- Selective Activation of Unstrained C(O)-C Bond in Ketone Suzuki-Miyaura Coupling Reaction Enabled by Hydride-Transfer Strategy
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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%.
- Zhong, Jing,Zhou, Wuxin,Yan, Xufei,Xia, Ying,Xiang, Haifeng,Zhou, Xiangge
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supporting information
p. 1372 - 1377
(2022/02/23)
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- Iron-catalyzed domino decarboxylation-oxidation of α,β-unsaturated carboxylic acids enabled aldehyde C-H methylation
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A practical and general iron-catalyzed domino decarboxylation-oxidation of α,β-unsaturated carboxylic acids enabling aldehyde C-H methylation for the synthesis of methyl ketones has been developed. This mild, operationally simple method uses ambient air as the sole oxidant and tolerates sensitive functional groups for the late-stage functionalization of complex natural-product-derived and polyfunctionalized molecules.
- Gong, Pei-Xue,Xu, Fangning,Cheng, Lu,Gong, Xu,Zhang, Jie,Gu, Wei-Jin,Han, Wei
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p. 5905 - 5908
(2021/06/18)
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- V2O5@TiO2 Catalyzed Green and Selective Oxidation of Alcohols, Alkylbenzenes and Styrenes to Carbonyls
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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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- Ruthenium(II) Complexes Bearing Schiff Base Ligands for Efficient Acceptorless Dehydrogenation of Secondary Alcohols?
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Four ruthenium(II) complexes 1—4 [RN=CH-(2,4-(tBu)2C6H2O)]RuH(PPh3)2(CO) (R = C6H5, 1; R = 4-MeC6H4, 2; R = 4-ClC6H4, 3; R = 4-BrC6H4, 4) bearing Schiff base ligands were prepared by treating RuHClCO(PPh3)3 with RN=CH-(2,4-(tBu)2C6H2OH (L1—L4) in the presence of triethylamine. Their structures were fully characterized by elemental analysis, IR, NMR spectroscopy and X-ray crystallography. These Ru(II) complexes exhibit high catalytic performance and good functional-group compatibility in the acceptorless dehydrogenation of secondary alcohols, affording the corresponding ketones in 82%—94% yields.
- Dong, Qing,Feng, Qi,Han, Zhangang,Hao, Zhiqiang,Lin, Jin,Liu, Kang,Lu, Guo-Liang,Ma, Dongzhu
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p. 121 - 128
(2020/12/25)
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- o-Quinone methide with overcrowded olefin component as a dehydridation catalyst under aerobic photoirradiation conditions
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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.
- Uraguchi, Daisuke,Kato, Kohsuke,Ooi, Takashi
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p. 2778 - 2783
(2021/03/14)
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- Merging N-Hydroxyphthalimide into Metal-Organic Frameworks for Highly Efficient and Environmentally Benign Aerobic Oxidation
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Two highly efficient metal-organic framework catalysts TJU-68-NHPI and TJU-68-NDHPI have been successfully synthesized through solvothermal reactions of which the frameworks are merged with N-hydroxyphthalimide (NHPI) units, resulting in the decoration of pore surfaces with highly active nitroxyl catalytic sites. When t-butyl nitrite (TBN) is used as co-catalyst, the as-synthesized MOFs are demonstrated to be highly efficient and recyclable catalysts for a novel three-phase heterogeneous oxidation of activated C?H bond of primary and secondary alcohols, and benzyl compounds under mild conditions. Based on the high efficiency and selectivity, an environmentally benign system with good sustainability, mild conditions, simple work-up procedure has been established for practical oxidation of a wide range of substrates.
- Wang, Man,Liang, Gan,Wang, Yunhao,Fan, Tao,Yuan, Baoling,Liu, Mingxian,Yin, Ying,Li, Liangchun
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supporting information
p. 9674 - 9685
(2021/06/09)
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- Preparation of trinuclear ruthenium clusters based on piconol ligands and their application in Oppenauer-type oxidation of secondary alcohols
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Treatment of Ru3(CO)12 with one equivalent of 2-indolyl-6-pyridinyl-alcohol ligands 2-(C8H6N)-6-(CR1R2OH)C5H3N (R1 = R2 = Me (L1H); R1 = R2 = C2H5 (L2H); R1, R2 = ?(CH2)4- (L3H);& R1, R2 = ?(CH2)5- (L4H)) in refluxing THF afforded the corresponding trinuclear ruthenium clusters L(μ2-H)Ru3(CO)9 (1a–1d), respectively. All the novel Ru complexes were well characterized by NMR, elemental analyses and IR spectra. Structures of complexes 1a, 1c, and 1d were further determined by X-ray crystallographic studies. Complexes 1a–1d were applied to catalytic Oppenauer-type oxidation of secondary alcohols with acetone as oxidant, and complex 1a was found to be the most efficient catalyst.
