- Electrosynthesis of heteroaromatic aldehydes by palladium-catalyzed carbonylation of heteroaromatic iodides in the presence of formic acid
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The palladium-catalyzed electrocarbonylation of heteroaromatic iodides, performed in the presence of formic acid under one atmosphere of carbon monoxide, affords heteroaromatic aldehydes in moderate to good yields. It has been developed a new application of palladium-catalyzed formylation using carbon monoxide, formic acid and tertiary amines as ligands under electrochemical reducing conditions.
- Chiarotto, Isabella,Feroci, Marta
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- Controlled reduction of activated primary and secondary amides into aldehydes with diisobutylaluminum hydride
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A practical method is disclosed for the reduction of activated primary and secondary amides into aldehydes using diisobutylaluminum hydride (DIBAL-H) in toluene. A wide range of aryl and alkyl N-Boc, N,N-diBoc and N-tosyl amides were converted into the corresponding aldehydes in good to excellent yields. Reduction susceptible functional groups such as nitro, cyano, alkene and alkyne groups were found to be stable. Broad substrate scope, functional group compatibility and quick conversions are the salient features of this methodology.
- Azeez, Sadaf,Kandasamy, Jeyakumar,Sabiah, Shahulhameed,Sureshbabu, Popuri
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supporting information
p. 2048 - 2053
(2022/03/31)
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- Palladium-Catalyzed Reductive Carbonylation of (Hetero) Aryl Halides and Triflates Using Cobalt Carbonyl as CO Source
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An efficient protocol for the reductive carbonylation of (hetero) aryl halides and triflates under CO gas-free conditions using Pd/Co2(CO)8 and triethylsilane has been developed. The mild reaction conditions, enhanced chemoselectivity and, easy access to heterocyclic and vinyl carboxaldehydes highlights its importance in organic synthesis.
- Dogga, Bhushanarao,Joseph, Jayan T.,Kumar, C. S. Ananda
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supporting information
p. 309 - 313
(2020/12/23)
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- Preparation method 3- thiophene formaldehyde
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The preparation method disclosed by the invention has the advantages that 3 -methylmorpholine - N N-oxide, is mixed and heated to: DEG 3 - to keep the first temperature unchanged, after being kept at first temperature for a period of time and then filtered, to obtain N -halothiophene in a mild reaction condition . The method first comprises, DEG C and, hours after being, heated to 3 - DEG C and then filtering the mixture solution; of, halogenomethylthiophene to prepare 3 -thiophene formaldehyde pure product N - through cooling, and washing second to obtain crude,halothiophene by further rectification, and the preparation method disclosed by the invention is suitable for 3 - industrial production,thieno-formaldehyde, in a high-selectivity, high yield 3 - The present invention discloses 3 -desolvoked,methyl, thiophenecarboxaldehyde is obtained, by further distillation . The preparation method disclosed by the invention, is simple.
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Paragraph 0041; 0043; 0056; 0058
(2020/03/23)
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- Visible-light mediated facile dithiane deprotection under metal free conditions
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Visible light mediated facile and selective dithiane deprotection under metal free conditions is developed. Eosin Y (1 mol%) proved to be an effective catalyst for the dithiane deprotection under the ambient photoredox conditions. The standard household compact fluorescent light source (CFL bulb) proved to be effective under open-air conditions in aqueous acetonitrile at room temperature. The protocol that exhibits a broad substrate scope and functional group tolerance has been shown to expand to a range of transformations for the electron-rich and -deficient thioacetals and thioketals. The synthetic utility of this protocol has also been demonstrated by gram-scale application.
- Dharpure, Pankaj D.,Bhowmick, Anindita,Warghude, Prakash K.,Bhat, Ramakrishna G.
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- 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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- Dual-fixations of europium cations and TEMPO species on metal-organic frameworks for the aerobic oxidation of alcohols
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The efficient and selective aerobic oxidation of alcohols has been investigated with judicious combinations of europium-incorporated and/or TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl)-functionalized zirconium-based porous metal-organic frameworks (MOFs). Although MOFs are well-known catalytic platforms for the aerobic oxidation with radical-functionalities and metal nanoparticles, these systematic approaches involving metal cations and/or radical species introduce numerous interesting aspects for cooperation between metals and TEMPO for the aerobic oxidation of alcohols. The role of TEMPO as the oxidant in the heterogeneous catalytic aerobic oxidation of alcohols was revealed through a series of comparisons between metal-anchored, TEMPO-anchored, and metal and TEMPO-anchored MOF catalysis. The fine tunability of the MOF allowed the homogeneously and doubly functionalized catalysts to undergo organic reactions in the heterogeneous media. In addition, the well-defined and carefully designed heterogeneous molecular catalysts displayed reusability along with better catalytic performance than the homogeneous systems using identical coordinating ligands. The role of metal-cation fixation should be carefully revised to control their coordination and maximize their catalytic activity. Lastly, the metal cation-fixed MOF displayed better substrate tolerance and reaction efficiencies than the TEMPO-anchored MOF or mixture MOF systems.
