585-74-0Relevant academic research and scientific papers
Selective Activation of Unstrained C(O)-C Bond in Ketone Suzuki-Miyaura Coupling Reaction Enabled by Hydride-Transfer Strategy
Zhong, Jing,Zhou, Wuxin,Yan, Xufei,Xia, Ying,Xiang, Haifeng,Zhou, Xiangge
supporting information, p. 1372 - 1377 (2022/02/23)
A Rh(I)-catalyzed ketone Suzuki-Miyaura coupling reaction of benzylacetone with arylboronic acid is developed. Selective C(O)-C bond activation, which employs aminopyridine as a temporary directing group and ethyl vinyl ketone as a hydride acceptor, occurs on the alkyl chain containing a β-position hydrogen. A series of acetophenone products were obtained in yields up to 75%.
Selective electrochemical oxidation of aromatic hydrocarbons and preparation of mono/multi-carbonyl compounds
Li, Zhibin,Zhang, Yan,Li, Kuiliang,Zhou, Zhenghong,Zha, Zhenggen,Wang, Zhiyong
, p. 2134 - 2141 (2021/09/29)
A selective electrochemical oxidation was developed under mild condition. Various mono-carbonyl and multi-carbonyl compounds can be prepared from different aromatic hydrocarbons with moderate to excellent yield and selectivity by virtue of this electrochemical oxidation. The produced carbonyl compounds can be further transformed into α-ketoamides, homoallylic alcohols and oximes in a one-pot reaction. In particular, a series of α-ketoamides were prepared in a one-pot continuous electrolysis. Mechanistic studies showed that 2,2,2-trifluoroethan-1-ol (TFE) can interact with catalyst species and generate the corresponding hydrogen-bonding complex to enhance the electrochemical oxidation performance. [Figure not available: see fulltext.]
Dimensional Reduction of Eu-Based Metal-Organic Framework as Catalysts for Oxidation Catalysis of C(sp3)–H Bond
Yan, Jun,Yu, Wei-Dong,Zhang, Yin,Zhao, Cai-Feng
, (2021/12/27)
Developing new catalysts for highly selectivity and conversion of saturated C(sp3)–H bonds is of great significance. In order to obtain catalysts with high catalytic performance, six Eu-based MOFs with different structural characteristics were obtained by using europium ions and different organic acid ligands, namely Eu-1~Eu-6. Eu-1, Eu-2 and Eu-3 featured three-dimensional structures, while Eu-4 and Eu-5 featured two-dimensional structures. Differently, a one-dimensional chain structure of Eu-6 was obtained by changing the ligand. All the six MOFs were applied to the catalytic reaction of C(sp3)–H bond, and it was found that the catalytic effect was gradually enhanced with the decrease of dimension and the increase of the size of channels. As expected, Eu-6 showed the highest selectivity (~99%) and conversion (~99%). Moreover, catalytic cycling and stability tests showed Eu-6 can be a reliable catalyst.
Organotellurium-catalyzed oxidative deoximation reactions using visible-light as the precise driving energy
Deng, Xin,Qian, Rongrong,Zhou, Hongwei,Yu, Lei
supporting information, p. 1029 - 1032 (2020/10/23)
Irradiated by visible light, the recyclable (PhTe)2-catalyzed oxidative deoximation reaction could occur under mild conditions. In comparison with the thermo reaction, the method employed reduced catalyst loading (1 mol% vs. 2.5 mol%), but afforded elevated product yields with expanded substrate scope. This work demonstrated that for the organotellurium-catalyzed reactions, visible light might be an even more precise driving energy than heating because it could break the Te–Te bond accurately to generate the active free radical catalytic intermediates without damaging the fragile substituents (e.g., heterocycles) of substrates. The use of O2 instead of explosive H2O2 as oxidant affords safer reaction conditions from the large-scale application viewpoint.
Decatungstate-mediated solar photooxidative cleavage of CC bonds using air as an oxidant in water
Du, Dongdong,Luo, Junfei,Shi, Sanshan,Xie, Pan,Xue, Cheng
, p. 5936 - 5943 (2021/08/23)
With the increasing attention for green chemistry and sustainable development, there has been much interest in searching for greener methods and sources in organic synthesis. However, toxic additives or solvents are inevitably involved in most organic transformations. Herein, we first report the combination of direct utilization of solar energy, air as the oxidant and water as the solvent for the selective cleavage of CC double bonds in aryl olefins. Various α-methyl styrenes, diaryl alkenes as well as terminal styrenes are well tolerated in this green and sustainable strategy and furnished the desired carbonyl products in satisfactory yields. Like heterogeneous catalysis, this homogeneous catalytic system could also be reused and it retains good activity even after repeating three times. Mechanism investigations indicated that both O2- and 1O2 were involved in the reaction. Based on these results, two possible mechanisms, including the electron transfer pathway and the energy transfer pathway, were proposed.