- Dong, Qing,Ma, Zongwen,Hao, Zhiqiang,Han, Zhangang,Lin, Jin,Lu, Guo-Liang
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- Ru(iii) -based polyoxometalate tetramers as highly efficient heterogeneous catalysts for alcohol oxidation reactions at room temperature
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A novel ruthenium-containing polyoxometalate-based organic-inorganic hybrid, K4Na9H7.4[(AsW9O33)4(WO2)4{Ru3.2(C3H3N2)2}]·42H2O (1), was successfully synthesized by a one-step hydrothermal method under acidic conditions, which applied a self-assembly strategy between inorganic polyoxometalate based on trivacant [B-α-AsW9O33]9?{AsW9} fragments and an organic ligand, imidazole (C3H4N2). Compound1was further characterized by single-crystal X-ray diffraction, PXRD, IR spectroscopy, UV-Vis spectroscopy, ESI-MS, elemental analysis and TGA. Single-crystal X-ray diffraction data reveal that the polyanion consists of four trivacant Keggin-type polyanion {AsW9} building blocks bridged by four {WO6} units, leading to a crown-shaped tetrameric structure [(AsW9O33)4(WO2)4{Ru3.2(C3H3N2)2}]20.4?. The ESI-MS result reveals that the polyanion unit has excellent structural integrity in water. Moreover, the catalysis study of1was also further investigated, and the experimental results indicate heterogeneous catalyst1presents high efficiency (yield = 98%), excellent selectivity (>99%), and good recyclability for the oxidation of 1-(4-chlorophenyl)ethanol to 4′-chloroacetophenone with commercially available 70% aqueoustert-butyl hydroperoxide {TBHP (aq.)} as the oxidant at room temperature.
- Li, Huafeng,Ma, Pengtao,Niu, Jingyang,Song, Junpeng,Wang, Jingping,Wang, Yaqiong,Zhao, Xue,Zou, Yan
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p. 12664 - 12673
(2021/09/28)
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- Photoinduced Acetylation of Anilines under Aqueous and Catalyst-Free Conditions
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A green and efficient visible-light induced functionalization of anilines under mild conditions has been reported. Utilizing nontoxic, cost-effective, and water-soluble diacetyl as photosensitizer and acetylating reagent, and water as the solvent, a variety of anilines were converted into the corresponding aryl ketones, iodides, and bromides. With advantages of environmentally friendly conditions, simple operation, broad substrate scope, and functional group tolerance, this reaction represents a valuable method in organic synthesis.
- Yang, Yu-Ming,Yan, Wei,Hu, Han-Wei,Luo, Yimin,Tang, Zhen-Yu,Luo, Zhuangzhu
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p. 12344 - 12353
(2021/09/02)
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- The Reactivity of α-Fluoroketones with PLP Dependent Enzymes: Transaminases as Hydrodefluorinases
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A chemical method for the treatment of harmful halogenated compounds that has recently become of interest is the reductive dehalogenation of carbon-halogen bonds. In the case of a fluorine atom, this process is called hydrodefluorination. While many transition metal-based approaches now exist to reductively defluorinate aromatic fluoroarenes, the cleavage of C?F bonds in aliphatic compounds is not so well-developed. Here we propose a biocatalytic approach exploiting a promiscuous activity exhibited by transaminases (TAs). Hence, a series of α-fluoroketones have been defluorinated with excellent conversions using Chromobacterium violaceum and Arthrobacter sp. TAs under mild conditions and in aqueous medium, using a stoichiometric amount of an amine (e. g. 2-propylamine) as reagent and formally releasing its oxidized form (e. g. acetone), with ammonia and hydrogen fluoride as by-products. It is also demonstrated that this process can be performed in a regio- or stereoselective fashion.
- García-Ramos, Marina,Cuetos, Aníbal,Kroutil, Wolfgang,Grogan, Gideon,Lavandera, Iván
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p. 3967 - 3972
(2021/08/09)
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- Interfacially synthesized 2D COF thin film photocatalyst: efficient photocatalyst for solar formic acid production from CO2and fine chemical synthesis
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The targeted synthesis of an efficient, visible light active, recyclable, freestanding covalent organic framework thin film photocatalyst for multi-faceted photocatalysis is the essence of the proposed work. A simple, scalable, reagent free synthesis of a thin film at the interface of 5,10,15,20-tetra-(4-aminophenyl)porphyrin, 2-vinylbenzene-1,4-dicarbaldehyde in nitrobenzene and aqueous glyoxal affords centimetre sized continuous 2D thin film with substantial stability, flexibility and efficient visible light activity. Strikingly different from the regular imine based COF, the incorporation of the glyoxal unit as a modulator helps in band gap tuning and induces flexibility within the thin film. An interplay between time and concentration helps in achieving a thin film photocatalyst with efficient photocatalytic activity for 1,4-NADH regeneration and selective formic acid formation from CO2. The optimum band edge position of the thin film photocatalyst also enables solar fine chemical synthesisviareductive dehalogenation under visible light illumination with excellent recyclability. The present work gives insight into visible light active thin film formation en route to metal-free sustainable photocatalysis.
- Yadav, Dolly,Kumar, Abhishek,Kim, Jae Young,Park, No-Joong,Baeg, Jin-Ook
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supporting information
p. 9573 - 9580
(2021/04/26)
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- Selective oxidation of alkenes to carbonyls under mild conditions
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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.
- Huo, Jie,Xiong, Daokai,Xu, Jun,Yue, Xiaoguang,Zhang, Pengfei,Zhang, Yilan
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supporting information
p. 5549 - 5555
(2021/08/16)
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- Organotellurium-catalyzed oxidative deoximation reactions using visible-light as the precise driving energy
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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.
- Deng, Xin,Qian, Rongrong,Zhou, Hongwei,Yu, Lei
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supporting information
p. 1029 - 1032
(2020/10/23)
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- A sodium trifluoromethanesulfinate-mediated photocatalytic strategy for aerobic oxidation of alcohols
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A sodium trifluoromethanesulfinate-mediated photocatalytic strategy for the aerobic oxidation of alcohols has been developed for the first time, and the photoredox aerobic oxidation of secondary and primary alcohols provided the corresponding ketones and carboxylic acids, respectively, in high to excellent yields.
