- 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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- Preparation method of methyl substituted benzaldehyde
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The invention relates to a preparation method of methyl substituted benzaldehyde, in particular to a method for preparing alkyl aromatic aldehyde through a carbonylation reaction by adopting methyl substituted aromatic hydrocarbon as raw materials. According to the method, ionic liquid with the high catalytic activity is adopted, and methyl substituted benzene is used for preparing the methyl substituted benzaldehyde under the alleviated condition with high conversion rate; meanwhile, the reaction time is shortened, waste water, gas and industrial residues are reduced, and no auxiliaries withhigh corrosivity are adopted.
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Paragraph 0050-0055; 0058-0063
(2021/03/06)
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- An aerobic oxidation of alcohols into carbonyl synthons using bipyridyl-cinchona based palladium catalyst
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We have reported an aerobic oxidation of primary and secondary alcohols to respective aldehydes and ketones using a bipyridyl-cinchona alkaloid based palladium catalytic system (PdAc-5) using oxygen at moderate pressure. ThePdAc-5catalyst was analysed using SEM, EDAX, and XPS analysis. The above catalytic system is used in experiments for different oxidation systems which include different solvents, additives, and bases which are cheap, robust, non-toxic, and commercially available on the industrial bench. The obtained products are quite appreciable in both yield and selectivity (70-85%). In addition, numerous important studies, such as comparisons with various commercial catalysts, solvent systems, mixture of solvents, and catalyst mole%, were conducted usingPdAc-5. The synthetic strategy of oxidation of alcohol into carbonyl compounds was well established and all the products were analysed using1H NMR,13CNMR and GC-mass analyses.
- Cheedarala, Ravi Kumar,Chidambaram, Ramasamy R.,Siva, Ayyanar,Song, Jung Il
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p. 32942 - 32954
(2021/12/02)
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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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- V2O5@TiO2 Catalyzed Green and Selective Oxidation of Alcohols, Alkylbenzenes and Styrenes to Carbonyls
-
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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- Nickel complex containing meta-carborane triazole ligand and preparation method and application of nickel complex
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The invention relates to a nickel complex containing a meta-carborane triazole ligand and a preparation method and application of the nickel complex. The nickel complex is prepared by the following steps of: (1) dropwise adding an n-BuLi solution into a meta-carborane m-C2B10H12 solution, stirring and reacting; then adding 3-propargyl bromide for a reaction, and separating after the reaction is finished so as to obtain 1, 3-dipropargyl meta-carborane; and (2) carrying out a reaction between 1, 3-dipropargyl meta-carborane and aryl azide under the catalytic condition of a catalyst CuI, then adding NiCl2 into the reaction system, continuing the reaction, carrying out separation after the reaction is finished so as to obtain the nickel complex containing the meta-carborane triazole ligand. The nickel complex is applied to preparation of aldehyde by catalyzing partial oxidation of primary alcohol. Compared with the prior art, the preparation method is simple and green, the complex can efficiently catalyze partial oxidation of primary alcohol to prepare aldehyde, the reaction conditions are mild, the universality is good, the catalytic efficiency is high, and few byproducts are produced; and the catalyst has high stability and is not sensitive to air and water.
- -
-
Paragraph 0078; 0085-0087
(2020/08/07)
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- Conversion of α‐hydroxy(2,4,6‐trimethylbenzyl)diphenylphosphine oxide to TPO: oxidation vs decomposition
-
This study details the oxidation of α-hydroxy(2,4,6-trimethylbenzyl)diphenylphosphine oxide (α-HDPO) to diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) by choosing the proper MnO2 as oxidant. In addition, the equilibrium of α-HDPO and 2,4
- Zhang, Jian-Qiu,Zhao, Jingzhuo,Li, Chunya,Ye, Jingjing,Han, Li-Biao
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p. 207 - 210
(2020/12/15)
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- Oxidative C-S Bond Cleavage of Benzyl Thiols Enabled by Visible-Light-Mediated Silver(II) Complexes
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The oxidative cleavage reaction of the C-S bond using singlet oxygen is challenging because of its uncontrollable nature. We have developed a novel method for the singlet-oxygen-mediated selective C-S bond cleavage reaction using silver(II)-ligand complexes. Visible-light-induced silver catalysis enables the controlled oxidative cleavage of benzyl thiols to afford carbonyl compounds, such as aldehydes or ketones, which are important synthetic components.
- Hong, Boseok,Aganda, Kim Christopher C.,Lee, Anna
-
supporting information
p. 4395 - 4399
(2020/06/05)
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- Synthesis of silyl formates, formamides, and aldehydesviasolvent-free organocatalytic hydrosilylation of CO2
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Carbon dioxide (CO2) was used as a C1 source to prepare silyl formates, formamides, and aldehydes. Tetrabutylammonium acetate (TBAA) catalyzed the solvent-freeN-formylation of amines with CO2and hydrosilane to give formamides including Weinreb formamide, Me(MeO)NCHO, which was successively converted into aldehydes by one-pot reactions with Grignard reagents.
