- Copper(II)-Ethanolamine Triazine Complex on Chitosan-Functionalized Nanomaghemite for Catalytic Aerobic Oxidation of Benzylic Alcohols
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Abstract: In this study a novel, effective and recoverable Cu(II)-catalyst was synthesized by incorporating of Cu(OAc)2 within ethanolamine-triazine derivative (TAETA) attached to chitosan (Chs)-functionalized γ-Fe2O3 nanoparticles [MNP@Chs/TAETA-Cu(II)]. It was characterized by different techniques such as FT-IR, EDS, ICP, TEM, TGA and VSM. The as-prepared nanocomposite demonstrated high oxidation activity and desired selectivity in the aerobic oxidation of structurally diverse set of benzyl alcohols. Spectral results and leaching experiments revealed that this magnetically recoverable heterogeneous catalyst preserved its structure after it was reused several?times. This protocol offers some beneficial features such as the use of oxygen as an ideal oxidant, stability of nanocomplex, easily catalyst separation by using an external magnetic field and efficient recycling as well as the lack of by-products. Graphic Abstract: [Figure not available: see fulltext.]
- Hasanpour, Benyamin,Jafarpour, Maasoumeh,Feizpour, Fahimeh,Rezaeifard, Abdolreza
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- Design and synthesis of a highly efficient heterogeneous MnCo2O4 oxide catalyst for alcohol oxidation: DFT insight into the synergistic effect between oxygen deficiencies and bimetal species
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The synergistic effect in multi-active site catalysts is difficult to monitor, and the effect of their intrinsic mechanism on their catalytic performance is important but very difficult to understand owing to the large quantities of active species. Based on the results of density functional theory, herein we report the design and synthesis of an oxygen vacancy-abundant spinel-structured MnCo2O4 oxide as a highly efficient catalyst for alcohol oxidation, which highlights the importance of the synergistic effect between oxygen deficiencies and bimetal species.
- Li, Dandan,Ruan, Fei,Jin, Yangxin,Ke, Qingping,Cao, Yali,Wang, Hao,Wang, Tingting,Song, Yujun,Cui, Ping
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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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- Aerobic oxidation and oxidative esterification of alcohols through cooperative catalysis under metal-free conditions
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The ABNO@PMO-IL-Br material obtained by anchoring 9-azabicyclo[3.3.1]nonane-3-oneN-oxyl (keto-ABNO) within the mesopores of periodic mesoporous organosilica with bridged imidazolium groups is a robust bifunctional catalyst for the metal-free aerobic oxidation of numerous primary and secondary alcohols under oxygen balloon reaction conditions. The catalyst, furthermore, can be successfully employed in the first metal-free self-esterification of primary aliphatic alcohols affording valued esters.
- Karimi, Babak,Ghahremani, Mina,Vali, Hojatollah,Ciriminna, Rosaria,Pagliaro, Mario
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supporting information
p. 8897 - 8900
(2021/09/10)
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- N-bromosuccinimide/HCl mediated reduction of sulfoxides to sulfides
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An efficient reduction of sulfoxides to sulfides mediated by N-bromosuccinimide (NBS)/HCl system has been developed. This protocol shows good functional group compatibility as well as broad substrates scope with operational simplicity.
- Wang, Jianqiang,Shi, Fangmin,Dai, Dongyan,Xiong, Liping,Yang, Yongpo
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supporting information
p. 439 - 443
(2021/02/03)
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- Preparation method of p-methylsulfonyl benzaldehyde
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The invention relates to a preparation method of p-methylsulfonyl benzaldehyde, and solves the technical problems that the existing preparation method is unreasonable, high in raw material toxicity, complex in operation, high in cost, high in three-waste yield, low in yield and unsuitable for industrial product. The preparation method of p-methylsulfonyl benzaldehyde takes p-nitroformaldehyde as a raw material and sodium sulfide as a reducing agent, and the preparation method comprises the following steps: carrying out a reduction reaction under an alkaline condition to generate p-aminobenzaldehyde, dropwise adding sodium methyl mercaptide into the p-aminobenzaldehyde in the presence of hydrochloric acid and sodium nitrite, carrying out a diazo reaction and a substitution reaction to generate p-methylthiobenzaldehyde, and oxidizing the p-methylthiobenzaldehyde by using hydrogen peroxide under an acidic condition to obtain the p-methylsulfonyl benzaldehyde. The method can be widely applied to the technical field of veterinary drug and medicine raw material medicine synthesis.
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Paragraph 0012; 0027; 0031; 0033; 0037; 0039; 0043; 0045...
(2021/07/24)
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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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- 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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- Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
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We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
- Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
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supporting information
p. 3723 - 3728
(2021/04/07)
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- Nickel catalyzed hydrosilane reduction of (het)arenecarboxylic acids into aldehydes
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Nickel-catalyzed reduction of (het)arenecarboxylic acids with hydrosilanes in the presence of dimethyl dicarbonate as the activator affords the corresponding aldehydes. The role of the activator is the conversion of the acids into their anhydrides undergoing C–O cleavage. The good yields were achieved in case of substrates bearing electron-donating and electron-neutral groups.
- Wang, Liang,Wang, Yaoyao,Tao, Yu,Zhang, Nana,Li, Shubai
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p. 271 - 273
(2021/05/04)
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- Nitrosoarene-Catalyzed HFIP-Assisted Transformation of Arylmethyl Halides to Aromatic Carbonyls under Aerobic Conditions
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A rare metal-free nucleophilic nitrosoarene catalysis accompanied by highly hydrogen-bond-donor (HBD) solvent, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), organocatalytically converts arylmethyl halides to aromatic carbonyls. This protocol offers an effective means to access a diverse array of aromatic carbonyls with good chemoselectivity under mild reaction conditions. The activation of arylmethyl halides by HFIP to generate stable carbocation and autoxidation of in situ generated hydroxylamine to nitrosoarene in the presence of atmospheric O2 are the keys to success.