- Zhu, Xianjin,Liu, Can,Liu, Yong,Yang, Haijun,Fu, Hua
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p. 12443 - 12446
(2020/10/30)
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- Highly efficient oxidation of alcohols catalyzed by Ru(II) carbonyl complexes bearing salicylaldiminato ligands
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Reaction of Ru3(CO)12 with 2.0 equiv of RN = CH(3,5-tBu2C6H2OH) (R = C6H5, L1; R = 4-MeC6H4, L2; R = 4-OMeC6H4, L3; R = 4-ClC6H4, L4; R = 4-BrC6H4, L5; R = 4-CF3C6H4, L6) in refluxing xylene afforded the corresponding bis-chelate Ru(II) complexes 1a–1f [RN = CH(3,5-tBu2C6H2O)]2Ru(CO)2 and one of the imine bonds reduced complexes {[RN = CH(3,5-tBu2C6H2O)]-[RNH-CH2(3,5-tBu2C6H2O)]}Ru(CO)2 2a–2f. All the ruthenium complexes were fully characterized by NMR, IR and elemental analysis. In addition, the structures of complexes 1a–1f, 2b, 2d and 2f were further confirmed by single-crystal X-ray diffraction. When activated with N-methylmorpholine-N-oxide (NMO), these Ru complexes displayed high catalytic activities toward oxidation of both 1° and 2° alcohols. For most cases, the reaction can complete within 1 h in refluxing CH3CN.
- Dong, Qing,Han, Zhangang,Hao, Zhiqiang,Huo, Shuaicong,Lin, Jin,Liu, Kang,Lu, Guo-Liang,Zhang, Junhua
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- A Simple Biosystem for the High-Yielding Cascade Conversion of Racemic Alcohols to Enantiopure Amines
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The amination of racemic alcohols to produce enantiopure amines is an important green chemistry reaction for pharmaceutical manufacturing, requiring simple and efficient solutions. Herein, we report the development of a cascade biotransformation to aminate racemic alcohols. This cascade utilizes an ambidextrous alcohol dehydrogenase (ADH) to oxidize a racemic alcohol, an enantioselective transaminase (TA) to convert the ketone intermediate to chiral amine, and isopropylamine to recycle PMP and NAD+ cofactors via the reversed cascade reactions. The concept was proven by using an ambidextrous CpSADH-W286A engineered from (S)-enantioselective CpSADH as the first example of evolving ambidextrous ADHs, an enantioselective BmTA, and isopropylamine. A biosystem containing isopropylamine and E. coli (CpSADH-W286A/BmTA) expressing the two enzymes was developed for the amination of racemic alcohols to produce eight useful and high-value (S)-amines in 72–99 % yield and 98–99 % ee, providing with a simple and practical solution to this type of reaction.
- Li, Zhi,Tian, Kaiyuan
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supporting information
p. 21745 - 21751
(2020/09/21)
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- PROCESS FOR THE PREPARATION OF DIHALOBENZOPHENONES, NEW CHEMICALS USEFUL FOR ITS IMPLEMENTATION AND METHODS FOR PREPARING SAID CHEMICALS
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The invention relates to new compounds of formulae (IV), wherein X represents a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine, said compounds being useful as precursors and/or intermediates for the preparation of 4,4'dihalobenzophenones of formula (I), wherein X is as defined above.
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Page/Page column 10-11
(2020/12/01)
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- Mild Deprotection of Dithioacetals by TMSCl/NaI Association in CH3CN
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A mild process using a combination of TMSCl and NaI in acetonitrile is used to regenerate carbonyl compounds from a variety of dithiane and dithiolane derivatives. This easy to handle and inexpensive protocol is also efficient to deprotect oxygenated and mixed acetals as 1,3-dioxanes, 1,3-dioxolanes and 1,3-oxathianes quantitatively. As a possible extension of this method, it was also shown that nitrogenated substrates such as hydrazones, N-tosylhydrazones, and ketimines reacted well under these conditions to give the expected ketones in high yields. The methodology proposed herein is a good alternative to the existing methods since it does not use metals, oxidants, reducing agents, acidic or basic media, and keto-products were obtained in high to excellent yields.
- Yao, Yunxin,Zhao, Guangkuan,Hamze, Abdallah,Alami, Mouad,Provot, Olivier
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p. 5775 - 5779
(2020/08/17)
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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
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supporting information
p. 4395 - 4399
(2020/06/05)
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- 1,2-Diethoxyethane catalyzed oxidative cleavage of gem-disubstituted aromatic alkenes to ketones under minimal solvent conditions
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Aerobic oxidation using pure dioxygen gas as the oxidant has attracted much attention, but its application in synthetic chemistry has been significantly hampered by the complexity of catalytic system and potential risk of high-energy dioxygen gas. By employing 1,2-diethoxyethane as a catalyst and ambient air as an oxidant, an efficient protocol for the construction of various aryl-alkyl and diaryl ketones through oxidative cleavage of gem-disubstituted aromatic alkenes under minimal solvent conditions has been achieved.