- Ema, Tadashi,Hasegawa, Jun-Ya,Hiyoshi, Mahoko,Murata, Takumi,Ratanasak, Manussada
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supporting information
p. 5783 - 5786
(2020/06/03)
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- Convenient synthesis of 2,3-dihydro-1,2,4-thiadiazoles, 4,5-dihydro-1,3-thiazoles, and 1,3-thiazoles through a [4+1]-type oxidative ring closure of 1,3-thiaza-1,3-butadienes
-
1,3-Thiaza-1,3-butadienes bearing an N,N-dimethylamino group at the C-2 position were efficiently converted into 5H-1,2,4-oxathiazoles, 2,3-dihydro-1,2,4-thiadiazoles, 4,5-dihydro-1,3-thiazoles, and 1,3-thiazoles through an oxidative ring closure by treating with mCPBA, chloramine-T, metal carbenoids, or dichlorocarbene, respectively, via the ring closure of in situ generated heterocumulene-type reactive species involving thione S-oxides, thione S-imides, and thiocarbonyl ylides.
- Shimada, Kazuaki,Isogami, Megumi,Maeda, Kitami,Nishinomiya, Rei,Korenaga, Toshinobu
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p. 881 - 900
(2020/09/09)
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- Rhodium-catalyzed reductive carbonylation of aryl iodides to arylaldehydes with syngas
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The reductive carbonylation of aryl iodides to aryl aldehydes possesses broad application prospects. We present an efficient and facile Rh-based catalytic system composed of the commercially available Rh salt RhCl3·3H2O, PPh3 as phosphine ligand, and Et3N as the base, for the synthesis of arylaldehydes via the reductive carbonylation of aryl iodides with CO and H2 under relatively mild conditions with a broad substrate range affording the products in good to excellent yields. Systematic investigations were carried out to study the experimental parameters. We explored the optimal ratio of Rh salt and PPh3 ligand, substrate scope, carbonyl source and hydrogen source, and the reaction mechanism. Particularly, a scaled-up experiment indicated that the catalytic method could find valuable applications in industrial productions. The low gas pressure, cheap ligand and low metal dosage could significantly improve the practicability in both chemical researches and industrial applications.
- Chen, Suqing,Liu, Zhenghui,Mu, Tiancheng,Wang, Peng,Yan, Zhenzhong,Yu, Dongkun,Zhao, Xinhui
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p. 645 - 656
(2020/05/14)
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- A method for preparation of aromatic aldehydes (by machine translation)
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The invention provides a process for preparing aromatic aldehydes method, comprises the following steps: alkyl substituted benzene and carbon monoxide in the catalyst under catalysis of carbonylation reaction, to obtain the aromatic aldehyde; the catalyst is hydrogen chloride or concentrated hydrochloric acid. The present invention provides a preparation method is simple, solved in the prior art to aluminum chloride as the catalyst, aluminum chloride with an aromatic aldehyde complex problems; and the present invention provides prepared by the preparation method of the aromatic aldehyde high purity, can reach 97.89% -99.12%; in addition, the present invention provides a preparation method can be continuous reaction, it is suitable for industrial large-scale production. (by machine translation)
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Paragraph 0047-0049
(2019/03/15)
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- Aerobic oxidation of alcohols with air catalyzed by decacarbonyldimanganese
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The oxidation of alcohols to carbonyl compounds using air as the terminal oxidant is highly desirable. As described in previous reports, the abstraction of α-H of the alcohol is the most important step, and it typically requires not only a metal catalyst but also complex ligands, co-catalysts and bases. Herein, we report a practical and efficient method for the oxidation of primary alcohols, secondary alcohols, 1,2-diols, 1,2-amino alcohols, and other α-functionalized alcohols using a commercially available catalyst, Mn2(CO)10, and no additives. Preliminary mechanistic studies indicated that an alkoxyl radical intermediate existed in our system, and a plausible mechanism consistent with the experimental results and literature was proposed.
- Meng, Shan-Shui,Lin, Li-Rong,Luo, Xiang,Lv, Hao-Jun,Zhao, Jun-Ling,Chan, Albert S. C.