- Pradhan, Suman,Sharma, Vishali,Chatterjee, Indranil
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supporting information
p. 6148 - 6152
(2021/08/03)
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- Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids
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Metal single-atom catalysts (SACs) promise great rewards in terms of metal atom efficiency. However, the requirement of particular conditions and supports for their synthesis, together with the need of solvents and additives for catalytic implementation, often precludes their use under industrially viable conditions. Here, we show that palladium single atoms are spontaneously formed after dissolving tiny amounts of palladium salts in neat benzyl alcohols, to catalyze their direct aerobic oxidation to benzoic acids without ligands, additives, or solvents. With this result in hand, the gram-scale preparation and stabilization of Pd SACs within the functional channels of a novel methyl-cysteine-based metal-organic framework (MOF) was accomplished, to give a robust and crystalline solid catalyst fully characterized with the help of single-crystal X-ray diffraction (SCXRD). These results illustrate the advantages of metal speciation in ligand-free homogeneous organic reactions and the translation into solid catalysts for potential industrial implementation.
- Tiburcio, Estefanía,Greco, Rossella,Mon, Marta,Ballesteros-Soberanas, Jordi,Ferrando-Soria, Jesús,López-Haro, Miguel,Hernández-Garrido, Juan Carlos,Oliver-Meseguer, Judit,Marini, Carlo,Boronat, Mercedes,Armentano, Donatella,Leyva-Pérez, Antonio,Pardo, Emilio
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p. 2581 - 2592
(2021/02/16)
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- Aerobic oxidation of alcohols catalyzed by in situ generated gold nanoparticles inside the channels of periodic mesoporous organosilica with ionic liquid framework
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In situ generated gold nanoparticles inside the nanospaces of periodic mesoporous organosilica with an imidazolium framework (Au?PMO-IL) were found to be highly active, selective, and reusable catalysts for the aerobic oxidation of activated and nonactivated alcohols under mild reaction conditions. The catalyst was characterized by nitrogen adsorption-desorption measurement, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), elemental analysis (EA), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The catalyst exhibited excellent catalytic activity in the presence of either Cs2CO3 (35 °C) or K2CO3 (60 °C) as reaction bases in toluene as a reaction solvent. Under both reaction conditions, various types of alcohols (up to 35 examples) including activated benzylic, primary and secondary aliphatic, heterocyclic, and challenging cyclic aliphatic alcohols converted to the expected carbonyl compounds in good to excellent yields and selectivity. The catalyst was also recovered and reused for at least seven reaction cycles. Data from three independent leaching tests indicated that amounts of leached gold particles were negligible (0.2 ppm). It is believed that the combination of bridged imidazolium groups and confined nanospaces of PMO-IL might be a major reason explaining the remarkable stabilization and homogeneous distribution of in situ generated gold nanoparticles, thus resulting in the highly active and recyclable catalyst system.
- Bigdeli, Akram,Karimi, Babak,Khodadadi Karimvand, Somaiyeh,Khorasani, Mojtaba,Safari, Ali Asghar,Vali, Hojatollah
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supporting information
p. 70 - 79
(2020/06/08)
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- A Star-Shaped Triazine-Based Vitamin B5 Copper(II) Nanocatalyst for Tandem Aerobic Synthesis of Bis(indolyl)methanes
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In this work, the catalytic efficiency of a novel bio-relevant triazine (TA)-based pantothenate (vitamin B5) copper(II) complex [Cu(II)-TA/B5] in the aerobic oxidation of benzyl alcohols and tandem synthesis of bis(indolyl)methanes was exploited. The star-shaped catalyst was characterized by different techniques such as FT-IR, EDX, ICP, TEM, and TGA. TEM images revealed a honeycomb structure resulting from the accumulation of nanoparticles with size ranging between 2–6 nm. The high yields and excellent selectivity were obtained for the production of various benzaldehydes and bis(indolyl)methanes under aerobic conditions. Recycling tests, spectroscopic data, and leaching experiments testified that the title heterogeneous bio-relevant catalyst preserved its activity and structural integrity during oxidation and coupling reactions. The presented catalytic systems qualify all requirements for efficient catalytic systems for applied goals.
- Hasanpour, Benyamin,Jafarpour, Maasoumeh,Eskandari, Ameneh,Rezaeifard, Abdolreza
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p. 4122 - 4129
(2020/07/08)
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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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- Electrophilic Chlorine from Chlorosulfonium Salts: A Highly Chemoselective Reduction of Sulfoxides
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Herein, we describe a selective late-stage deoxygenation of sulfoxides based on a novel application of chlorosulfonium salts and demonstrate a new process using these species generated in situ from sulfoxides as the source of electrophilic chlorine. The use of highly nucleophilic 1,3,5-trimethoxybenzene (TMB) as the reducing agent is described for the first time and applied in the deoxygenation of simple and functionalized sulfoxides. The method is easy to handle, economic, suitable for gram-scale operations, and readily applied for poly-functionalized molecules, as demonstrated with more than 45 examples, including commercial medicines and analogues. We also report the results of competition experiments that define the more reactive sulfoxide and we present a mechanistic proposal based on substrate and product observations.