- Jeoung, Sungeun,Kim, Min,Kim, Seongwoo,Lee, Jooyeon,Moon, Hoi Ri
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supporting information
p. 8060 - 8066
(2020/07/10)
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- Sequential Connection of Mutually Exclusive Catalytic Reactions by a Method Controlling the Presence of an MOF Catalyst: One-Pot Oxidation of Alcohols to Carboxylic Acids
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A functionalized metal-organic framework (MOF) catalyst applied to the sequential one-pot oxidation of alcohols to carboxylic acids controls the presence of a heterogeneous catalyst. The conversion of alcohols to aldehydes was acquired through aerobic oxidation using a well-known amino-oxy radical-functionalized MOF. In the same flask, a simple filtration of the radical MOF with mild heating of the solution completely altered the reaction media, providing radical scavenger-free conditions suitable for the autoxidation of the aldehydes formed in the first step to carboxylic acids. The mutually exclusive radical-catalyzed aerobic oxidation (the first step with MOF) and radical-inhibited autoxidation (the second step without MOF) are sequentially achieved in a one-pot manner. Overall, we demonstrate a powerful and efficient method for the sequential oxidation of alcohols to carboxylic acids by employing a readily functionalizable heterogeneous MOF. In addition, our MOF in-and-out method can be utilized in an environmentally friendly way for the oxidation of alcohols to carboxylic acids of industrial and economic value with broad functional group tolerance, including 2,5-furandicarboxylic acid and 1,4-benzenedicarboxylic acid, with good yield and reusability. Furthermore, MOF-TEMPO, as an antioxidative stabilizer, prevents the undesired oxidation of aldehydes, and the perfect "recoverability"of such a reactive MOF requires a re-evaluation of the advantages of MOFs from heterogeneity in catalytic and related applications.
- Kim, Seongwoo,Lee, Ha-Eun,Suh, Jong-Min,Lim, Mi Hee,Kim, Min
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supporting information
p. 17573 - 17582
(2020/12/22)
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- Europium-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones and Photoluminescence Tracking
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Europium is a lanthanide rare-earth metal and is known as a key element in luminophore development. Since europium has two relatively stable oxidation states, Eu2+ and Eu3+, which is exceptional among the various lanthanide elements, we have developed a europium-catalyzed aerobic oxidation with external oxidants utilizing the redox cycle of Eu2+/Eu3+. The reaction was performed under mild conditions with a wide substrate scope. The photoluminescence spectra clearly demonstrate the oxidation state changes that occur during the presented europium-catalyzed aerobic oxidation. (Figure presented.).
- Kim, Seongwoo,Kim, Youngik,Jin, Hyomin,Park, Myung Hwan,Kim, Youngjo,Lee, Kang Mun,Kim, Min
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supporting information
(2019/02/05)
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- Efficient acceptorless photo-dehydrogenation of alcohols and: N -heterocycles with binuclear platinum(ii) diphosphite complexes
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Although photoredox catalysis employing Ru(ii) and Ir(iii) complexes as photocatalysts has emerged as a versatile tool for oxidative C-H functionalization under mild conditions, the need for additional reagents acting as electron donor/scavenger for completing the catalytic cycle undermines the practicability of this approach. Herein we demonstrate that photo-induced oxidative C-H functionalization can be catalysed with high product yields under oxygen-free and acceptorless conditions via inner-sphere atom abstraction by binuclear platinum(ii) diphosphite complexes. Both alcohols (51 examples), particularly the aliphatic ones, and saturated N-heterocycles (24 examples) can be efficiently dehydrogenated under light irradiation at room temperature. Regeneration of the photocatalyst by means of reductive elimination of dihydrogen from the in situ formed platinum(iii)-hydride species represents an alternative paradigm to the current approach in photoredox catalysis.
- Zhong, Jian-Ji,To, Wai-Pong,Liu, Yungen,Lu, Wei,Che, Chi-Ming
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p. 4883 - 4889
(2019/05/16)
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- 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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p. 418 - 424
(2019/01/28)
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- Pd-Catalyzed Dehydrogenative Oxidation of Alcohols to Functionalized Molecules
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A dehydrogenative oxidation reaction of primary alcohols to aldehydes catalyzed by a simple Pd/Xantphos catalytic system was developed under an argon or nitrogen atmosphere without oxidizing agents or hydrogen acceptors. The reaction product could be easily changed: under aerobic conditions, esters were obtained in aprotic solvents, whereas the corresponding carboxylic acids were produced in aqueous media. These oxidizing processes were applicable to the efficient synthesis of useful nitrogen-containing heterocyclic compounds such as indole, quinazoline, and benzimidazole via intramolecular versions of this reaction from amino alcohols.