- Liu, Kai-Jian,Deng, Ji-Hui,Zeng, Tang-Yu,Chen, Xin-Jie,Huang, Ying,Cao, Zhong,Lin, Ying-Wu,He, Wei-Min
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supporting information
p. 1868 - 1872
(2020/01/31)
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- Heterogeneous carbon nitride photocatalyst for C-C bond oxidative cleavage of vicinal diols in aerobic micellar medium
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A green and efficient visible-light promoted aerobic oxidative C-C bond cleavage of vicinal diols in micellar medium has been developed. This protocol used graphitic carbon nitride with nitrogen vacancies (CN620) as a metal-free recyclable photocatalyst and CTAB as surfactant in water. Control experiments and the ESR results indicated that superoxide radicals and valence band holes played an important role in the reaction. Further isotope experiments suggested both a β-scission/HAT pathway and an oxidation/hydrolysis/dehydration pathway for the reaction, which is different from previous reports. The semiconductor/micellar catalyst system can be recycled at least 10 times without a significant reduction in activity. Furthermore, this reaction could be carried out under solar light irradiation and was applicable to large-scale reactions with similar results.
- Chen, Jiayang,Chen, Shengjun,Dong, Xinyu,Hong, Mei,Ni, Bangqing,Niu, Tengfei,Zhang, Tianhao
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supporting information
p. 5042 - 5049
(2020/08/25)
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- Synthesis and Catalytic Properties of Metal- N-Heterocyclic-Carbene-Decorated Covalent Organic Framework
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We demonstrate herein that the N-heterocyclic-carbene (NHC)-metal complex (NHC-M)-involved covalent organic framework (COF) can be prepared by the direct polymerization of the NHC-M monomer with its counterpart under solvothermal conditions. The NHC-M-COF with different counterions is readily achieved via solid-state anion exchange. The obtained NHC-AuX-COF (X = Cl- and SbF6-) can be a highly active reusable catalyst to separately promote the carboxylation of the terminal alkyne with CO2 and alkyne hydration under mild conditions.
- Dong, Ying,Dong, Yu-Bin,Kan, Jing-Lan,Li, Yue,Wu, Xiaowei
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supporting information
p. 7363 - 7368
(2020/10/12)
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- Method for producing methyl ketone by catalytic oxidation of olefin by palladium
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The invention discloses a method for generating methyl ketone by catalyzing oxidization of olefin with palladium. The method comprises the following steps: performing a full reaction and a TLC (Thin Layer Chromatography) track reaction in an organic solvent by taking end-position olefin or a nonterminal olefin compound as a raw material, hydrogen peroxide or hydrogen peroxide tertiary butanol as an oxidizing agent, palladium acetate as a catalyst and inorganic acid as a promoter; extracting with ethyl acetate after finishing the reaction, and performing suction filtration, concentration and purification to obtain a corresponding methyl ketone compound. By adopting the method, the palladium acetate is taken as the catalyst, the application of an expensive palladium complex catalyst is avoided; the hydrogen peroxide or the hydrogen peroxide tertiary butanol is taken as the oxidizing agent, a completely-decomposed product is environment-friendly; the inorganic acid is used in a catalytic amount, so that the influences on the environment and equipment are small; treatment difficulty is lowered by using a low-boiling-point organic solvent; the reaction process is environment-friendly, and treatment is easy after reaction; meanwhile, the method is suitable for the end-position olefin or the nonterminal olefin compound, and is wide in application substrate rang; the defect of low applicability of the conventional Wacker oxidizing reaction is overcome.
- -
-
Paragraph 0032; 0033
(2020/09/20)
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- Isopropanol as a hydrogen source for single atom cobalt-catalyzed Wacker-type oxidation
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The first example of a heterogeneous cobalt catalytic system for Wacker-type oxidation catalyzed by a single atom dispersed Co-N/C catalyst using alcohol as the hydrogen source under an oxygen atmosphere is presented. By combining a well-designed, controlled experiment and various methods of characterization, we determined that single atom cobalt was the active center rather than nanoparticle or oxide counterparts.
- An, Yue,Chen, Bo,Gao, Shuang,Huang, Guanwang,Luo, Huihui,Shang, Sensen,Wang, Lianyue
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p. 2769 - 2773
(2020/06/17)
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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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- Electrochemical performance of ABNO for oxidation of secondary alcohols in acetonitrile solution
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The ketones was successfully prepared from secondary alcohols using 9-azabicyclo[3.3.1]nonane-N-oxyl (ABNO) as the catalyst and 2,6-lutidine as the base in acetonitrile solution. The electrochemical activity of ABNO for oxidation of 1-phenylethanol was investigated by cyclic voltammetry, in situ Fourier transform infrared spectroscopy (FTIR) and constant current electrolysis experiments. The resulting cyclic voltammetry indicated that ABNO exhibited much higher electrochemical activity when compared with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) under the similar conditions. A reasonable reaction mechanism of the electrocatalytic oxidation of 1-phenylethanol to acetophenone was proposed. In addition, a series of secondary alcohols could be converted to the corresponding ketones at room temperature in 80-95% isolated yields.
- Niu, Pengfei,Liu, Xin,Shen, Zhenlu,Li, Meichao
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- Iron–PNP-Pincer-Catalyzed Transfer Dehydrogenation of Secondary Alcohols
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The well-defined iron PNP pincer complex catalyst [Fe(H)(BH4)(CO)(HN{CH2CH2P(iPr)2}2] was used for the catalytic dehydrogenation of secondary alcohols to give the corresponding ketones. Using acetone as inexpensive hydrogen acceptor enables the oxidation with good to excellent yields. DFT computations indicate an outer-sphere mechanism and support the importance of an acceptor to achieve this transformation under milder conditions.