- Acosta-Guzmán, Paola,Mahecha-Mahecha, Camilo,Gamba-Sánchez, Diego
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p. 10348 - 10354
(2020/07/13)
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- Nickel phosphide nanoalloy catalyst for the selective deoxygenation of sulfoxides to sulfides under ambient H2pressure
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Exploring novel catalysis by less common, metal-non-metal nanoalloys is of great interest in organic synthesis. We herein report a titanium-dioxide-supported nickel phosphide nanoalloy (nano-Ni2P/TiO2) that exhibits high catalytic activity for the deoxygenation of sulfoxides. nano-Ni2P/TiO2 deoxygenated various sulfoxides to sulfides under 1 bar of H2, representing the first non-noble metal catalyst for sulfoxide deoxygenation under ambient H2 pressure. Spectroscopic analyses revealed that this high activity is due to cooperative catalysis by nano-Ni2P and TiO2. This journal is
- Fujita, Shu,Mitsudome, Takato,Mizugaki, Tomoo,Yamaguchi, Sho,Yamasaki, Jun,Yamazoe, Seiji
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supporting information
p. 8827 - 8833
(2020/11/23)
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- Synthetic method of p-methylsulfonyl benzaldehyde
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The invention relates to a synthetic method of p-methylsulfonyl benzaldehyde. The synthetic method comprises the following steps: 1, adding an aqueous solution of sodium methyl mercaptide, an organicsolvent, p-chlorobenzaldehyde and a phase transfer catalyst, carrying out heating to a temperature of 50-90 DEG C, carrying out a heat-preserved reaction, carrying out standing layering on a reactionproduct after the reaction is finished, taking an organic layer, and removing the organic solvent to obtain p-methylmercaptobenzaldehyde; 2, adding the p-methylmercaptobenzaldehyde obtained in the step 1 and water, controlling a temperature to be 0-20 DEG C, dropwise adding an aqueous peroxyacetic acid solution into a reactor, controlling the temperature to be 0-30 DEG C in the adding process, andcarrying out a heat-preserved reaction at 0-40 DEG C after dropwise adding is finished, then dropwise adding an aqueous sodium hydroxide solution into the reactor to adjust a pH value to 7-12, carrying out suction filtration on a reaction product, taking the obtained solid, rinsing the solid, and drying the solid to obtain an off-white solid which is p-methylsulfonyl benzaldehyde. With the method, product purity can reach 99% or above at a time, secondary refining is not needed, and yield is high.
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Paragraph 0059-0061; 0063-0065; 0067-0069; 0072; 0077
(2020/04/02)
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- Cu(ii) vitamin C tunes photocatalytic activity of TiO2 nanoparticles for visible light-driven aerobic oxidation of benzylic alcohols
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The incorporation of Cu(OAc)2 into ascorbic acid coated TiO2 nanoparticles easily provided a new heterogeneous visible-light active titania-based photocatalyst (TiO2-AA-Cu(ii)) which was characterized by different techniques such as FT-IR, XPS, ICP-AES, TGA and TEM. A red-shift of the band-edge and a reduction of the band-gap (2.8 eV vs. 3.08 for TiO2) were demonstrated by UV-DRS and Tauc plots. The combination of the as-prepared TiO2-AA-Cu(ii) nanoparticles with TEMPO and molecular oxygen (air) afforded an active catalytic system for the selective oxidation of diverse set of benzylic alcohols under solvent-free conditions. A photoassisted pathway was confirmed for oxidation reactions evidenced by good correlation between apparent quantum yield (AQY) and diffuse reflectance spectra (DRS) of the as-prepared nanohybrid. The spectral data and recycling experiments demonstrated the structural stability of the title copper photocatalyst during oxidation reactions.
- Pourmorteza, Narges,Jafarpour, Maasoumeh,Feizpour, Fahimeh,Rezaeifard, Abdolreza
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p. 12053 - 12059
(2020/04/27)
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- Preparation method of P-methylthiobenzaldehyde (by machine translation)
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The invention discloses a method for preparing p-methylthiobenzaldehyde by using sodium thiosulfate instead, of sodium thiomethyl mercaptan and then bunte hydrolyzing, the sodium methoxide with, sodium thiosulfate to synthesize p-methylthio benzaldehyde . thereby effectively solving the problem of odor, in the use process of sodium methyl mercaptan. (by machine translation)
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- A Simple, Mild and General Oxidation of Alcohols to Aldehydes or Ketones by SO2F2/K2CO3 Using DMSO as Solvent and Oxidant
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A practical, general and mild oxidation of primary and secondary alcohols to carbonyl compounds proceeds in yields of up to 99% using SO2F2 as electrophile in DMSO as both the oxidant and the solvent at ambient temperature. No moisture- and oxygen-free conditions are required. Stoichiometric amount of inexpensive K2CO3, which generates easy to separate by-products, is used as the base. Thus, 5-gram scale runs proceeded in nearly quantitative yields by a simple filtration as the work-up. The use of a polar solvent such as DMSO, which usually promotes competing Pummerer rearrangement, is also noteworthy. This protocol is compatible with a variety of common N-, O-, and S-functional groups on (hetero)arene, alkene and alkyne substrates (68 examples). The protocol was applied (99% yield) to a formal synthesis of the important cholesterol-lowering drug Rosuvastatin. (Figure presented.).