-
supporting information
p. 6187 - 6193
(2019/11/20)
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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
-
supporting information
p. 2262 - 2267
(2019/04/17)
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- Highly efficient and practical aerobic oxidation of alcohols by inorganic-ligand supported copper catalysis
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The oxidation of alcohols to aldehydes or ketones is a highly relevant conversion for the pharmaceutical and fine-chemical industries, and for biomass conversion, and is commonly performed using stoichiometric amounts of highly hazardous oxidants. The aerobic oxidation of alcohols with transition metal complex catalysts previously required complicated organic ligands and/or nitroxyl radicals as co-catalysts. Herein, we report an efficient and eco-friendly method to promote the aerobic oxidation of alcohols using an inorganic-ligand supported copper catalyst 1, (NH4)4[CuMo6O18(OH)6], with O2 (1 atm) as the sole oxidant. Catalyst 1 is synthesized directly from cheap and commonly available (NH4)6Mo7O24·4H2O and CuSO4, which consists of a pure inorganic framework built from a central CuII core supported by six MoVIO6 inorganic scaffolds. The copper catalyst 1 exhibits excellent selectivity and activity towards a wide range of substrates in the catalytic oxidation of alcohols, and can avoid the use of toxic oxidants, nitroxyl radicals, and potentially air/moisture sensitive and complicated organic ligands that are not commercially available. Owing to its robust inorganic framework, catalyst 1 shows good stability and reusability, and the catalytic oxidation of alcohols with catalyst 1 could be readily scaled up to gram scale with little loss of catalytic activity, demonstrating great potential of the inorganic-ligand supported Cu catalysts in catalytic chemical transformations.
- Wei, Zheyu,Ru, Shi,Zhao, Qixin,Yu, Han,Zhang, Gang,Wei, Yongge
-
supporting information
p. 4069 - 4075
(2019/08/07)
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- Direct Observation of Aryl Gold(I) Carbenes that Undergo Cyclopropanation, C?H Insertion, and Dimerization Reactions
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Mesityl gold(I) carbenes lacking heteroatom stabilization or shielding ancillary ligands have been generated and spectroscopically characterized from chloro(mesityl)methylgold(I) carbenoids bearing JohnPhos-type ligands by chloride abstraction with GaCl3. The aryl carbenes react with PPh3 and alkenes to give stable phosphonium ylides and cyclopropanes, respectively. Oxidation with pyridine N-oxide and intermolecular C?H insertion to cyclohexane have also been observed. In the absence of nucleophiles, a bimolecular reaction, similar to that observed for other metal carbenes, leads to a symmetrical alkene.
- García-Morales, Cristina,Pei, Xiao-Li,Sarria Toro, Juan M.,Echavarren, Antonio M.
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p. 3957 - 3961
(2019/02/19)
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- Highly practical and efficient preparation of aldehydes and ketones from aerobic oxidation of alcohols with an inorganic-ligand supported iodine catalyst
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Herein, we divulge an efficient protocol for aerobic oxidation of alcohols with an inorganic-ligand supported iodine catalyst, (NH4)5[IMo6O24]. The catalyst system is compatible with a wide range of groups and exhibits high selectivity, and shows excellent stability and reusability, thus serving as a potentially greener alternative to the classical transformations.
- Zhang, Mengqi,Zhai, Yongyan,Ru, Shi,Zang, Dejin,Han, Sheng,Yu, Han,Wei, Yongge
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supporting information
p. 10164 - 10167
(2018/09/13)
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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 0036-0040
(2018/03/23)
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- Preparation method of 2,4,6-trimethylbenzaldehyde
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The invention discloses a preparation method of intermediate 2,4,6-trimethylbenzaldehyde of herbicide tralkoxydim and belongs to the technical field of agricultural chemical materials. The method comprises the steps as follows: N,N-dimethylformamide and an anhydrous organic solvent are added to a reaction bottle, a certain amount of POCl3 is slowly dropwise added, stirring is performed at subzero10 DEG C for 20 min, 2,4,6-trimethylbenzene is dropwise added, stirring is performed at the temperature of subzero 5 DEG C for 10 min, a reflux reaction is conducted for 4.0-8.0 h, after the reaction,the organic solvent is removed under reduced pressure, a certain amount of ice water is slowly added, the mixed solution is neutralized with saturated sodium carbonate until the pH is 7, extraction is performed multiple times with ethyl acetate, organic layers are mixed, and 2,4,6-trimethylbenzaldehyde (I) is obtained after drying and desolvation.
- -
-
Paragraph 0031; 0032; 0033; 0034
(2019/01/08)
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- Carbocation catalysed ring closing aldehyde-olefin metathesis
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A highly efficient aldehyde-olefin metathesis catalysed by the carbocation, 4-phenylphenyl-diphenylmethylium ion, has been developed. This protocol is characterized by high yields, low catalyst loading (down to 2 mol%), good functional group compatibility and mild reaction conditions.
- Ni, Shengjun,Franzén, Johan
-
supporting information
p. 12982 - 12985
(2018/11/23)
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- Rhodium-Catalyzed Formylation of Aryl Halides with CO2 and H2
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The reductive formylation of aryl iodides/bromides to aryl aldehydes using CO2/H2 is presented for the first time. It was realized over a catalytic system composed of RhI3 or RhI3/Pd(dppp)Cl2 (dppp = 1,3-bis(diphenyphosphino)propane) and PPh3 in the presence of Ac2O/Et3N at 100 °C, affording aromatic aldehydes in good to excellent yields, together with good functional-group tolerance and broad substrate scope. The reaction proceeds through three cascade steps, involving HCOOH formation, CO release, and formylation of aryl halides.
