498-62-4Relevant academic research and scientific papers
Electrosynthesis of heteroaromatic aldehydes by palladium-catalyzed carbonylation of heteroaromatic iodides in the presence of formic acid
Chiarotto, Isabella,Feroci, Marta
, p. 2589 - 2592 (2006)
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.
Controlled reduction of activated primary and secondary amides into aldehydes with diisobutylaluminum hydride
Azeez, Sadaf,Kandasamy, Jeyakumar,Sabiah, Shahulhameed,Sureshbabu, Popuri
supporting information, p. 2048 - 2053 (2022/03/31)
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.
Palladium-Catalyzed Reductive Carbonylation of (Hetero) Aryl Halides and Triflates Using Cobalt Carbonyl as CO Source
Dogga, Bhushanarao,Joseph, Jayan T.,Kumar, C. S. Ananda
supporting information, p. 309 - 313 (2020/12/23)
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.
Rhodium-catalyzed reductive carbonylation of aryl iodides to arylaldehydes with syngas
Chen, Suqing,Liu, Zhenghui,Mu, Tiancheng,Wang, Peng,Yan, Zhenzhong,Yu, Dongkun,Zhao, Xinhui
, p. 645 - 656 (2020/05/14)
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.
Dual-fixations of europium cations and TEMPO species on metal-organic frameworks for the aerobic oxidation of alcohols
Jeoung, Sungeun,Kim, Min,Kim, Seongwoo,Lee, Jooyeon,Moon, Hoi Ri
supporting information, p. 8060 - 8066 (2020/07/10)
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.
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
Kim, Seongwoo,Lee, Ha-Eun,Suh, Jong-Min,Lim, Mi Hee,Kim, Min
supporting information, p. 17573 - 17582 (2020/12/22)
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.
Preparation method 3- thiophene formaldehyde
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Paragraph 0044; 0046-0047; 0049-0050; 0052-0053; 0055, (2020/03/23)
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.
Visible-light mediated facile dithiane deprotection under metal free conditions
Dharpure, Pankaj D.,Bhowmick, Anindita,Warghude, Prakash K.,Bhat, Ramakrishna G.
, (2019/12/09)
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.
Europium-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones and Photoluminescence Tracking
Kim, Seongwoo,Kim, Youngik,Jin, Hyomin,Park, Myung Hwan,Kim, Youngjo,Lee, Kang Mun,Kim, Min
supporting information, (2019/02/05)
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.).
Efficient acceptorless photo-dehydrogenation of alcohols and: N -heterocycles with binuclear platinum(ii) diphosphite complexes
Zhong, Jian-Ji,To, Wai-Pong,Liu, Yungen,Lu, Wei,Che, Chi-Ming
, p. 4883 - 4889 (2019/05/16)
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.