- Zha, Gao-Feng,Fang, Wan-Yin,Leng, Jing,Qin, Hua-Li
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supporting information
p. 2262 - 2267
(2019/04/17)
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- A molybdenum based metallomicellar catalyst for controlled and chemoselective oxidation of activated alcohols in aqueous medium
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A surfactant based oxodiperoxo molybdenum complex, which could activate molecular oxygen, has been employed as a catalyst for controlled oxidation of benzylic alcohols to corresponding carbonyls. The oxidation reactions were carried out under aqueous environment, however, in the absence of any extraneous base or co-catalyst. Sensitive/oxidizable functional groups like cyano, sulfide, hydroxyl, aryl-hydroxyl, alkene (internal/terminal), alkyne (internal/terminal), and acetal were tolerated during the transformations. Such selectivity is attributed to the mild nature of the catalyst. The methodology could also be scaled-up for multi-gram synthesis and the protocol is likely to find practical use since it requires an inexpensive recyclable-catalyst and easily available oxidant (under green conditions). A plausible mechanism is proposed with the help of preliminary computational study.
- Thiruvengetam, Prabaharan,Chakravarthy, Rajan Deepan,Chand, Dillip Kumar
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p. 123 - 133
(2019/07/19)
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- Temperature responsive polymer-supported TEMPO: An efficient and recoverable catalyst for the selective oxidation of alcohols
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This study aimed to combine the advantages of homogeneous catalysis and heterogeneous catalysis by immobilizing TEMPO into a water-soluble temperature responsive polymer. The supported TEMPO was water soluble and displayed excellent activity in the selective oxidation of alcohols below the LCST and can be easily recovered.
- Chen, Tao,Xu, Zhenkai,Zhou, Lei,Hua, Laiyu,Zhang, Shuo,Wang, Jiping
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supporting information
p. 419 - 422
(2019/01/08)
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- 3-BocNH-ABNO-catalyzed aerobic oxidation of alcohol at room temperature and atmospheric pressure
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A transition-metal-free catalytic system has been developed for selective transformation of alcohol to aldehydes or ketones. The reactions were performed with 3-(tert-butoxycarbonylamino)-9-azabicyclo[3.3.1]nonane N-oxyl (3-BocNH-ABNO) as the catalyst, NaNO2 as the co-catalyst, molecular oxygen as the terminal oxidant, and AcOH as the solvent under room temperature. This catalytic system exhibited broad functional group tolerance. A series of alcohol substrates, including primary and secondary benzylic alcohols, heteroaromatic analogues, primary and secondary aliphatic alcohols, could be converted into their corresponding aldehydes and ketones in good conversions and selectivities.
- Zhao, Yajing,Li, Yutong,Shen, Zhenlu,Hu, Xinquan,Hu, Baoxiang,Jin,Sun, Nan,Li, Meichao
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supporting information
(2019/08/06)
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- A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
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A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
- Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
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supporting information
p. 3190 - 3194
(2019/05/21)
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- Highly efficient polymer-based nanoreactors for selective oxidation of alcohols in water
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In this study, we demonstrate the fabrication of thermo-responsive polymer-based TEMPO nanoreactors and their application in the catalytic selective oxidation of alcohols as a highly efficient and recoverable catalyst in aqueous media. First, a diblock amphiphilic copolymer NHS-P(MMA25-b-OEGMA75) consisting of poly(methyl methacrylate) (PMMA) and poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA300) with a terminal N-hydroxysuccinimide (NHS) activated ester was synthesized utilizing reversible addition–fragmentation chain transfer polymerization (RAFT) techniques. Free radical 2,2,6,6,-tetramethyipiperidinooxy (TEMPO) was then introduced into the end of the copolymer based on activated ester functionalization to afford the temperature responsive polymer-supported catalyst TEMPO-P(MMA25-b-OEGMA75). Next, core-shell TEMPO nanoreactors were formed through self-assembly of the amphiphilic block polymers in deionized water. The morphology of the nanoreactors was well characterized by dynamic light scattering (DLS) and scanning electron microscopy (SEM). The nanoreactors were then successfully applied in the selective oxidative of alcohols in water. A variety of aldehydes and ketones were achieved in excellent yields and selectivities in high reaction rates with low catalyst loading. The high efficiency in catalysis of the nanoreactors may attributed to the ideal environment where enhancing the interactions between the catalyst and the alcohol substrate, mimicking the environment of enzymes. The thermo-responsive polymer-based nanoreactors could be conveniently recovered in the temperature above the LCST of the polymer after extraction of product from the reaction mixture. This strategy provides an effective and cleaner way for the selective oxidative of alcohols in organic synthesis and industrial application.
- Chen, Tao,Xu, Zhenkai,Zhou, Lei,Qiu, Jiaqi,Wang, Maolin,Wang, Jiping
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- Iron-Catalyzed Direct Transformation of Benzylic Amines into Carbonyl Compounds in Water
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Fe-catalyzed direct transformation of benzylic amines into carbonyl compounds was performed in H 2 O. The reaction of benzylic amines with formaldehyde in the presence of FeCl 3 ·6H 2 O in H 2 O afforded the corresponding carbonyl compounds (80 °C to reflux conditions; 14 examples, up to 94percent yield). O 18 -labeling experiments indicated that the O atom in the generated carbonyl is derived from H 2 O.
- Minakawa, Maki,Sasaki, Takashi
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supporting information
p. 1597 - 1601
(2019/08/07)
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- Transition-Metal-Free Aryl-Heteroatom Bond Formation via C-S Bond Cleavage
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Aryl-heteroatom bonds (C-Het) are almost ubiquitously present in chemical molecules. However, methods for diverse C-Het bond formations from a simple substrate are limited. Herein, we report a convenient and efficient C-S bond transformation of aryl sulfoniums to various C-Het bonds (C-O, C-S, C-Sn, C-Si, C-Se) in the absence of any transition-metal catalyst. These reactions proceeded in mild conditions with a wide substrate scope.