- Liu, Zhenghui,Yang, Zhenzhen,Yu, Bo,Yu, Xiaoxiao,Zhang, Hongye,Zhao, Yanfei,Yang, Peng,Liu, Zhimin
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supporting information
p. 5130 - 5134
(2018/09/13)
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- Chemoselective Reduction of Sterically Demanding N,N-Diisopropylamides to Aldehydes
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A sequential one-pot process for chemoselectively reducing sterically demanding N,N-diisopropylamides to aldehydes has been developed. In this reaction, amides are activated with EtOTf to form imidates, which are reduced with LiAlH(OR)3 [R = t-Bu, Et] to give aldehydes by hydrolysis of the resulting hemiaminals. The non-nucleophilic base 2,6-DTBMP remarkably improves reaction efficiency. The combination of EtOTf/2,6-DTBMP and LiAlH(O-t-Bu)3 was found to be optimal for reducing alkyl, alkenyl, alkynyl, and 2-monosubstituted aryl N,N-diisopropylamides. In contrast, EtOTf and LiAlH(OEt)3 in the absence of base were found to be optimal for reducing extremely sterically demanding 2,6-disubstituted N,N-diisopropylbenzamides. The reaction tolerates various reducible functional groups, including aldehyde and ketone. 1H NMR studies confirmed the formation of imidates stable in water. The synthetic usefulness of this methodology was demonstrated with N,N-diisopropylamide-directed ortho-metalation and C-H bond activation.
- Xiao, Peihong,Tang, Zhixing,Wang, Kai,Chen, Hua,Guo, Qianyou,Chu, Yang,Gao, Lu,Song, Zhenlei
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p. 1687 - 1700
(2018/02/23)
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- Visible-Light-Driven Photocatalytic Oxidation of Organic Chlorides Using Air and an Inorganic-Ligand Supported Nickel-Catalyst Without Photosensitizers
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Engineering photoredox-triggered chemical transformation via visible light has been an emerging area in organic synthesis. However, most of the well-established photocatalysts are based upon either transition metal complexes involved with noble metals and organic ligands or photosensitive organic dyes, the development of pure inorganic molecular photocatalysts that could provide better stability and durability is greatly retarded. Herein we discover that the Anderson polyoxometalate (POM) Na4[NiMo6O18(OH)6] (1), which consists of pure inorganic framework built from a central NiII core supported by six MoVIO6 inorganic scaffold/ligands, can be used as a powerful photocatalyst. Upon irradiation with visible light (>400 nm), the compound can catalyze, in high efficiency, a wide range of reactions, including the oxidative cross-coupling reaction of chlorides with amines, as well as oxidation of chlorides using molecular oxygen, affording various imines, aldehydes, and ketones, respectively in high selectivity and good yields. Owing to the robust inorganic framework, this catalyst exhibits excellent stability during the catalysis and reusability with little loss of the catalytic activity, thus providing an alternative without use of complicated organic ligands and expensive noble metal-based photosensitizers.
- Yu, Han,Wang, Jingjing,Zhai, Yongyan,Zhang, Mengqi,Ru, Shi,Han, Sheng,Wei, Yongge
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p. 4274 - 4279
(2018/09/10)
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- Selective aerobic oxidation of halides and amines with an inorganic-ligand supported zinc catalyst
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A practical, efficient and environmentally benign catalytic protocol for the oxidative cross-coupling reaction of halides with amines, oxidative self-coupling of amines and oxidation of halides was developed with inorganic-ligand supported ZnPOM (NH4)4[ZnMo6O18(OH)6] using molecular oxygen. This method mainly utilizes an inorganic polymolybdate ligand to support the Zn2+ ion, avoiding the use of complicated organic ligands.
- Wang, Jingjing,Zhai, Yongyan,Wang, Ying,Yu, Han,Zhao, Wenshu,Wei, Yongge
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supporting information
p. 13323 - 13327
(2018/10/15)
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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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- Simple formylation of aromatic compounds using a sodium formate/triphenylphosphine ditriflate system
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A new procedure was developed for formylation of arenes to produce aromatic aldehydes using a sodium formate/triphenylphosphine ditriflate system in ethanol at room temperature in good yields. The simplicity of the procedure, short reaction times, and mild reaction conditions are the other advantages of this metal- and carbon monoxide-free protocol.