Selective oxidation of alkenes to carbonyls under mild conditions
Huo, Jie,Xiong, Daokai,Xu, Jun,Yue, Xiaoguang,Zhang, Pengfei,Zhang, Yilan
supporting information, p. 5549 - 5555 (2021/08/16)
Herein, a practical and sustainable method for the synthesis of aldehydes, ketones, and carboxylic acids from an inexpensive olefinic feedstock is described. This transformation features very sustainable and mild conditions and utilizes commercially available and inexpensive tetrahydrofuran as the additive, molecular oxygen as the sole oxidant and water as the solvent. A wide range of substituted alkenes were found to be compatible, providing the corresponding carbonyl compounds in moderate-to-good yields. The control experiments demonstrated that a radical mechanism is responsible for the oxidation reaction.
Method for preparing carbonyl compound through oxidative cleavage of visible light excitation aqueous solution quantum dot catalytic olefin compound
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Paragraph 0036, (2021/11/10)
The invention provides a method for preparing carbonyl compounds through oxidative cleavage of a visible light excitation aqueous solution quantum dot catalytic olefin compound. Belong to photocatalysis synthesis technical field. To the method, an aqueous solution quantum dot is used as a photocatalyst, and an aqueous solution quantum dot activated molecular oxygen catalytic oxidation aromatic alkene compound is excited by visible light to be cracked to prepare a carbonyl compound. Low-loading capacity is used, a simple aqueous solution quantum dot is used as a catalyst, the yield of the carbonyl compound is high, TON more than ten millions are obtained. The reaction conditions are mild, water serves as a main solvent for the reaction, and the carbonyl compound can be obtained by catalytic olefin compound oxidation cracking without addition of a cocatalyst or the like. The method is simple to operate, wide in substrate range and low in cost.
Visible-Light-Driven Oxidative Cleavage of Alkenes Using Water-Soluble CdSe Quantum Dots
Li, Jianing,Zhao, Jingnan,Ma, Cunfei,Yu, Zongyi,Zhu, Hongfei,Yun, Lei,Meng, Qingwei
, p. 4985 - 4992 (2021/10/16)
The oxidative cleavage of C=C bonds is an important chemical reaction, which is a popular reaction in the photocatalytic field. However, high catalyst-loading and low turnover number (TON) are general shortcomings in reported visible-light-driven reactions. Herein, the direct oxidative cleavage of C=C bonds through water-soluble CdSe quantum dots (QDs) is described under visible-light irradiation at room temperature with high TON (up to 3.7×104). Under the same conditions, water-soluble CdSe QDs could also oxidize sulfides to sulfoxides with 51–84 % yields and TONs up to 3.4×104. The key features of this photocatalytic protocol include high TONs, wide substrates scope, low catalyst loadings, simple and mild reaction conditions, and molecular O2 as the oxidant.
One-Pot Chemoenzymatic Conversion of Alkynes to Chiral Amines
Mathew, Sam,Renn, Dominik,Rueping, Magnus,Sagadevan, Arunachalam
, p. 12565 - 12569 (2021/10/21)
A one-pot chemoenzymatic sequential cascade for the synthesis of chiral amines from alkynes was developed. In this integrated approach, just ppm amounts of gold catalysts enabled the conversion of alkynes to ketones (>99%) after which a transaminase was used to catalyze the production of biologically valuable chiral amines in a good yield (up to 99%) and enantiomeric excess (>99%). A preparative scale synthesis of (S)-methylbenzylamine and (S)-4-methoxy-methylbenzylamine from its alkyne form gave a yield of 59 and 92%, respectively, withee> 99%.
o-Quinone methide with overcrowded olefin component as a dehydridation catalyst under aerobic photoirradiation conditions
Uraguchi, Daisuke,Kato, Kohsuke,Ooi, Takashi
, p. 2778 - 2783 (2021/03/14)
Ano-quinone methide (o-QM) featuring an overcrowded olefinic framework is introduced, which exhibits dehydridation activity owing to its enhanced zwitterionic character, particularly through photoexcitation. The characteristics of thiso-QM enable the operation of dehydridative catalysis in the oxidation of benzylic secondary alcohols under aerobic photoirradiation conditions. An experimental analysis and density functional theory calculations provide mechanistic insights; the ground-state zwitterionic intermediate abstracts a hydride and proton simultaneously, and the active oxygen species facilitate catalyst regeneration.