- Zhao, Jian-Nan,Kayumov, Muzaffar,Wang, Dong-Yu,Zhang, Ao
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supporting information
p. 7303 - 7306
(2019/10/02)
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- Identification of MsrA homologues for the preparation of (R)-sulfoxides at high substrate concentrations
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Here we report a methionine sulfoxide reductase A (MsrA) homologue with extremely high substrate tolerance and a wide substrate scope for the biocatalytic preparation of enantiopure sulfoxides. This MsrA homologue which was obtained from Pseudomonas alcaliphila (named paMsrA) showed good activity and enantioselectivity towards a series of aryl methyl/ethyl sulfoxides 1a-1k, with electron-withdrawing or electron-donating substituents at the aromatic ring. Chiral sulfoxides in the R configuration were prepared with approximately 50% of yield and up to 99% enantiomeric excess through the asymmetric reductive resolution of racemic sulfoxide catalyzed by the recombinant paMsrA protein. More importantly, kinetic resolution has been successfully accomplished with high enantioselectivity (E > 200) at initial substrate concentrations up to 320 mM (approximately 45 g L-1), which represents a great improvement in the aspect of the substrate concentration for the biocatalytic preparation of chiral sulfoxides.
- Yang, Jiawei,Wen, Yuanmei,Peng, Liaotian,Chan, Yu,Cheng, Xiaoling,Chen, Yongzheng
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p. 3381 - 3388
(2019/04/01)
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- Fe(NO3)3/2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ): An efficient catalyst system for selective oxidation of alcohols under aerobic conditions
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A practical and efficient catalyst system for the oxidation of alcohols to carbonyl compounds using catalytic amounts of DDQ and Fe(NO3)3 with air as the environmentally benign oxidant has been developed. A variety of benzylic, heterocyclic, allylic and propargylic alcohols were smoothly converted into aldehydes or ketones in good to excellent yields. In case of large-scale reaction for the oxidation of benzyl alcohol, benzaldehyde was obtained in 93% isolated yield. Moreover, a possible reaction mechanism was proposed.
- Hu, Yongke,Chen, Lei,Li, Bindong
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- 2-Azaadamantane N-oxyl (AZADO)/Cu Catalysis Enables Chemoselective Aerobic Oxidation of Alcohols Containing Electron-Rich Divalent Sulfur Functionalities
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The chemoselective oxidation of alcohols containing electron-rich sulfur functionalities (e.g., 1,3-dithianes and sulfides) into their corresponding carbonyl compounds with the sulfur groups can sometimes be a demanding task in modern organic chemistry. A reliable method for this transformation, which features azaadamantane-type nitroxyl radical/copper catalysis using ambient air as the terminal oxidant is reported. The superiority of the developed method was demonstrated by comparing it with various conventional alcohol oxidation methods.
- Sasano, Yusuke,Kogure, Naoki,Nagasawa, Shota,Kasabata, Koki,Iwabuchi, Yoshiharu
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supporting information
p. 6104 - 6107
(2018/09/27)
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- NH3?H2O: The Simplest Nitrogen-Containing Ligand for Selective Aerobic Alcohol Oxidation to Aldehydes or Nitriles in Neat Water
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Aqueous ammonia (NH3?H2O) has been shown to serve as the simplest nitrogen-containing ligand to effectively promote copper-catalyzed selective alcohol oxidation under air in water. A series of alcohols with varying electronic and steric properties were selectively oxidized to aldehydes with up to 95 % yield. Notably, by increasing the amount of aqueous ammonia in neat water, the exclusive formation of aryl nitriles was also accomplished with good-to-excellent yields. Additionally, the catalytic system exhibits a high level of functional group tolerance with ?OH, ?NO2, esters, and heteroaryl groups all being amenable to the reaction conditions. This one-pot and green oxidation protocol provides an important synthetic route for the selective preparation of either aldehydes or nitriles from commercially available alcohols.
- Zhang, Guofu,Ma, Danting,Zhao, Yiyong,Zhang, Guihua,Mei, Guangyao,Lyu, Jinghui,Ding, Chengrong,Shan, Shang
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p. 885 - 889
(2018/12/10)
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- Magnetic crosslinked copoly(ionic liquid) nanohydrogel supported palladium nanoparticles as efficient catalysts for the selective aerobic oxidation of alcohols
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Nowadays it is still a great sustainable processes challenge to produce efficient, selective and easy magnetic recovery and recycling catalysts for oxidation of alcohols using air as the oxidant. In this work, a new magnetic nanohydrogel comprising [DABCO-allyl][Br] ionic liquid, allyl alcohol and N,N’-methylenebis(acrylamide) is used for stabilization of small and highly uniform palladium nanoparticles of 3–4 nm size MXCPILNHG@Pd. This material has been characterized by Fourier-transform infrared spectroscopy (FTIR), atomic adsorption spectroscopy (AAS), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), SEM-Map, energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectra (XPS), vibrating-sample magnetometer (VSM) and dynamic light scattering (DLS). According to optimization of cross-linking degree and ratio of DABCO-IL, MXCPILNHG-2@Pd is found as a highly selective catalyst in oxidations of primary alcohols to the corresponding aldehydes in toluene and to acids in water. Furthermore, secondary alcohols were reacted efficiently to the corresponding ketones in both toluene and water. Catalyst is magnetically recovered and recycled for several times in both toluene and water and the reused catalysts are characterized by TEM and XPS.