- Khodaei, Mohammad M.,Alizadeh, Abdolhamid,Hezarkhani, Hadis Afshar
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supporting information
p. 840 - 843
(2017/06/13)
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- Acceptorless and Base-free Dehydrogenation of Cyanohydrin with (η6-Arene)halide(Bidentate Phosphine)ruthenium(II) Complex
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Ruthenium-catalyzed dehydrogenation of cyanohydrins under acceptorless and base-free conditions was demonstrated for the first time in the synthesis of acyl cyanide. As opposed to the thermodynamically preferred elimination of hydrogen cyanide, the dehydrogenation of cyanohydrins could be kinetically controlled with ruthenium (II) bidentate phosphine complexes. The effects of the arene, phosphine ligands and counter anions were investigated in regard to catalytic activity and selectivity. Selective dehydrogenation can occur via β-hydride elimination with the experimentally observed [(alkoxide)Ru] complex. (Figure presented.).
- Kim, Kicheol,Moeljadi, Adhitya Mangala Putra,Hirao, Hajime,Hong, Soon Hyeok
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supporting information
p. 3292 - 3298
(2017/09/06)
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- Green and Practical Oxidative Deoximation of Oximes to Ketones or Aldehydes with Hydrogen Peroxide/Air by Organoselenium Catalysis
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Organoselenium-catalyzed oxidative deoximations afforded ketones and aldehydes under mild conditions. The reactions employ hydrogen peroxide and air as clean oxidants and lead to a waste-free and metal-free deprotection protocol for carbonyl protection strategies as well as the green synthesis of ketones and aldehydes. The mechanisms of this interesting organoselenium-catalyzed reaction have been investigated by control experiments as well as the selenium 77 nuclear magnetic resonance (77Se NMR) tests. This novel reaction largely expands the application scope of organoselenium catalysis. (Figure presented.).
- Jing, Xiaobi,Yuan, Dandan,Yu, Lei
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p. 1194 - 1201
(2017/04/13)
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- Palladium-Catalyzed Formylation of Arylzinc Reagents with S-Phenyl Thioformate
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The first example of palladium-catalyzed direct formylation of arylzinc reagents using S-phenyl thioformate is reported. The reaction proceeded under mild conditions, allowing high functional group tolerance. In addition, the developed formylation method
- Haraguchi, Ryosuke,Tanazawa, Sho-Go,Tokunaga, Naoya,Fukuzawa, Shin-Ichi
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p. 1646 - 1649
(2017/04/11)
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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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- Simple and Efficient Ruthenium-Catalyzed Oxidation of Primary Alcohols with Molecular Oxygen
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Oxidative transformations utilizing molecular oxygen (O2) as the stoichiometric oxidant are of paramount importance in organic synthesis from ecological and economical perspectives. Alcohol oxidation reactions that employ O2are scarce in homogeneous catalysis and the efficacy of such systems has been constrained by limited substrate scope (most involve secondary alcohol oxidation) or practical factors, such as the need for an excess of base or an additive. Catalytic systems employing O2as the “primary” oxidant, in the absence of any additive, are rare. A solution to this longstanding issue is offered by the development of an efficient ruthenium-catalyzed oxidation protocol, which enables smooth oxidation of a wide variety of primary, as well as secondary benzylic, allylic, heterocyclic, and aliphatic, alcohols with molecular oxygen as the primary oxidant and without any base or hydrogen- or electron-transfer agents. Most importantly, a high degree of selectivity during alcohol oxidation has been predicted for complex settings. Preliminary mechanistic studies including18O labeling established the in situ formation of an oxo–ruthenium intermediate as the active catalytic species in the cycle and involvement of a two-electron hydride transfer in the rate-limiting step.
- Ray, Ritwika,Chandra, Shubhadeep,Maiti, Debabrata,Lahiri, Goutam Kumar
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supporting information
p. 8814 - 8822
(2016/07/06)
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- Design of recyclable TEMPO derivatives bearing an ionic liquid moiety and N, N-bidentate group for highly efficient Cu(i)-catalyzed conversion of alcohols into aldehydes and imines
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Four different types of TEMPO derivatives incorporated with an ionic liquid moiety and N,N-bidentate coordination group (IL-TEMPO-N,N) were prepared. The CuBr/IL-TEMPO-N,N system showed high catalytic activity toward the synthesis of aldehydes and imines via the aerobic oxidation of alcohols in 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF4). Both the Cu catalyst and IL-TEMPO-N,N co-catalyst in homogeneous catalytic systems could simultaneously be recovered from the products by extraction using Et2O. The remaining catalyst system in the ionic liquid phase could be reused for several cycles without obvious loss of catalytic activity. Protocols for highly efficient and recyclable aerobic oxidation of alcohols to aldehydes and imines were established.