- Mori, Takamichi,Ishii, Chihiro,Kimura, Masanari
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supporting information
p. 1709 - 1717
(2019/09/04)
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- Preparation method of 3-thiophenecarboxaldehyde
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The invention relates to the technical field of organic synthesis, in particular to a preparation method of 3-thiophenecarboxaldehyde. The preparation method of 3-thiophenecarboxaldehyde comprises thefollowing steps: performing reaction on 1,1,3,3-tetramethoxypropane under the acidic condition, performing mixed reaction on the reaction product and 1,4-dithio-2,5-diol under the alkaline conditionand performing aftertreatment to obtain the 3-thiophenecarboxaldehyde. By the preparation method of 3-thiophenecarboxaldehyde, the 3-thiophenecarboxaldehyde product with the purity exceeding 98 percent can be prepared only through simple mixing and stirring reaction, reaction does not need ultralow temperature and dangerous reagents in the preparation process, and the production safety coefficientis increased. Furthermore, the preparation method provided by the invention is simple in operation, the raw materials are easily available, operation cost and raw material cost are reduced, and the preparation method is suitable for industrialized production of 3-thiophenecarboxaldehyde.
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Page/Page column 6-8
(2018/06/15)
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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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- Studies on Iron-Catalyzed Aerobic Oxidation of Benzylic Alcohols to Carboxylic Acids
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A comprehensive study on aerobic oxidation of benzylic alcohols to carboxylic acids with a catalytic amount each of Fe(NO 3) 3 ·9H 2 O, TEMPO, and KCl is conducted. Various synthetically useful functional groups are well tolerated in the reaction. Distinct electronic and steric effects are observed in the reaction: electron-withdrawing groups accelerate the reaction while electron-donating groups make the reaction slower, and ortho -substituted substrates react slower than meta -substituted substrates. Several large-scale reactions (100 mmol) are conducted using a slow air flow of 30 mL/min to demonstrate the practicality of this method in an academic laboratory.
- Jiang, Xingguo,Ma, Shengming
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p. 1629 - 1639
(2018/02/26)
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- Oxygen-Rich Carbon Quantum Dots as Catalysts for Selective Oxidation of Amines and Alcohols
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Metal-free carbocatalysis has been widely utilized for aerobic oxidative reactions. Here, we report that oxygen-rich carbon quantum dots (O-CQDs) demonstrate a catalytic performance superior to graphene oxide, if used as a metal-free nanocatalyst for the direct transformation of amines and alcohols, under mild and solvent-free conditions. O-CQDs show a yield of 75 % for the oxidative coupling of amine to imine (with 5 wt % catalyst loading) and a conversion of 3.8 % for benzyl alcohol (with 2 wt % catalyst loading). The catalytic activities of thermally treated O-CQDs are further improved for benzylamine, for example, indicated by a yield of up to 98 % with 4 wt % catalyst loading. In addition, O-CQDs show a photoenhanced catalytic ability of amine (98 % yield with 5 wt % catalyst loading for 6 h reaction). Characterizations and simulations show that numerous carboxyl oxygen functional groups and unpaired electrons at the edge sites of O-CQDs are likely involved in the aerobic oxidation of amines.
- Ye, Jianglin,Ni, Kun,Liu, Jie,Chen, Guanxiong,Ikram, Mujtaba,Zhu, Yanwu
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p. 259 - 265
(2018/01/17)
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- Efficient aerobic oxidation of alcohols catalyzed by NiGa hydrotalcites in the absence of any additives
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The aerobic oxidation of alcohol catalyzed by NiGa hydrotalcites in the absence of any additives has been studied in detail. The research results revealed that the surface basicity significantly affected the catalytic performance. Moreover, the Br?nsted OH basic site on Ni-containing hydrotalcites was suggested to be the key active site and accelerated the oxidation. The catalytic system had good tolerance for various alcohols, and an excellent selectivity of aldehyde could be obtained for the oxidation of primary alcohol. A probable non-radical reaction path for the transformation has been proposed according to the catalytic results, isotope labelling experiments and Hammett experiments.
- Sun, Fuan,Zhou, Jiacheng,Zhou, Weiyou,Pan, Jiugao,Qian, Junfeng,He, Mingyang,Chen, Qun
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p. 4029 - 4035
(2018/03/21)
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- Palladium-Catalyzed Ligand-Controlled Selective Synthesis of Aldehydes and Acids from Aryl Halides and Formic Acid
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Selective synthesis is in the core of modern organic chemistry. In this communication, a novel ligand-dependent palladium-catalyzed carbonylation procedure for the divergent synthesis of aldehydes and carboxylic acids from easily available aryl halides was established. Under the same reaction conditions, the reaction pathway could be controlled by the ligands applied to give formylated and carboxylated products selectively. Sterically hindered monodentate ligands facilitated the reductive carbonylation and provided aldehydes, whereas bidentate ligands preferred the carboxylation reaction and produced carboxylic acids. A wide range of functional groups were tolerated, and the products were, in general, obtained in moderate to excellent yields.