- Gholinejad, Mohammad,Afrasi, Mahmoud,Nikfarjam, Nasser,Nájera, Carmen
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p. 185 - 195
(2018/07/14)
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- Highly Productive Oxidative Biocatalysis in Continuous Flow by Enhancing the Aqueous Equilibrium Solubility of Oxygen
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We report a simple, mild, and synthetically clean approach to accelerate the rate of enzymatic oxidation reactions by a factor of up to 100 when compared to conventional batch gas/liquid systems. Biocatalytic decomposition of H2O2 is used to produce a soluble source of O2 directly in reaction media, thereby enabling the concentration of aqueous O2 to be increased beyond equilibrium solubility under safe and practical conditions. To best exploit this method, a novel flow reactor was developed to maximize productivity (g product L?1 h?1). This scalable benchtop method provides a distinct advantage over conventional bio-oxidation in that no pressurized gas or specialist equipment is employed. The method is general across different oxidase enzymes and compatible with a variety of functional groups. These results culminate in record space-time yields for bio-oxidation.
- Chapman, Michael R.,Cosgrove, Sebastian C.,Turner, Nicholas J.,Kapur, Nikil,Blacker, A. John
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supporting information
p. 10535 - 10539
(2018/08/17)
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- Correlation analysis of reactivity in the oxidation of substituted benzyl alcohols by benzimidazolium dichromate - A kinetic and mechanistic aspects
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The oxidation of a number of para- and meta-substituted benzyl alcohols by benzimidazolium dichromate (BIDC), in dimethyl sulphoxide, leads to the formation of the corresponding benzaldehydes. The reaction is first order with respect to each BIDC and alcohol. The reaction is catalyzed by hydrogen ions and the dependence has the form kobs = a + b[H+]. The oxidation of [1,1-2H2]benzyl alcohol exhibited the presence of a substantial kinetic isotope effect. The rates of the oxidation of meta-substituted benzyl alcohols correlated best with Taft's σ1 and σR0 constants. The para-substituted compounds exhibited excellent correlation with σ1 and σRBA values. The polar reaction constants are negative. The rate of oxidation of benzyl alcohol was determined in nineteen organic solvents. An analysis of the solvent effect by multiparametric equations indicated the greater importance of the cation-solvating power of the solvents. Suitable mechanisms have been discussed.
- Kumar, Pravesh,Panday, Dinesh,Kothari, Seema
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p. 1207 - 1215
(2020/06/27)
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- METHOD FOR PRODUCING CARBONYL COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for producing a carbonyl compound, allowing for improvement of ease of production and furthermore allowing for reduction of production cost, by positively utilizing inexpensive iodine. SOLUTION: A carbonyl compound is produced by mixing primary alcohol or secondary alcohol, and iodic acid (HIO3) in a non-solvent or an aprotic polar solvent based on the following general formula (1), where R1 is an optionally substituted linear- or branched 1-12C aliphatic group, or an optionally substituted aromatic group; R2 is a hydrogen atom, an optionally substituted linear- or branched 1-12C alkyl group, or an optionally substituted aromatic group; R1 and R2 each may be coupled with each other to form a ring of aromatic group or a non-aromatic group. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0032-0035; 0037-0040
(2018/03/23)
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- Generation of Phosphoranyl Radicals via Photoredox Catalysis Enables Voltage-Independent Activation of Strong C-O Bonds
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Despite the prevalence of alcohols and carboxylic acids as functional groups in organic molecules and the potential to serve as radical precursors, C-O bonds remain difficult to activate. We report a synthetic strategy for direct access to both alkyl and acyl radicals from these ubiquitous functional groups via photoredox catalysis. This method exploits the unique reactivity of phosphoranyl radicals, generated from a polar/SET crossover between a phosphine radical cation and an oxygen-centered nucleophile. We show the desired reactivity in the reduction of benzylic alcohols to the corresponding benzyl radicals with terminal H atom trapping to afford the deoxygenated products. Using the same method, we demonstrate access to synthetically versatile acyl radicals, which enables the reduction of aromatic and aliphatic carboxylic acids to the corresponding aldehydes with exceptional chemoselectivity. This protocol also transforms carboxylic acids to heterocycles and cyclic ketones via intramolecular acyl radical cyclizations to forge C-O, C-N, and C-C bonds in a single step.
- Stache, Erin E.,Ertel, Alyssa B.,Rovis, Tomislav,Doyle, Abigail G.
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p. 11134 - 11139
(2018/11/21)
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- Metal-free hypervalent iodine/TEMPO mediated oxidation of amines and mechanistic insight into the reaction pathways
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A highly efficient metal free approach for the oxidation of primary and secondary amines to their corresponding aldehydes and ketones using PhI(OAc)2 in combination with a catalytic amount of TEMPO as an oxidizing agent is described. This protocol is rapid and provides diverse products under milder reaction conditions in excellent yields. In addition, the mechanistic study is well demonstrated by spectroscopic methods.
- Bansode, Ajay H.,Suryavanshi, Gurunath
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p. 32055 - 32062
(2018/09/29)
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- The Hydrazine–O2 Redox Couple as a Platform for Organocatalytic Oxidation: Benzo[c]cinnoline-Catalyzed Oxidation of Alkyl Halides to Aldehydes
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An organocatalytic oxidation platform that capitalizes on the capacity of hydrazines to undergo rapid autoxidation to diazenes is described. Commercially available benzo[c]cinnoline is shown to catalyze the oxidation of alkyl halides to aldehydes in a novel mechanistic paradigm involving nucleophilic attack, prototropic shift, and hydrolysis. The hydrolysis and reoxidation events occur readily with only adventitious oxygen and water. A survey of the scope of viable substrates is shown along with mechanistic and computational studies that give insight into this mode of catalysis.