- Guo, Bin,Xue, Jiang-Yan,Li, Hong-Xi,Tan, Da-Wei,Lang, Jian-Ping
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p. 51687 - 51693
(2016/06/13)
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- Electronic Structure and Multicatalytic Features of Redox-Active Bis(arylimino)acenaphthene (BIAN)-Derived Ruthenium Complexes
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The article examines the newly designed and structurally characterized redox-active BIAN-derived [Ru(trpy)(R-BIAN)Cl]ClO4 ([1a]ClO4-[1c]ClO4), [Ru(trpy)(R-BIAN)(H2O)](ClO4)2 ([3a](ClO4)2-[3c](ClO4)2), and BIAO-derived [Ru(trpy)(BIAO)Cl]ClO4 ([2a]ClO4) (trpy = 2,2′:6′,2′′-terpyridine, R-BIAN = bis(arylimino)acenaphthene (R = H (1a+, 3a2+), 4-OMe (1b+, 3b2+), 4-NO2 (1c+, 3c2+), BIAO = [N-(phenyl)imino]acenapthenone). The experimental (X-ray, 1H NMR, spectroelectrochemistry, EPR) and DFT/TD-DFT calculations of 1an-1cn or 2an collectively establish {RuII-BIAN0} or {RuII-BIAO0} configuration in the native state, metal-based oxidation to {RuIII-BIAN0} or {RuIII-BIAO0}, and successive electron uptake processes by the α-diimine fragment, followed by trpy and naphthalene π-system of BIAN or BIAO, respectively. The impact of the electron-withdrawing NO2 function in the BIAN moiety in 1c+ has been reflected in the five nearby reduction steps within the accessible potential limit of -2 V versus SCE, leading to a fully reduced BIAN4- state in [1c]4-. The aqua derivatives ({RuII-OH2}, 3a2+-3c2+) undergo simultaneous 2e-/2H+ transfer to the corresponding {RuIV-O} state and the catalytic current associated with the RuIV/RuV response probably implies its involvement in the electrocatalytic water oxidation. The aqua derivatives (3a2+-3c2+) are efficient and selective precatalysts in transforming a wide variety of alkenes to corresponding epoxides in the presence of PhI(OAc)2 as an oxidant in CH2Cl2 at 298 K as well as oxidation of primary, secondary, and heterocyclic alcohols with a large substrate scope with H2O2 as the stoichiometric oxidant in CH3CN at 343 K. The involvement of the {RuIV-O} intermediate as the active catalyst in both the oxidation processes has been ascertained via a sequence of experimental evidence.
- Singha Hazari, Arijit,Ray, Ritwika,Hoque, Md Asmaul,Lahiri, Goutam Kumar
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p. 8160 - 8173
(2016/08/24)
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- The preparation method of compound acyl method
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The invention relates to the technical field of radiation polymerization curing novel materials, and especially relates to a chemical preparation novel process of an acyl phosphine (oxide) compound represented by the general formula (I). A core characteristic of the method is that: a Grignard reagent of an aromatic compound substituted by an appropriate trichloromethyl group is subjected to condensation with related (substituted) phosphorus halide, such that a critical phosphorus-carbon bond is obtained. The innovativeness, cost economic competitiveness, and environment-friendliness of the process and chemical reaction technology provided by the invention are substantially advantaged than those of literatures and existing process routes.
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Paragraph 0024-0026
(2017/03/08)
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- Expanding the scope of the Babler–Dauben oxidation: 1,3-oxidative transposition of secondary allylic alcohols
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We report the catalytic chromium-mediated oxidation of secondary allylic alcohols to give α,β-unsaturated aldehydes with exclusive (E)-stereoselectivity. This facile procedure employs catalytic PCC (5?mol?%) and periodic acid (H5IO6) as a co-oxidant. This transformation occurs specifically with aromatic substituted allyl alcohols containing both electron withdrawing and electron donating substituents as well as a range of functional groups.
- Killoran, Patrick M.,Rossington, Steven B.,Wilkinson, James A.,Hadfield, John A.
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supporting information
p. 3954 - 3957
(2016/08/09)
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- Formylation of electron-rich aromatic rings mediated by dichloromethyl methyl ether and TiCl4: Scope and limitations
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Here the aromatic formylation mediated by TiCl4 and dichloromethyl methyl ether previously described by our group has been explored for a wide range of aromatic rings, including phenols, methoxy- and methylbenzenes, as an excellent way to produce aromatic aldehydes. Here we determine that the regioselectivity of this process is highly promoted by the coordination between the atoms present in the aromatic moiety and those in the metal core.
- Ramos-Tomillero, Iván,Paradís-Bas, Marta,De Pinho Ribeiro Moreira, Ibério,Bofill, Josep María,Nicolás, Ernesto,Albericio, Fernando
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supporting information
p. 5409 - 5422
(2015/05/13)
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- Organic inorganic hybrid cobalt phthalocyanine/polyaniline as efficient catalyst for aerobic oxidation of alcohols in liquid phase
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Organic inorganic hybrid catalyst synthesized by doping of cobalt phthalocyanine (CoPc) on polyaniline support (CoPc/PANI) exhibited higher activity for the oxidation of various alcohols to the corresponding carbonyl compounds in high to excellent yield using molecular oxygen as oxidant and isobutyraldehyde as a sacrificial agent. Notably, the synthesized catalyst was found to be truly heterogeneous in nature and could be easily recovered, recycled for several recycling runs without loss of catalytic activity.