- Wu, Fu-Peng,Peng, Jin-Bao,Meng, Ling-Shen,Qi, Xinxin,Wu, Xiao-Feng
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p. 3121 - 3124
(2017/08/29)
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- Ligandless Palladium-Catalyzed Reductive Carbonylation of Aryl Iodides under Ambient Conditions
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Ligandless palladium-catalyzed reductive carbonylation of aryl iodides for the synthesis of aromatic aldehydes has been developed. This carbonylation process proceeded effectively even under ambient temperature and pressure. In addition, this method enables successive reductive carbonylation of diiodobenzenes to furnish dialdehydes in satisfactory yields. Finally, the nature of the active catalytic species is discussed.
- Han, Wei,Liu, Binbin,Chen, Junjie,Zhou, Qing
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supporting information
p. 835 - 840
(2017/04/06)
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- Method for preparing aldehyde ketone by efficiently catalyzing molecular oxygen to oxidize alcohol by taking hydrotalcite-like material as catalyst
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The invention belongs to the technical field of liquid-phase catalytic oxidation and provides a method for preparing aldehyde ketone by efficiently catalyzing molecular oxygen to oxidize alcohol by taking a hydrotalcite-like material as a catalyst. The catalyst can be expressed as A-NixM-LDHs (A=OH, CO3, CH3COO and PO4; M is Ga or In; the ratio of Ni to M is (2-4) to 1). The method is characterized by preparing aldoketones compounds by carrying out aerobic oxidation reaction on alcohol under mild condition without adding additives in the presence of the catalyst. The hydrotalcite-like material can be synthesized in quantity and can be recycled; the method has the advantages of high selectivity and yield of aldehyde ketone, mild reaction condition, low cost and easiness in realizing industrialization.
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Paragraph 0036; 0037; 0038; 0039; 0041
(2017/09/29)
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- Aerobic Oxidation of Alcohols to Carbonyl Compounds Catalyzed by N-Hydroxyphthalimide (NHPI) Combined with CoTPP-Zn2Al-LDH
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A catalytic system for the aerobic oxidation of alcohols by N-hydroxyphthalimide (NHPI) combined with cobalt porphyrin intercalated heterogeneous hybrid catalyst (CoTPP-Zn 2Al-LDH) has been developed. The results showed that this catalytic system can effectively catalyze the oxidation of alcohols to the corresponding carbonyl compounds. And the hybrid catalyst can be reused for five times with no appreciable reduction of activity. [Figure not available: see fulltext.]
- Zhou, Weiyou,Chen, Dongwei,Cui, Aijun,Qian, Junfeng,He, Mingyang,Chen, Qun
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p. 295 - 299
(2017/03/23)
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- Green method for preparation of aldehyde or ketone by iron catalyzed alcohol oxidation
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The invention provides a green method for preparation of aldehyde or ketone by iron catalyzed alcohol oxidation. The method adopts a common iron salt as the catalyst, uses an oxynitride as the cocatalyst, can realize oxidation of various alcohols in a non-halogen solvent and under open air room temperature conditions, and especially can achieve oxidation of high selectivity non-active fatty primary alcohol. The catalytic system uses a cheap and easily available, non-toxic and high activity iron catalyst system, and uses economical, safe and green air as the oxidant. The reaction temperature can be set at room temperature condition. The catalytic system has few components, and additional adding of a ligand or alkali compound is unnecessary. The reaction is easy in operation, and especially can realize oxidation of non-active fatty primary alcohol into aldehyde or ketone efficiently. The method provided by the invention has very mild requirements for reaction conditions, and has good research and industrial application prospects.
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Paragraph 0073; 0074; 0075
(2017/08/29)
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- A Convenient Palladium-Catalyzed Reductive Carbonylation of Aryl Iodides with Dual Role of Formic Acid
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Palladium-catalyzed reductive carbonylation of aryl halides represents a straightforward pathway for the synthesis of aromatic aldehydes. The known reductive carbonylation procedures either require CO gas or complexed compounds as CO sources. In this communication, we developed a palladium-catalyzed reductive carbonylation of aryl iodides with formic acid as the formyl source. As a convenient, practical, and environmental friendly methodology, no additional silane or H2 was required. A variety of aromatic aldehydes were isolated in moderate to excellent yields under mild reaction conditions. Notably, this is the first procedure on using formic acid as the formyl source. Say no to CO gas! A convenient, practical, and environmental friendly palladium-catalyzed reductive carbonylation of aryl iodides with formic acid as the formyl source has been developed (see scheme). No additional silane or H2 was required here. A variety of aromatic aldehydes were isolated in moderate to excellent yields under mild reaction conditions.