- Stone, Ilana B.,Jermaks, Janis,MacMillan, Samantha N.,Lambert, Tristan H.
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supporting information
p. 12494 - 12498
(2018/09/18)
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- Biocatalytic Preparation of Chiral Sulfoxides through Asymmetric Reductive Resolution by Methionine Sulfoxide Reductase A
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Here we report an environmentally friendly method for the preparation of chiral sulfoxides under high substrate concentration using recombinant methionine sulfoxide reductase A from Pseudomonas monteilii (pmMsrA) as a biocatalyst. Our results show that this enzyme can effectively accomplish the preparation of (R)-sulfoxides with approximately 50 % yield and 94–99 % enantiomeric excess through asymmetric reductive resolution of racemic sulfoxide. With the establishment of the enzyme regeneration system, the initial substrate concentration could be increased 40–100 times compared to our original report. The (R)-sulfoxides were obtained with high enantioselectivity under the substrate concentration up to 200 mm (approximately 32 g L?1), representing a quite high substrate concentration in biocatalytic preparation of chiral sulfoxides. Moreover, this system showed fairly good activity and enantioselectivity towards a series of ortho- and para-substituted phenyl methyl sulfoxides under high substrate concentration.
- Peng, Liaotian,Wen, Yuanmei,Chen, Yu,Yuan, Zhimei,Zhou, Yang,Cheng, Xiaoling,Chen, Yongzheng,Yang, Jiawei
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p. 3284 - 3290
(2018/06/04)
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- Palladium-Catalyzed Reductive Conversion of Acyl Fluorides via Ligand-Controlled Decarbonylation
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Ligand-controlled non-decarbonylative and decarbonylative conversions of acyl fluorides were developed using a Pd(OAc)2/Et3SiH combination. When tricyclohexylphosphine (PCy3) was used as the ligand, aldehydes were obtained as simple reductive conversion products. The use of 1,2-bis(dicyclohexylphosphino)ethane (Cy2P(CH2)2PCy2, DCPE) as the ligand, however, favored the formation of hydrocarbons, which are decarbonylative reduction products.
- Ogiwara, Yohei,Sakurai, Yuka,Hattori, Hiroyuki,Sakai, Norio
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supporting information
p. 4204 - 4208
(2018/07/29)
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- Preparation method of 4-methylsulphonylphenylacetic acid
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The invention belongs to the field of organic synthesis and provides a preparation method of 4-methylsulphonylphenylacetic acid. According to the preparation method, 4-methylthio benzaldehyde is prepared from thioanisole as a starting material through a Vilsmeier reaction and subjected to a Darzen reaction; a product is subjected to hydrolysis and decarboxylation, and 4-methylthio phenylacetaldehyde is obtained; 4-methylsulphonylphenylacetic acid is prepared from 4-methylthio phenylacetaldehyde through oxidization.
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Paragraph 0028-0030
(2018/04/01)
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- Controlled Aerobic Oxidation of Primary Benzylic Alcohols to Aldehydes Catalyzed by Polymer-Supported Triazine-Based Dendrimer-Copper Composites
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A controlled aerobic oxidation of primary benzylic alcohols to the corresponding benzaldehydes by using polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported triazine-based polyethyleneamine dendrimer-copper complexes [PS-PEG-TD2-Cu(II)] was developed. In particular, PS-PEG-TD2-Cu(OAc) 2 efficiently catalyzed the aerobic oxidation of benzylic alcohols in the presence of a catalytic amount of TEMPO under atmospheric conditions to give the corresponding aldehydes in up to quantitative yield. The catalyst was readily recovered by simple filtration and reused four times without significant loss of its catalytic activity.
- Pan, Shiguang,Yan, Shuo,Osako, Takao,Uozumi, Yasuhiro
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supporting information
p. 1152 - 1156
(2018/04/16)
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- Recyclable copper-catalyzed ambient aerobic oxidation of primary alcohols to aldehydes in water using water-soluble PEG-functionalized pyridine triazole as ligand
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A water-soluble PEG-PyTa ligand, conveniently derived from commercially available reagents via a simple synthetic approach, could efficiently promote copper/2, 2, 6, 6-tetramethyl piperidine-1-oxyl (TEMPO)-catalyzed aerobic oxidation of primary alcohols to aldehydes in water under room temperature. A number of primary benzylic, allylic alcohols and heteroaryl methanols were selectively converted into their corresponding aldehydes with excellent yields. The oxidation products could be isolated by simple extraction, and the residual aqueous phase containing the catalyst Cu(OTf)2/PEG-PyTa could be reused at least 7 times.
- Sun, Nan,Zhang, Xiaonan,Jin, Liqun,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
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- Water as a proton mediator for dioxygen-selective oxidation of alcohols by a planar dinuclear butterfly-like CuCu bonding complex: A combined experimental and computational study
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The selective catalytic oxidation of alcohols is important both in laboratory and industrial production, and traditional oxidants cause environmentally lethal wastes. The development of dioxygen selective oxidation efficient has been pursued from atom-efficient, economic and environmental view of points. Using DFT calculation and ESI-MS experiments, we studied the activation of the CuCu bonded planar complex Cu2(ophen)2 to dioxygen and the application of the dioxygen-copper system for the selective oxidation of alcohols. For practical application and green chemistry, this catalytic system avoided the use of a large excess of base and expensive nitroxyl derivatives. In the cycle of oxidation, two oxidative dehydrogenation processes featuring superoxide/peroxide (I) and hydroperoxide (II) occurred along with a series of conformational changes of the butterfly-like Cu-complex from stretched to folded to stretched. Additionally, we characterized the role of the water molecule as a proton mediator in the dioxygen-copper system.