- Budweg, Svenja,Wei, Zhihong,Jiao, Haijun,Junge, Kathrin,Beller, Matthias
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- A Stable Polyoxometalate-Based Metal-Organic Framework as Highly Efficient Heterogeneous Catalyst for Oxidation of Alcohols
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A novel copper-containing 3D polyoxometalate-based metal-organic framework (POMOF), H[Cu5ICuII(pzc)2(pz)4.5{P2W18O62}]·6H2O (HENU-1, HENU = Henan University; Hpzc = pyrazine-2-carboxylic acid, pz = pyrazine), was successfully isolated by a one-step hydrothermal method. In this compound, the {P2W18} polyanion acts as a seven-connected linker bridging adjacent 2D double-layer networks, as well as a template to induce the formation of the desired 3D framework. Particularly, the pz ligands are generated from pzc ligands in situ during the reaction process. HENU-1 exhibits not only good stability in air but also tolerance to acidic and basic media. It was first employed as a highly efficient heterogeneous catalyst for the oxidation of 1-phenylethanol into acetophenone, which shows 97% yield using tert-butyl hydroperoxide as oxidant with a turnover frequency of up to 9690·h-1, and was reused for at least five cycles without significant catalytic activity loss. No POM leaching or framework decomposition was observed in our study.
- Li, Dandan,Xu, Qiaofei,Li, Yingguang,Qiu, Yueting,Ma, Pengtao,Niu, Jingyang,Wang, Jingping
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p. 4945 - 4953
(2019/04/25)
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- Pyrazine dicarboxylate-bridged arsenotungstate: Synthesis, characterization, and catalytic activities in epoxidation of olefins and oxidation of alcohols
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A praseodymium(iii)-containing arsenotungstate K16H15Li7[Pr2(H2O)3(pzdc)As3W29O103]2·38H2O (1) (pzdc = pyrazine-2,3-dicarboxylic acid) was synthesized by a conventional aqueous solution method and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and single crystal X-ray diffraction. Structural analysis revealed that compound 1 was constructed by two identical subunits {Pr2(H2O)3(AsW9O33)3W2O4} bridged together by two pzdc ligands. In addition, compound 1 could act as an efficient catalyst for the epoxidation of olefins and oxidation of alcohols with hydrogen peroxide (H2O2) as the oxidant. In particular, the turnover frequency (TOF) in the oxidation of 1-phenylethanol reached up to 10170 h-1, which is higher than that of previously reported catalysts.
- Ma, Xinyi,He, Peipei,Xu, Baijie,Lu, Jingkun,Wan, Rong,Wu, Hechen,Wang, Yuan,Ma, Pengtao,Niu, Jingyang,Wang, Jingping
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p. 12956 - 12963
(2019/09/07)
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- Enantiocomplementary decarboxylative hydroxylation combining photocatalysis and whole-cell biocatalysis in a one-pot cascade process
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Designing a green, highly efficient and stereoselective catalytic system to generate valuable enantioenriched products is a long-standing goal in green chemistry. Here, we report a one-pot cascade combining photocatalysts with (R)- or (S)-selective ketoreductases for the decarboxylative carbonylation of carboxylic acids and the subsequent bioreduction to generate valuable chiral alcohols. Using this approach, various chiral alcohols with complementary (R)- or (S)-configurations were prepared with good yields (up to 93%) and excellent stereoselectivity (up to 99% ee). Such a photochemo-enzymatic one-pot whole-cell process combines the advantages of both photocatalysts and enzyme catalysts and provides a mild, green, metal-free and highly stereoselective alternative in asymmetric decarboxylative hydroxylation reactions.
- Xu, Jian,Arkin, Mamatjan,Peng, Yongzhen,Xu, Weihua,Yu, Huilei,Lin, Xianfu,Wu, Qi
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supporting information
p. 1907 - 1911
(2019/04/27)
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- Synthesis method of primary amine hydrochloride
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The invention discloses a synthesis method of primary amine hydrochloride. According to the synthesis method, in the presence of a gold complex, water and alkyne carry out catalytic hydrolysis to generate ketones, and then ketones and ammonium formate are catalyzed by a rhodium complex to generate primary amine. Compared with a conventional primary amine synthesis method, the synthesis method hasthe advantages that no alkali is added during the reaction process, no side product is generated, the atomic economy is good, the reaction conditions are mild, and the synthesis method has a wide prospect.
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Paragraph 0089-0092
(2019/03/09)
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- Iron-Enabled Utilization of Air as the Terminal Oxidant Leading to Aerobic Oxidative Deoximation by Organoselenium Catalysis
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In contrast to conventional organoselenium-catalyzed oxidation reactions that require peroxide oxidants such as hydrogen peroxide, in this work we found that, addition of a low loading of iron (II) could enable the successful utilization of air as the terminal oxidant in organoselenium-catalyzed oxidative deoximation reaction of ketoximes. This led to a new mild and relatively green aerobic oxidative deoximation method. Control reactions and X-ray photoelectron spectroscopy (XPS) analysis suggest that iron is crucial in the catalytic cycle, working to prohibit the deactivation of selenium catalyst through an iron-catalyzed aerobic oxidation of low valent selenium species by air to the active high valent selenium species. Since air can be utilized as the terminal oxidant, this work may contribute to the advance of organoselenium catalysis. (Figure presented.).