- Qi, Xinxin,Li, Chong-Liang,Wu, Xiao-Feng
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supporting information
p. 5835 - 5838
(2016/04/26)
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- Synthesis and characterization of new nematic liquid crystalline compounds-based thiophene units
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Four new liquid crystalline thiophene compounds (M1-M4) with a long flexible spacer were prepared. Their structures were characterized by Fourier transform infrared and proton nuclear magnetic resonance. The mesomorphism and thermal stability were investigated with differential scanning calorimetry, polarizing optical microscopy, and thermogravimetric analysis. The photo-physical properties were evaluated using ultraviolet/visible spectroscopy and photoluminescence. M1-M4 all showed thermotropic mesogenic properties with excellent thermal stability, and exhibited nematic threaded texture, droplet texture, and Schlieren texture on heating and cooling cycles. The effect of flexible spacer and terminal groups on mesomorphic and spectroscopic property is discussed. The experimental results demonstrated that the tendency toward melting temperature (Tm) decreased, while isotropic temperature (Ti) increased with increasing the flexible spacer length. In CHCl3 solution, these thiophene compounds displayed an intense broad absorption band peaking within 230-340 nm and a maximum fluorescent emission wavelength at 426-439 nm.
- Jia, Ying-Gang,Su, Dong,Guo, Zhi-Hao,Hu, Jian-She
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- An Efficient and General Method for Formylation of Aryl Bromides with CO2 and Poly(methylhydrosiloxane)
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The formylation of aryl halides with CO2 to generate aryl aldehydes is challenging. Herein, we report a novel synthesis of aryl aldehydes by formylation of aryl bromides with CO2 and a waste silane, poly(methylhydrosiloxane) (PMHS). It has been discovered that a simple combination of 1,3-bis(diphenyphosphino)propane (DPPP)-chelated Pd catalyst, Pd(DPPP)Cl2, with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is able to effectively catalyze the reaction, leading to aryl aldehydes in moderate to excellent yields, and without any by-products in most cases. Moreover, this route could be extended to the formylation of aryl iodides with high efficiency. This approach is simple, less costly, and environmentally friendly, and also widens the applications of CO2 to form value-added chemicals by the construction of new C-C bonds.
- Yu, Bo,Yang, Zhenzhen,Zhao, Yanfei,Hao, Leiduan,Zhang, Hongye,Gao, Xiang,Han, Buxing,Liu, Zhimin
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supporting information
p. 1097 - 1102
(2016/01/16)
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- Visible light mediated chemo-selective oxidation of benzylic alcohols
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A highly chemoselective visible light mediated strategy has been developed for oxidation of benzylic alcohols. The method circumvents the use of toxic metal catalysts, high energy light source, and operates at room temperature. Furthermore reaction is easily scalable to gram levels.
- Devari, Shekaraiah,Rizvi, Masood Ahmad,Shah, Bhahwal Ali
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supporting information
p. 3294 - 3297
(2016/07/11)
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- Highly efficient transformation of alcohol to carbonyl compounds under a hybrid bifunctional catalyst originated from metalloporphyrins and hydrotalcite
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The development of a highly active and selective catalytic system that is economical, environmentally benign, and easily recoverable is highly desirable. Bifunctional hybrid catalysts originated from metalloporphyrins (MTSPP; M = Co, Fe, and Mn), and hydrotalcite have been synthesized, characterized, and investigated in the aerobic oxidation of alcohols in the presence of isobutyraldehyde. The designed catalysts exhibited excellent activity, broad applicable scope, and good stability in the oxidation. The effect of surface basicity on the catalytic performance has been studied in detail. The research results showed that as well as protecting the metalloporphyrin molecule, the surface basicity of hydrotalcite also contributed to improving the catalytic activity and the selectivity of aldehyde, and a synergistic effect was observed in the catalytic system. A proposed mechanism for the reaction involving the formation of high-valence cobalt-oxo porphyrin intermediate was postulated based on catalytic results and Hammett and H218O experiments.
- Zhou, Wei-You,Tian, Peng,Sun, Fu'An,He, Ming-Yang,Chen, Qun
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p. 105 - 116
(2016/01/26)
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- Iron/ABNO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes and Ketones under Ambient Atmosphere
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We report a new Fe(NO3)3·9H2O/9-azabicyclo[3.3.1]nonan-N-oxyl catalyst system that enables efficient aerobic oxidation of a broad range of primary and secondary alcohols to the corresponding aldehydes and ketones at room temperature with ambient air as the oxidant. The catalyst system exhibits excellent activity and selectivity for primary aliphatic alcohol oxidation. This procedure can also be scaled up. Kinetic analysis demonstrates that C-H bond cleavage is the rate-determining step and that cationic species are involved in the reaction.