- Zhang, Lingjuan,Liu, Jie,Zhang, Fuqiang,Zhang, Xian-Ming
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- Method for preparing aldehyde by oxidizing primary alcohol
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The invention discloses a method for preparing aldehyde by catalytic oxidation of primary alcohol. The method comprises the steps that the primary alcohol as shown in a formula (I) or (III) is taken as a raw material, copper salt is taken as a catalyst, air is taken as an oxidizing agent, TEMPO (2,2,6,6-tetramethyl-1-piperidine-N-oxyl compound) is taken as a pro-oxygenic agent, ammonium hydroxide is taken as a co-catalyst and solvent, the primary alcohol, the copper salt, the air, the TEMPO and the ammonium hydroxide are mixed uniformly and react for 9 to 24 hours at the temperature of 60 to 120 DEG C; after the reaction, reaction liquid is subjected to aftertreatment to obtain aldehyde as shown in a formula (II) or (IV). The method has the advantages of high reaction rate and yield, low cost, convenience in operation and safety in reaction. The whole process is environmental friendly and free of pollution.
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Paragraph 0026; 0027; 0028; 0029; 0030; 0066; 0067-0070
(2017/07/21)
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- Rapid and efficient deoxygenation of sulfoxides to sulfides with tantalum(V) chloride/sodium iodide system
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TaCl5/NaI system converts a wide range of sulfoxides to the corresponding sulfides in high yields with short reaction times, under mild conditions. It is worth mentioning that this protocol is chemoselective and tolerates various functional groups (such as –Br, –Cl, –OCH3, –CHO, and –NO2) and double bond.
- Yoo, Byung Woo,Park, Jeeyeon,Shin, Hyo Jong,Yoon, Cheol Min
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p. 597 - 603
(2017/10/06)
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- Synthesis of Aldehydes by Organocatalytic Formylation Reactions of Boronic Acids with Glyoxylic Acid
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Reported herein is a conceptually novel organocatalytic strategy for the formylation of boronic acids. New reactivity is engineered into the α-amino-acid-forming Petasis reaction occurring between aryl boronic acids, amines, and glyoxylic acids to prepare aldehydes. The operational simplicity of the process and its ability to generate structurally diverse and valued aryl, heteroaryl, and α,β-unsaturated aldehydes containing a wide array of functional groups, demonstrates the practical utility of the new synthetic strategy.
- Huang, He,Yu, Chenguang,Li, Xiangmin,Zhang, Yongqiang,Zhang, Yueteng,Chen, Xiaobei,Mariano, Patrick S.,Xie, Hexin,Wang, Wei
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supporting information
p. 8201 - 8205
(2017/06/30)
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- Synergistic catalysis within TEMPO-functionalized periodic mesoporous organosilica with bridge imidazolium groups in the aerobic oxidation of alcohols
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Anchoring 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) within the nanospaces of a periodic mesoporous organosilica with bridged imidazolium groups led to an unprecedented powerful bifunctional catalyst (TEMPO@PMO-IL-Br), which showed enhanced activity in the metal-free aerobic oxidation of alcohols. The catalyst and its precursors were characterized by N2 adsorption-desorption analysis, transmission electron microscopy (TEM), small angle X-ray scattering (SAXS), thermal gravimetric analysis (TGA), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), solid state electron paramagnetic resonance (EPR) spectroscopy, elemental analysis, transmission electron microscopy (TEM) and high resolution TEM. It was clearly found that the catalytic activity of SBA-15-functionalized TEMPO (TEMPO@SBA-15) not bearing IL, TEMPO@PMO-IL-Cl, PMO-IL-AMP, or individual catalytic functionalities (PMO-IL/TEMPO@SBA-15) was inferior as compared with those obtained from TEMPO@PMO-IL-Br in the metal-free aerobic oxidation of benzyl alcohol, suggesting the critical role of co-supported TEMPO and imidazolium bromide in obtaining high catalytic activity in the described catalyst system. Our observation clearly points to the fact that the combination of imidazolium bromide units in close proximity to TEMPO moieties in the nanospaces of TEMPO@PMO-IL-Br might be indeed one of the key factors explaining the enhanced catalytic activity observed for this catalyst in the oxidation of benzyl alcohol, possibly through a synergistic catalysis relay pathway. A proposed model was suggested for the observed synergistic effect.
- Karimi, Babak,Vahdati, Saleh,Vali, Hojatollah
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p. 63717 - 63723
(2016/07/19)
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- Synthetic utility of iodic acid in the oxidation of benzylic alcohols to aromatic aldehydes and ketones
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Various primary and secondary benzylic alcohols were efficiently oxidized to aromatic aldehydes and aromatic ketones with iodic acid in DMF at 60?°C for 2?h and with iodic acid in the presence of TEMPO (5?mol?%) in DMF at room temperature, respectively. The former method was effective for the oxidation of sterically hindered alcohols at 60?°C and the latter method was effective for the oxidation of less sterically hindered alcohols at room temperature.
- Imai, Sho,Togo, Hideo
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p. 6948 - 6954
(2016/10/13)
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