- Chen, Chao,Zhang, Xu,Cao, Hongen,Wang, Fang,Yu, Lei,Xu, Qing
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p. 603 - 610
(2018/12/14)
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- Efficient Palladium(0) supported on reduced graphene oxide for selective oxidation of olefins using graphene oxide as a ‘solid weak acid’
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Selective oxidation of olefin derivatives to ketones has made innovative development over palladium(0) supported on reduced graphene oxide. Compared to traditional Wacker oxidation, the novel method offers an economical and environment-friendly option by using graphene oxide (GO) as a ‘solid weak acid’ instead of classical homogeneous catalysts like H2SO4 and CF3COOH. X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscope and transmission electron microscopy images of Pd0/RGO showed that the nanoscaled Pd particles generated at the flake structure of reduced graphene oxide. Under optimized condition, up to 44 kinds of ketones with different structures can be prepared with excellent yields.
- Gao, Xi,Zhou, Jianhao,Peng, Xinhua
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- A palladium catalyzed oxidation of olefin compound method of preparing methyl ketone (by machine translation)
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The invention discloses a palladium catalyzed oxidation of olefin compound preparation methyl ketone of the method, the method comprises: sequentially added in the reaction vessel to olefin compound, supported palladium catalyst and reaction solvent, is then heated to a 20 - 50 °C, then adding in the cocatalyst and the oxidizing agent, the secondary mixed reaction solution, then the secondary mixed reaction solution is heated to 65 - 75 °C, 4 - 8 h after, its solid-liquid separation, to obtain the supported palladium catalyst and three times the mixed reaction solution; after the step of ethyl acetate 3 to obtain the three mixed reaction solution extraction, the organic phase obtained; sequentially to the organic phase washed by water, drying, filtering, is distilled under reduced pressure to obtain the crude product then eluting after the purification, to obtain the target product; the method of the invention applied to the preparation of methyl substance of high utilization rate of atom, the process is simple, mild reaction conditions, yield and good selectivity, with industrial application environmental and economic characteristics. (by machine translation)
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Paragraph 0045-0048
(2019/02/04)
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- Design, synthesis and structure-based optimization of novel isoxazole-containing benzamide derivatives as FtsZ modulators
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Antibiotic resistance among clinically significant bacterial pathogens is becoming a prevalent threat to public health, and new antibacterial agents with novel mechanisms of action hence are in an urgent need. Utilizing computational docking method and structure-based optimization strategy, we rationally designed and synthesized two series of isoxazol-3-yl- and isoxazol-5-yl-containing benzamide derivatives that targeted the bacterial cell division protein FtsZ. Evaluation of their activity against a panel of Gram-positive and -negative pathogens revealed that compounds B14 and B16 that possessed the isoxazol-5-yl group showed strong antibacterial activity against various testing strains, including methicillin-resistant Staphylococcus aureus and penicillin-resistant S. aureus. Further molecular biological studies and docking analyses proved that the compound functioned as an effective inhibitor to alter the dynamics of FtsZ self-polymerization via a stimulatory mechanism, which finally terminated the cell division and caused cell death. Taken together, these results could suggest a promising chemotype for development of new FtsZ-targeting bactericidal agent.
- Bi, Fangchao,Song, Di,Zhang, Nan,Liu, Zhiyang,Gu, Xinjie,Hu, Chaoyu,Cai, Xiaokang,Venter, Henrietta,Ma, Shutao
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- Regio- and chemoselective rearrangement of terminal epoxides into methyl alkyl and aryl ketones
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The development of the highly active pincer-type rhodium catalyst 2 for the nucleophilic Meinwald rearrangement of functionalised terminal epoxides into methyl ketones under mild conditions is presented. An excellent regio- and chemoselectivity is obtained for the first time for aryl oxiranes.
- Tian, Yingying,Jürgens, Eva,Kunz, Doris
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p. 11340 - 11343
(2018/10/31)
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- Method for removing oxime through catalysis of tellurium
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The invention provides a method for removing oxime through catalysis of tellurium and relates to the technical field of oxime removal. According to the method provided by the invention, commercializeddiphenyl ditelluride ether is used as a catalyst; oxygen gas is used as an oxidant under a solvent-free condition and oxime is heated so that oxime can be removed to obtain a carbonyl compound; the catalyst also can be repeatedly utilized. The method is clean and environmentally friendly, low in cost and safe to operate, so that the method is an effective oxime removing method. According to the method provided by the invention, raw materials are selected from various aryl or alkyl substituted oxime. According to the method provided by the invention, reaction does not need a solvent so that the reaction cost can be reduced and a process is clean and environmentally friendly. The oxidant provided by the invention is the oxygen gas and can be used for sufficiently oxidizing a substrate, andthe yield is the highest.
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Paragraph 0014; 0023; 0024
(2018/07/15)
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- Highly selective aerobic oxidation of alkylarenes catalyzed by cobalt-based nanocatalyst in aqueous solution
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The catalytic aerobic oxidation of alkylarenes catalyzed by cobalt supported on a highly crystalline γ-Al2O3 support (Co/Al2O3 nanocatalyst) is reported. The catalyst was prepared by a co-precipitation method and characterized using scanning and high-resolution transmission electron microscopies, energy-dispersive X-ray spectroscopy, X-ray diffraction and surface area measurements. A wide range of alkylarenes were converted to corresponding ketones. The catalyst can be recovered by simple filtration is recyclable for up to six consecutive runs.