- Wang, Lianyue,Shang, SenSen,Li, Guosong,Ren, Lanhui,Lv, Ying,Gao, Shuang
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p. 2189 - 2193
(2016/03/15)
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- Effect of basicity on the catalytic properties of Ni-containing hydrotalcites in the aerobic oxidation of alcohol
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A series of Ni-containing hydrotalcites with different basicities have been prepared by introducing different Mg2+ contents, and characterized by XRD, SEM, TG-DTG, ICP, FTIR, Hammett analysis, DR UV–vis, XPS, etc. The effects of basicity on the catalytic performance in the selective aerobic oxidation of alcohols and the mechanism have been studied. The results showed that substituting Ni2+ in the structure by Mg2+ ions significantly increased the surface basicity of the catalysts. The surface basicity of Ni-containing hydrotalcites could accelerate the first acid-base reaction step in the oxidation and improve the catalytic activity. Varied alcohols were tested and discussed in the reaction system to verify the effect, and the results indicated that the activity of α-C[sbnd]H bond is the key factor for the benzyl alcohol derivatives, while the first base-acid reaction step may be more important for aliphatic alcohols. The comparison results between the hydrotalcites and the calcined samples showed that the type of basic site have significantly influence on the catalytic activity, and only the Br?nsted OH basic sites accelerate the oxidation. In addition, a probable mechanism for the reaction was postulated based on catalytic results, Hammett and a series of controlled experiments. The main factors affecting the catalytic oxidation of varied alcohols using molecular oxygen as the ultimate oxidant have been discussed, which may be helpful in designing more efficient catalyst.
- Zhou, Weiyou,Tao, Qianyun,Pan, Jiugao,Liu, Jie,Qian, Junfeng,He, Mingyang,Chen, Qun
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p. 255 - 265
(2016/10/30)
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- Palladium-catalyzed carbonylations of aryl bromides using paraformaldehyde: Synthesis of aldehydes and esters
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Carbonylation reactions represent useful tools for organic synthesis. However, the necessity to use gaseous carbon monoxide is a disadvantage for most organic chemists. To solve this problem, novel protocols have been developed for conducting palladium-catalyzed reductive carbonylations of aryl bromides and alkoxycarbonylations using paraformaldehyde as an external CO source (CO gas free). Hence, aromatic aldehydes and esters were synthesized in moderate to good yields.
- Natte, Kishore,Dumrath, Andreas,Neumann, Helfried,Beller, Matthias
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supporting information
p. 10090 - 10094
(2015/03/31)
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- Copper-catalyzed aerobic oxidative cleavage of C-C bonds in epoxides leading to aryl nitriles and aryl aldehydes
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Novel copper-catalyzed aerobic synthesis of aryl nitriles and aldehydes from epoxides via C-C single bond cleavage has been discovered. This reaction provides a practical method toward the synthesis of aryl nitriles and aldehydes, which are versatile intermediates and building blocks in organic synthesis. This journal is
- Gu, Lijun,Jin, Cheng
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supporting information
p. 6572 - 6575
(2015/04/14)
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- Fukuyama reduction and integrated thioesterification/fukuyama reduction of thioesters and acyl chlorides using continuous flow
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Fukuyama reduction of thioesters has been achieved using a polymer-supported Pd[0] catalyst (Pd/XAD-4), and continuous flow conditions. The generality of this reaction is good with a range of aldehydes prepared in excellent yields. In addition, an integrated multistep thioesterfication/ Fukuyama reduction has been developed that allows acyl chlorides to be directly converted to the corresponding aldehydes. Integral to this process is the use of polymer-supported amine and isocyanate reagents to achieve thioesterification and scavenge unreacted thiol. In addition, catch-and-release purification has been employed to enable isolation of the aldehyde from silylthioether byproducts without the need for chromatographic purification.
- Asadi, Mousa,Bonke, Shannon,Polyzos, Anastasios,Lupton, David W.
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p. 2070 - 2074
(2014/06/24)
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- Pd/C-catalyzed direct formylation of aromatic iodides to aryl aldehydes using carbon dioxide as a C1 resource
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Pd/C-catalyzed direct formylation of aromatic iodides to aryl aldehydes using CO2 as a C1 resource was realized for the first time in the presence of hydrosilanes and base DBU under mild conditions, giving a series of aldehydes in good yields. The Royal Society of Chemistry 2014.
- Yu, Bo,Zhao, Yanfei,Zhang, Hongye,Xu, Jilei,Hao, Leiduan,Gao, Xiang,Liu, Zhimin
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supporting information
p. 2330 - 2333
(2014/03/21)
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- A benzodithiophene-based semiconducting polymer for organic thin film transistor
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Benzodithiophene based organic semiconducting polymer was designed and synthesized by stille coupling reaction. The structure of polymer was confirmed by NMR and IR. The weight average molecular weight (Mw) of polymer was 8,400 using GPC with polydispersity index of 1.4. The thermal, optical and electrochemical properties of polymer were characterized by TGA and DSC, UV-vis absorption and cyclic voltammetry. OTFT device using PBDT-10 exhibited the mobility of 7.2 × 10-5 cm2 V-1 s -1 and Ion/Ioff of 2.41 × 103. The film morphology and crystallinity of PBDT-10, was studied using AFM and XRD.