- Panwar, Vineeta,Kumar, Pawan,Ray, Siddharth S.,Jain, Suman L.
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p. 3948 - 3953
(2015/06/08)
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- A highly efficient palladium(ii)/polyoxometalate catalyst system for aerobic oxidation of alcohols
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A simple catalyst system composed of Pd(OAc)2, phosphomolybdic acid and tetrabutylammonium acetate oxidises a range of alcohols efficiently, with turnover numbers (TONs) of up to 10000.
- Dornan, Laura M.,Muldoon, Mark J.
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p. 1428 - 1432
(2015/04/14)
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- Organoselenium-catalyzed mild dehydration of aldoximes: An unexpected practical method for organonitrile synthesis
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Areneselenenic acids (ArSeOH), readily generated from diaryl diselenides and H2O2 by in situ oxidation, were found to be effective and reusable catalysts for dehydration of aldoximes, leading to a practical and scalable preparation of useful organonitriles under mild conditions.
- Yu, Lei,Li, Hongyan,Zhang, Xu,Ye, Jianqing,Liu, Jianping,Xu, Qing,Lautens, Mark
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supporting information
p. 1346 - 1349
(2014/04/03)
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- Oxidation of alcohols to aldehydes or ketones with 1-acetoxy-1,2- benziodoxole-3(1H)-one derivatives
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Various benzylic and aliphatic alcohols were smoothly oxidized to the corresponding aromatic aldehydes and ketones as well as aliphatic ketones by treatment with 1-acetoxy-5-nitro-1,2-benziodoxole-3(1H)-one (ANBX), 1-acetoxy-5-bromo-1,2-benziodoxole-3(1H)-one (ABBX), 1-acetoxy-5-chloro-1,2- benziodoxole-3(1H)-one (ACBX), and 1-acetoxy-5-fluoro-1,2-benziodoxole-3(1H)-one (AFBX). These new tri-valent iodine compounds were prepared from 5-substituted 2-iodobenzoic acids and meta-chloroperoxybenzoic acid (m-CPBA). ANBX and ABBX were the most effective reagents for this oxidation of alcohols, and this present reaction is very attractive because of the ease of product isolation and the reusability of the reagents.
- Iinuma, Masataka,Moriyama, Katsuhiko,Togo, Hideo
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p. 772 - 780
(2014/03/21)
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- Oxidation of Alcohols to Aldehydes or Ketones with 1-Acetoxy-1,2-benziodoxole-3(1H)-one Derivatives
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Various benzylic and aliphatic alcohols were smoothly oxidized to the corresponding aromatic aldehydes and ketones as well as aliphatic ketones by treatment with 1-acetoxy-5-nitro-1,2-benziodoxole-3(1H)-one (ANBX), 1-acetoxy-5-bromo-1,2-benziodoxole-3(1H)-one (ABBX), 1-acetoxy-5-chloro-1,2-benziodoxole-3(1H)-one (ACBX), and 1-acetoxy-5-fluoro-1,2-benziodoxole-3(1H)-one (AFBX). These new trivalent iodine compounds were prepared from 5-substituted 2-iodobenzoic acids and meta-chloroperoxybenzoic acid (m-CPBA). ANBX and ABBX were the most effective reagents for this oxidation of alcohols, and this present reaction is very attractive because of the ease of product isolation and the reusability of the reagents.
- Iinuma, Masataka,Moriyama, Katsuhiko,Togo, Hideo
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p. 772 - 780
(2015/10/05)
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- IBX works efficiently under solvent free conditions in ball milling
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IBX (2-iodoxybenzoic acid), discovered in 1893, is an oxidant in synthetic chemistry whose extensive use is impeded by its explosiveness at high temperature and poor solubility in common organic solvents except DMSO. Since the discovery of Dess-Martin Periodinane in 1983, several modified IBX systems have been reported. However, under ball milling conditions, IBX works efficiently with various organic functionalities at ambient temperature under solvent free conditions. Also, the waste IBA (2-iodosobenzoic acid) produced from the reactions was in situ oxidized to IBX in the following step using oxone and thus reused for multiple cycles by conserving its efficiency (only ~6% loss after 15 cycles). This work describes an overview of a highly economical synthetic methodology which overcomes the problems of using IBX, efficiently in gram scale and in a non-explosive way. This journal is the Partner Organisations 2014.