- Albadi, Jalal,Alihosseinzadeh, Amir,Jalali, Mehdi,Mansournezhad, Azam
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- Ammonium Tungstate as an Effective Catalyst for Selective Oxidation of Alcohols to Aldehydes or Ketones with Hydrogen Peroxide under Water - A Synergy of Graphene Oxide
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Ammonium tungstate was found to be a facile and efficient catalyst for selective oxidation of alcohols to the corresponding carbonyl compounds with hydrogen peroxide as oxidant. Heterogeneous graphene oxide as acid effectively intensified the transformations and resulted in excellent yields. The use of water as solvent rendered the reactions promising both economically and environmentally.
- Fu, Huihui,Hu, Chuanfeng,Huang, Zhida,Zhou, Jianhao,Peng, Xinhua
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supporting information
p. 447 - 451
(2017/11/27)
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- Fe(NO3)3/2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ): An efficient catalyst system for selective oxidation of alcohols under aerobic conditions
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A practical and efficient catalyst system for the oxidation of alcohols to carbonyl compounds using catalytic amounts of DDQ and Fe(NO3)3 with air as the environmentally benign oxidant has been developed. A variety of benzylic, heterocyclic, allylic and propargylic alcohols were smoothly converted into aldehydes or ketones in good to excellent yields. In case of large-scale reaction for the oxidation of benzyl alcohol, benzaldehyde was obtained in 93% isolated yield. Moreover, a possible reaction mechanism was proposed.
- Hu, Yongke,Chen, Lei,Li, Bindong
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- Cp*CoIII-Catalyzed Efficient Dehydrogenation of Secondary Alcohols
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A novel, well-defined molecular Cp*CoIII complex was isolated and structurally characterized for the first time. The efficiency of this cobalt catalyst was demonstrated in the alcohol dehydrogenation and dehydrative coupling of secondary alcohols under mild conditions into ketones and ethers, respectively.
- Gangwar, Manoj Kumar,Dahiya, Pardeep,Emayavaramban, Balakumar,Sundararaju, Basker
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supporting information
p. 2445 - 2448
(2018/09/10)
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- Polyoxovanadate catalysts for oxidation of 1-phenyl ethanol: From the discrete [V4O12]4- and [V10O28]6- anions to the anionic [V6O17]:N4 n - Coordination polymer
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Three polyoxovanadate-based hybrids {[Ru(phen)3]2[V4O12]}·13H2O (1), [Ru(phen)3]2[V10O28]·15H2O (2), and [Ru(phen)3]2[V6O17]Cl·11H2O (3) (phen = 1,10-phenanthroline) were prepared under hydrothermal conditions and characterized by electron paramagnetic resonance (EPR) spectroscopy, infrared spectroscopy (IR), powder X-ray diffraction (PXRD), thermogravimetric (TG) analysis, X-ray photoelectron spectroscopy (XPS), and single crystal X-ray diffraction analysis. Although the structures of both the cyclic vanadate [V4O12]4- and the [V10O28]6- anions are well-known, interestingly, a novel 1-dimensional (1-D) coordination polymer [V6O17]n4n- anion was constructed from tetranuclear [V4O12]4- and dinuclear [V2O7]4- building blocks, which were linked alternately through corner-shared oxygen atoms. Furthermore, the negative charges of polyoxovanadate [V4O12]4-, [V10O28]6- and [V6O17]4- anions were balanced by two [Ru(phen)3]2+/3+ complex cations. The catalytic properties of compounds 1-3 for the oxidation of 1-phenyl ethanol by tert-butyl hydroperoxide (TBHP) were investigated, and the results demonstrated that 1 and 3 exhibited excellent catalytic activities for the oxidation of 1-phenyl ethanol under mild catalytic conditions.
- Wang, Ke,Xu, Qiaofei,Ma, Pengtao,Zhang, Chao,Wang, Jingping,Niu, Jingyang
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p. 6273 - 6279
(2018/10/23)
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- Biocompatible metal-assisted C-C cross-coupling combined with biocatalytic chiral reductions in a concurrent tandem cascade
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In this study, we present a concurrent chemo/biocatalytic one pot reaction cascade by combining a metal (Pd/Cu) assisted Liebeskind-Srogl (L-S) coupling with an enantioselective enzymatic reduction for the production of chiral amines and alcohols. The latter transformation was realized by applying enantiocomplementary alcohol dehydrogenases from Lactobacillus kefir (R-selective) and Rhodococcus ruber (S-selective). Compatibility issues were solved by investigating first the L-S-coupling protocol in water at room temperature. Subsequently, we investigated two different biphasic systems and applied a biomimicking approach to separate enzyme-deactivating components. By using a lipophilic membrane in a smart reactor design, we were able to perform concurrent catalytic cascades with overall concentrations up to 100 mM substrate and to produce 1-phenylethylamine and several chiral alcohols in high yields (up to 81% over 2 steps) and enantiomeric purity ((+) and (?)-enantiomers both with 99% ee).
- Schaaf, Patricia,Bayer, Thomas,Koley, Moumita,Schnürch, Michael,Bornscheuer, Uwe T.,Rudroff, Florian,Mihovilovic, Marko D.
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p. 12978 - 12981
(2018/11/23)
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- Nickel-Catalyzed Addition of Arylboronic Acids to Alkyl Nitriles for Synthesis of Aryl Ketones in Fluorinated Solvent
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A mild and efficient nickel-catalyzed addition of arylboronic acids to alkyl nitriles in a fluorinated solvent for the synthesis of various aryl ketones is described. A broad range of arylboronic acids and alkyl nitriles were investigated, and the desired products were obtained with good to excellent yields under the optimized conditions. This method provides an opportunity for the synthesis of aryl ketones from alkyl nitriles, especially acetonitrile, with a non-noble metal catalyst in one pot.