- Hong, Jung-A,Kim, Ran,Yun, Hui-Jun,Park, Joung-Man,Shin, Sung Chul,Kim, Yun-Hi
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p. 1170 - 1174
(2013/07/28)
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- Chemoselective oxidative C(CO)-C(methyl) bond cleavage of methyl ketones to aldehydes catalyzed by CuI with molecular oxygen
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Aldehyde Termination: A novel copper-catalyzed transformation from methyl ketones into aldehydes has been accomplished. This method is applicable to a wide range of aromatic and aliphatic methyl ketones and chemoselectively produces aldehydes, accompanied by the release of hydrogen (H2) and carbon dioxide (CO2) as by-products. Copyright
- Zhang, Lin,Bi, Xihe,Guan, Xiaoxue,Li, Xingqi,Liu, Qun,Barry, Badru-Deen,Liao, Peiqiu
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supporting information
p. 11303 - 11307
(2013/11/06)
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- Palladium-catalyzed reductive carbonylation of aryl halides with N-formylsaccharin as a CO source
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Easy peasy: The title reaction employs N-formylsaccharin, which is an easily accessible crystalline compound, as an effective CO source. The reactions proceed with a small excess of the CO source at moderate temperatures and were successfully applied to a wide range of aryl bromides. DMF=N,N- dimethylformamide, dppb=1,4-bis-(diphenylphosphino)butane. Copyright
- Ueda, Tsuyoshi,Konishi, Hideyuki,Manabe, Kei
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supporting information
p. 8611 - 8615
(2013/09/12)
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- Solid supported Ru(0) nanoparticles: An efficient ligand-free heterogeneous catalyst for aerobic oxidation of benzylic and allylic alcohol to carbonyl
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Polymer immobilized stable, spherical ruthenium nanoparticles were prepared, characterized, and acted as a heterogeneous catalyst for the selective benzylic and allylic alcohol oxidation into the corresponding carbonyls using molecular oxygen. The solid supported Ru(0) (SS-Ru) as a heterogeneous catalyst exhibits good reusability and easy separation from the reaction mixture by filtration.
- Das, Pralay,Aggarwal, Nidhi,Guha, Nitul Ranjan
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supporting information
p. 2924 - 2928
(2013/06/27)
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- Osmium (VI) catalyzed chemoselective oxidation of allylic and benzylic alcohols
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A mild and highly chemoselective approach to oxidation of allylic, electron rich/deficient benzylic, and heterocyclic alcohols employing catalytic quantities of K2[OsO2(OH)4] (3 mol %) and chloramine-T (50 mol %) is described. The protocol offers short reaction times (25 min-2 h), controlled oxidation, and tolerance to a variety of substrates. A systematic mechanistic study based on the LC-ESI-MS/MS reveals the presence of imidotriooxoosmium species which further reacts with alcohol to give the oxidized product.
- Devari, Shekaraiah,Deshidi, Ramesh,Kumar, Manjeet,Kumar, Arvind,Sharma, Simmi,Rizvi, Masood,Kushwaha, Manoj,Gupta, Ajai Prakash,Shah, Bhahwal Ali
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supporting information
p. 6407 - 6410
(2013/11/19)
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- PROCESS FOR PRODUCTION OF OXIDATION REACTION PRODUCT OF AROMATIC COMPOUND
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The present invention provides a process for producing an oxidation reaction product of an aromatic compound, having excellent environmental load reduction performance, cost reduction performance, etc. Provided is a process for producing an oxidation reaction product of a raw material aromatic compound by reacting the raw material aromatic compound with an oxidizing agent. The process further uses an electron donor-acceptor linked molecule. The process includes the step of: reacting the electron donor-acceptor linked molecule in an electron-transfer state, the oxidizing agent, and the raw material aromatic compound, thereby generating an oxidation reaction product resulting from oxidation of the raw material aromatic compound.
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Page/Page column 19
(2012/07/14)
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- Palladium-catalyzed reductive carbonylation of aryl bromides with phosphinite ligands
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A palladium-catalyzed reductive carbonylation of aryl bromides into the corresponding aryl aldehydes has been described using synthesis gas in the presence of phosphinite ligands. Several products have been synthesized in moderate to good yields (35-97 %) under mild reaction conditions. Copyright
- Neumann, Helfried,Kadyrov, Renat,Wu, Xiao-Feng,Beller, Matthias
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p. 2213 - 2216
(2012/10/29)
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- MULTICYCLIC COMPOUNDS AND METHODS OF USE THEREOF
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Provided herein are multicyclic compounds, methods of their synthesis, pharmaceutical compositions comprising the compounds, and methods of their use. The compounds provided herein are useful for the treatment, prevention, and/or management of various neurological disorders, including but not limited to, psychosis and schizophrenia.
