion
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A Fe(III)-promoted highly selective photo-oxidation of benzylic C–H bond delivering relative carbonyl products is reported. By altering the concentration of ferric salt, methylarenes can be selectively oxidized under UV irradiation to furnish aromatic aldehydes or acids, respectively. By this protocol, the oxidation of ethylarenes provides the corresponding acetophenones. The reaction is inferred to involve divergent pathways in different concentrations of catalyst for the alternative selectivity between aldehydes and aicds. The reusable catalyst, high conversion and selectivity make this oxidation a green and economic protocol for the synthesis of aromatic carbonyl compounds.
- Bu, Hongzhong,Gu, Jiefan,Li, Yufeng,Ma, Hongfei,Wan, Yuting,Wu, Zheng-Guang,Zhang, Weijian,Zhou, Ying'ao,Zhu, Hongjun
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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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- Metal- And additive-free C-H oxygenation of alkylarenes by visible-light photoredox catalysis
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A metal- and additive-free methodology for the highly selective, photocatalyzed C-H oxygenation of alkylarenes under air to the corresponding carbonyls is presented. The process is catalyzed by an imide-acridinium that forms an extremely strong photooxidant upon visible light irradiation, which is able to activate inert alkylarenes such as toluene. Hence, this is an easy to perform, sustainable and environmentally friendly oxidation that provides valuable carbonyls from abundant, readily available compounds.
- García Manche?o, Olga,Kuhlmann, Jan H.,Pérez-Aguilar, María Carmen,Piekarski, Dariusz G.,Uygur, Mustafa
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supporting information
p. 3392 - 3399
(2021/05/21)
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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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- Spatially Ordered Arrangement of Multifunctional Sites at Molecule Level in a Single Catalyst for Tandem Synthesis of Cyclic Carbonates
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With fossil energy resources increasingly drying up and gradually causing serious environmental impacts, pursuing a tandem and green synthetic route for a complex and high-value-Added compound by using low-cost raw materials has attracted considerable attention. In this regard, the selective and efficient conversion of light olefins with CO2 into high-value-Added organic cyclic carbonates (OCCs) is of great significance owing to their high atom economy and absence of the isolation of intermediates. To fulfill this expectation, a multifunctional catalytic system with controllable spatial arrangement of varied catalytic sites and stable texture, in particular, within a single catalyst, is generally needed. Here, by using a stepwise electrostatic interaction strategy, imidazolium-based ILs and Au nanoparticles (NPs) were stepwise immobilized into a sulfonic group grafted MOF to construct a multifunctional single catalyst with a highly ordered arrangement of catalytic sites. The Au NPs and imidazolium cation are separately responsible for the selective epoxidation and cycloaddition reaction. The mesoporous cage within the MOF enriches the substrate molecules and provides a confined catalytic room for the tandem catalysis. More importantly, the highly ordered arrangement of the varied active sites and strong electrostatic attraction interaction result in the intimate contact and effective mass transfer between the catalytic sites, which allow for the highly efficient (>74% yield) and stable (repeatedly usage for at least 8 times) catalytic transformation. The stepwise electrostatic interaction strategy herein provides an absolutely new approach in fabricating the controllable multifunctional catalysts, especially for tandem catalysis.
- Chang, Gang-Gang,Chen, Jian,Huang, Ke-Xin,Ke, Shan-Chao,Li, Jia-Xin,Luo, Ting-Ting,Ma, Xiao-Chen,Wu, Jian,Yang, Xiao-Yu
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- Selective and solventless oxidation of organic sulfides and alcohols using new supported molybdenum (VI) complex in microwave and conventional methods
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A new dioxo-molybdenum (VI) complex supported on functionalized Merrifield resin (MR-Mo) has been synthesized and characterized by elemental, scanning electron mcroscopy, energy-dispersive X-ray analysis, TGA, Brunauer–Emmett–Teller method, powder-X-ray d
- Das, Siva Prasad,Boruah, Jeena Jyoti
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- A Strategy for Accessing Aldehydes via Palladium-Catalyzed C?O/C?N Bond Cleavage in the Presence of Hydrosilanes
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We report the catalytic reduction of both active esters and amides by selective C(acyl)?X (X=O, N) cleavage to access aldehyde functionality via a palladium-catalyzed strategy. Reactions are promoted by hydrosilanes as reducing reagents with good to excellent yields and with excellent chemoselectivity for C(acyl)?N and C(acyl)?O bond cleavage. Carboxylic acid C(acyl)?O bonds are activated by 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) to form triazine ester intermediates, which further react with hydrosilanes to yield aldehydes in one-pot two-step procedures. We demonstrate that C(acyl)?O cleavage/formylation offers higher yields and broader substrate scopes compared with C(acyl)?N cleavage under the same reaction conditions.
- He, Zhanyu,Liu, Tingting,Ru, Junxiang,Wang, Yulin,Wang, Zijia,Zeng, Zhuo
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supporting information
p. 5794 - 5800
(2020/12/01)
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- Reverse Polarity Reductive Functionalization of Tertiary Amides via a Dual Iridium-Catalyzed Hydrosilylation and Single Electron Transfer Strategy
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A strategy for the mild generation of synthetically valuable α-amino radicals from robust tertiary amide building blocks has been developed. By combining Vaska's complex-catalyzed tertiary amide reductive activation and photochemical single electron reduction into a streamlined tandem process, metastable hemiaminal intermediates were successfully transformed into nucleophilic α-amino free radical species. This umpolung approach to such reactive intermediates was exemplified through coupling with an electrophilic dehydroalanine acceptor, resulting in the synthesis of an array of α-functionalized tertiary amine derivatives, previously inaccessible from the amide starting materials. The utility of the strategy was expanded to include secondary amide substrates, intramolecular variants, and late-stage functionalization of an active pharmaceutical ingredient. Density functional theory analyses were used to establish the reaction mechanism and elements of the chemical system that were responsible for the reaction's efficiency.
- Dixon, Darren J.,Duarte, Fernanda,Gabriel, Pablo,Leitch, Jamie A.,Rogova, Tatiana,Zavitsanou, Stamatia
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p. 11438 - 11447
(2020/11/17)
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- Palladium-catalyzed external-CO-free reductive carbonylation of aryl sulfonates
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Pd-catalyzed reductive carbonylation of aryl sulfonates using N-formylsaccharin as a carbon monoxide (CO) surrogate was developed. This external-CO-free carbonylation provides a safe and practical access to aldehydes from phenol derivatives. The reaction has a broad substrate scope, rendering it an attractive method for synthesizing aldehydes.
- Konishi, Hideyuki,Kumon, Minoru,Yamaguchi, Miyuki,Manabe, Kei
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