- Tu, Dong-Huai,Li, Yang,Zhao, Bo,Gu, Yu-Jie,Wang, Bo,Lu, Ju-You,Lu, Jian
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supporting information
p. 593 - 596
(2017/12/06)
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- Biomimetic synthesis of 2-substituted N-heterocycle alkaloids by one-pot hydrolysis, transamination and decarboxylative Mannich reaction
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Heterocycles based on piperidine and pyrrolidine are key moieties in natural products and pharmaceutically active molecules. A novel multi-enzymatic approach based on the combination of a lipase with an α,ω-diamine transaminase is reported, opening up the synthesis, isolation and characterisation of a broad range of 2-substituted N-heterocycle alkaloids.
- Galman, James L.,Slabu, Iustina,Parmeggiani, Fabio,Turner, Nicholas J.
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supporting information
p. 11316 - 11319
(2018/10/24)
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- Biomimetic Oxidative Deamination Catalysis via ortho-Naphthoquinone-Catalyzed Aerobic Oxidation Strategy
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An ortho-naphthoquinone-catalyzed oxidative deamination reaction has been developed where the molecular oxygen and water serve as the sole oxidant and nucleophile. The current aerobic deamination reaction proceeds via the ketimine formation between ortho-naphthoquinones and amines followed by the prototropic rearrangement and hydrolysis by water, representing a biomimetic oxidative deamination of amine species in the human body by the liver and kidneys. The compatibility of ortho-naphthoquinone organocatalysts with molecular oxygen and water opens up a new biomimetic catalyst system that can function as versatile deaminases for a variety of amine-containing molecules such as amino acids and DNA nuclear bases.
- Golime, Gangadhararao,Bogonda, Ganganna,Kim, Hun Young,Oh, Kyungsoo
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p. 4986 - 4990
(2018/05/14)
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- Conversion of Olefins into Ketones by an Iron-Catalyzed Wacker-type Oxidation Using Oxygen as the Sole Oxidant
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We describe a mild and operationally simple procedure for the oxidation of olefins into ketones. The reaction is catalyzed by the hexadecafluorinated iron–phthalocyanine complex FePcF16 with stoichiometric amounts of triethylsilane as an additive under oxygen atmosphere to give ketones in good to high yields with excellent chemoselectivity and functional group tolerance. Ketone formation proceeds in up to 95 % yield and with 100 % regioselectivity while the corresponding alcohols were observed as side products.
- Puls, Florian,Kn?lker, Hans-Joachim
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supporting information
p. 1222 - 1226
(2018/01/01)
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- Easy Access to Enantiopure (S)- and (R)-Aryl Alkyl Alcohols by a Combination of Gold(III)-Catalyzed Alkyne Hydration and Enzymatic Reduction
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Chemoenzymatic one-pot processes based on the combination of metal catalysis and biocatalysis open up highly attractive perspectives regarding the production of enantiopure compounds. By combining a gold-catalyzed hydration reaction with an enzymatic reduction, we present a straightforward and atom-economical chemoenzymatic method for the synthesis of secondary alcohols with excellent optical purity. Efficient cofactor recycling exploits the solvent of the metal-catalyzed step as an auxiliary substrate for the enzymatic step.
- Schaaf, Patricia,Gojic, Vladimir,Bayer, Thomas,Rudroff, Florian,Schnürch, Michael,Mihovilovic, Marko D.
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p. 920 - 924
(2018/02/23)
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- Fe(NO3)3·9H2O-catalyzed aerobic oxidative deoximation of ketoximes and aldoximes under mild conditions
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A mild, simple process for the effective aerobic oxidative deoximation of a wide range of ketoximes and aldoximes has been developed that utilizes Fe(NO3)3·9H2O as the single catalyst and molecular oxygen as the green oxidant. The environmentally benign protocol provides moderate to excellent yield and broad functional groups tolerance and is a valuable synthetic method for practical applications. According the relevant verification experiment, a plausible mechanism has been proposed.
- Li, Yongshu,Xu, Nizhou,Mei, Guangyao,Zhao, Yun,Zhao, Yiyong,Lyu, Jinghui,Zhang, Guofu,Ding, Chengrong
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supporting information
p. 810 - 814
(2018/08/09)
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- Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide
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The highly efficient catalytic oxidation and oxidative kinetic resolution (OKR) of secondary alcohols has been achieved using a synthetic manganese catalyst with low loading and hydrogen peroxide as an environmentally benign oxidant in the presence of a small amount of sulfuric acid as an additive. The product yields were high (up to 93%) for alcohol oxidation and the enantioselectivity was excellent (>90% ee) for the OKR of secondary alcohols. Mechanistic studies revealed that alcohol oxidation occurs via hydrogen atom (H-atom) abstraction from an α-CH bond of the alcohol substrate and a two-electron process by an electrophilic Mn-oxo species. Density functional theory calculations revealed the difference in reaction energy barriers for H-atom abstraction from the α-CH bonds of R- and S-enantiomers by a chiral high-valent manganese-oxo complex, supporting the experimental result from the OKR of secondary alcohols.
- Miao, Chengxia,Li, Xiao-Xi,Lee, Yong-Min,Xia, Chungu,Wang, Yong,Nam, Wonwoo,Sun, Wei
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p. 7476 - 7482
(2017/10/30)
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