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Page/Page column 89
(2011/06/25)
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- A one-pot oxidation/allylation/oxidation sequence for the preparation of β,γ-unsaturated ketones directly from primary alcohols
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A one-pot oxidation/allylation/oxidation procedure has been developed for the conversion of primary alcohols into β,γ-unsaturated ketones. The methodology has been applied to a range of alcohols, and in some cases, isomerisation to produce the corresponding α,β-unsaturated ketones has been carried out.
- Moody, Catherine L.,Pugh, David S.,Taylor, Richard J.K.
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experimental part
p. 2511 - 2514
(2011/05/09)
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- Low-pressure hydrogenation of arenecarboxylic acids to aryl aldehydes
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A highly effective palladium catalyst has been developed that allows the selective hydrogenation of arenecarboxylic acids to the aryl aldehydes in the presence of pivalic anhydride already at 5 bar hydrogen pressure. With the new catalyst, diversely functionalized aromatic and heteroaromatic aldehydes are conveniently accessible from the corresponding carboxylic acids in a single reaction step without any overreduction to the alcohols.
- Goossen, Lukas J.,Khan, Bilal Ahmad,Fett, Thomas,Treu, Matthias
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supporting information; experimental part
p. 2166 - 2170
(2010/11/04)
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- Synthesis and catalytic applications of stable palladium dioxygen complexes
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The synthesis and characterization of air-stable palladium dioxygen complexes Pd(O2)L2 of basic phosphines L = P(1-Ad) 2nBu, PtBu2nBu is described. Contrary to general belief, these dioxygen complexes are stable catalyst precursors for palladium-catalyzed coupling reactions. Specifically, palladium-catalyzed formylations and alkoxy carbonylations of aryl bromides proceed in high yield in air using commercial non-degassed solvents. It is shown that Pd(O2)L2 complexes are reduced back to the catalytically active palladium(0) species in the reductive atmosphere of CO or H2 at the onset of the carbonylation reaction.
- Sergeev, Alexey G.,Neumann, Helfried,Spannenberg, Anke,Beller, Matthias
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experimental part
p. 3368 - 3373
(2010/10/04)
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- Catalysis in flow: The practical and selective aerobic oxidation of alcohols to aldehydes and ketones
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A safe, practical and selective process for the aerobic oxidation of alcohols to aldehydes and ketones has been developed using an Ru catalyst in a continuous flow reactor. Benzylic and allylic alcohols are oxidised selectively to their corresponding aldehydes and ketones, including substrates containing N- and S-heteroatoms. The rate of turnover is compatible with that previously reported using batch or microchannel reactors under optimised conditions. A preliminary kinetic model is derived that is supported by experimental observations. Last but not least, tandem oxidation-olefination may be achieved without the need to isolate the alcohol intermediate or to switch solvent.
- Zotova, Natalia,Hellgardt, Klaus,Kelsall, Geoffrey H.,Jessiman, Alan S.,Hii, King Kuok Mimi
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experimental part
p. 2157 - 2163
(2011/02/21)
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- TRPA1 ANTAGONISTS
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Compounds of formula (I), wherein R1, R2, R3, and Y are defined in the description are TRPA1 antagonists. Compositions comprising such compounds and methods for treating conditions and disorders using such compounds and compositions are also disclosed.
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Page/Page column 30
(2009/09/04)
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- Palladium/di-1-adamantyl-n-butylphosphine-catalyzed reductive carbonylation of aryl and vinyl halides
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A general and efficient palladium-catalyzed reductive carbonylation with low catalyst loadings (0.5 mol % Pd or below) has been developed. The formylation of aryl and heteroaryl bromides proceeds smoothly in the presence of palladium/di-1-adamantyl-n-butylphosphine at ambient pressure of synthesis gas to afford the corresponding aromatic aldehydes in good yields and excellent selectivity. In addition, vinyl halides react under similar conditions to form α,β-unsaturated aldehydes in good yield.
- Brennführer, Anne,Neumann, Helfried,Klaus, Stefan,Riermeier, Thomas,Almena, Juan,Beller, Matthias
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p. 6252 - 6258
(2008/02/04)
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- PROCESS FOR PRODUCING 3-SUBSTITUTED THIOPHENE
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A process for producing a 3-substituted thiophene represented by the general formula (2): (wherein R represents cyano, formyl, carboxy, optionally substituted hydrocarbyloxycarbonyl, or optionally substituted acyl), characterized by reacting a vinyl compound represented by the general formula (1): RCH=CHY (wherein R has the same meaning as defined above; and Y is a leaving group) with α-mercaptoacetaldehyde or a polymer thereof.
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Page/Page column 14
(2008/06/13)
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