- Achar, Tapas Kumar,Maiti, Saikat,Mal, Prasenjit
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p. 12834 - 12839
(2014/04/03)
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- A mild and highly efficient laccase-mediator system for aerobic oxidation of alcohols
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With the aid of the highly active nitroxyl radical AZADO (2-azaadamantane N-oxyl), a simple method for the aerobic catalytic oxidation of alcohols is presented. The oxidations could typically proceed under practical ambient conditions (room temperature, air atmosphere, no moisture effect, metal-free, etc.) with a broad generality of the alcohol substrates, and especially for the oxidation of complex and highly functionalized alcohols. An ionic mechanism is proposed for the present system.
- Zhu, Chenjie,Zhang, Zhi,Ding, Weiwei,Xie, Jingjing,Chen, Yong,Wu, Jinglan,Chen, Xiaochun,Ying, Hanjie
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supporting information
p. 1131 - 1138
(2014/03/21)
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- A direct and mild formylation method for substituted benzenes utilizing dichloromethyl methyl ether-silver trifluoromethanesulfonate
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A silver trifluoromethanesulfonate (AgOTf)-promoted direct and mild formylation of benzenes has been developed. The reaction utilizing dichloromethyl methyl ether (Cl2CHOMe) and AgOTf powerfully formylated various substituted benzenes under temperature conditions as low as -78 C without losing the protecting groups on the phenolic hydroxyl group.
- Ohsawa, Kosuke,Yoshida, Masahito,Doi, Takayuki
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p. 3438 - 3444
(2013/06/26)
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- Thiourea dioxide with TBHP: A fruitful and greener recipe for the catalytic oxidation of alcohols
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Thiourea dioxide, owing to its hydrogen bonding ability, has been established as an exceptional, widely applicable organocatalyst. In the present paper, thiourea dioxide, an organocatalyst, in combination with t-butyl hydroperoxide (TBHP), a non-toxic and environmentally benign oxidant, serves to be a greener and more fruitful approach for the oxidation of alcohols to corresponding carbonyl compounds in excellent yields under mild reaction conditions. The Royal Society of Chemistry 2013.
- Verma, Sanny,Singh, Raghuvir,Tripathi, Deependra,Gupta, Piyush,Bahuguna, Gajendra Mohan,Jain, Suman L.
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p. 4184 - 4188
(2013/04/23)
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- Hypervalent iodine/TEMPO-mediated oxidation in flow systems: A fast and efficient protocol for alcohol oxidation
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Hypervalent iodine(III)/TEMPO-mediated oxidation of various aliphatic, aromatic and allylic alcohols to their corresponding carbonyl compounds was successfully achieved by using microreactor technology. This method can be used as an alternative for the oxidation of various alcohols achieving excellent yields and selectivities in significantly shortened reaction times.
- Ambreen, Nida,Kumar, Ravi,Wirth, Thomas
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p. 1437 - 1442
(2013/08/23)
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- METHOD FOR OXIDIZING ALCOHOLS
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A method for oxidizing an alcohol, wherein oxidation is performed in the presence of a compound represented by the following formula (I) and a bulk oxidant, which enables efficient oxidation of secondary alcohols as well as primary alcohols, and can attain high reaction efficiency even when air is used as a bulk oxidant.
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Paragraph 0111; 0112
(2013/06/05)
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- SnCl4-induced unsymmetrical cleavage of Bis(N,N- diethylcarbamoyltelluro)-arylmethanes: Generation of tellurobenzaldehydes
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Tellurobenzaldehydes bearing an electron-withdrawing substituent were generated by way of SnCl4-induced unsymmetrical cleavage of bis(N,N-dialkylcarbamoyltelluro)arylmethanes, and were trapped using 2,3-dimethyl-1,3-butadiene.
- Shimada, Kazuaki,Higashi, Takumi,Gong, Yaling,Aoyagi, Shigenobu,Takikawa, Yuji,Ogawa, Satoshi
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p. 482 - 489
(2013/12/04)
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- A facile procedure for the conversion of oximes to ketones and aldehydes by the use of jones reagent adsorbed on kieselguhr reagent
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An efficient oxidation of oximes to their corresponding ketones and aldehydes with Jones reagent supported on kieselguhr under heterogeneous conditions at room temperature in the yield between 84 and 93% is described. The present procedure is an extension of application of Jones reagent supported on kieselguhr.
- Lou, Ji-Dong,Lin, Fang,Lu, Xiu Lian,Wang, Qiang,Zou, Xiao-Nan
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experimental part
p. 282 - 284
(2012/05/31)
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- A mild and environmentally benign procedure for the oxidative cleavage of oximes with potassium permanganate supported on kieselguhr
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A facile, mild, and relative environmentally friendly procedure for the regeneration of aldehydes and ketones from their oximes with potassium permanganate supported on kieselguhr reagent at room temperature under heterogeneous conditions in the yield between 82-96% is described.
- Lou, Ji-Dong,Lin, Fang,Huang, Lihong,Zou, Xiao-Nan
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p. 1027 - 1029
(2012/11/07)
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