105-07-7Relevant articles and documents
Selectivity Modulation of the Ley–Griffith TPAP Oxidation with N-Oxide Salts
Moore, Peter W.,Jiao, Yanxiao,Mirzayans, Paul M.,Sheng, Lexter Ng Qi,Hooker, Jordan P.,Williams, Craig M.
, p. 3401 - 3407 (2016)
A wide variety of novel non-hygroscopic N-oxide tetraphenylborate salts were synthesized and evaluated as co-oxidants in the Ley–Griffith (TPAP) oxidation of benzylic and allylic alcohols under non-anhydrous conditions. The novel DABCOO·TPB (2:1) salt was herein unearthed as a viable competitor to the first-generation NMO·TPB (2:1) salt, but more importantly gave increased performance under oxidative competition. X-ray crystal structure analysis and NMR spectroscopy revealed that depending on the crystallization conditions 1:1, 2:1 or 3:2 N-oxide–tetraphenylborate salts could be formed.
Copper-catalyzed cyanation of arylboronic acids using DDQ as cyanide source
Zhang, Guangyou,Chen, Shuyou,Fei, Haiyang,Cheng, Jiang,Chen, Fan
, p. 2247 - 2250 (2012)
In this paper, a copper-catalyzed cyanation of arylboronic acids is achieved with DDQ, providing nitriles with good yields. This new approach represents a safe method for the synthesis of aryl nitriles. Georg Thieme Verlag Stuttgart ? New York.
An effective synthesis of N,N-dimethylamides from carboxylic acids and a new route from N,N-dimethylamides to 1,2-diaryl-1,2-diketones
Kumagai, Takashi,Anki, Tomohiro,Ebi, Takahiro,Konishi, Akihito,Matsumoto, Kouzou,Kurata, Hiroyuki,Kubo, Takashi,Katsumoto, Kenta,Kitamura, Chitoshi,Kawase, Takeshi
, p. 8968 - 8973 (2010)
Carboxylic acids were heated at 150 °C in DMF in the presence of 1.25 equiv of thionyl chloride to give corresponding N,N-dimethylamides in good yields. Tandem chlorination and amidation reactions occurred in the one-pot procedure. Dicarboxylic acids needed prolonged reaction time to produce bisamides in good yields. Some benzamides were efficiently converted into corresponding 1,2-diaryl-1,2-diketones (benzils) under acyloin condensation conditions in the presence of 4,4′-di-tert-butylbiphenyl (DBB) in THF. Ultrasonic irradiation effectively accelerates the reaction, but it is not critical. However, the presence of DBB is fatal to the reaction. Although a few synthetic methods for benzils from benzoic acids have been reported so far, this method is one of the most convenient and highly reproducible procedures.
New selective metal-free oxidations of primary alcohols by HNO3 or HNO3 and O2, catalyzed by Br2
Minisci, Francesco,Porta, Ombretta,Recupero, Francesco,Punta, Carlo,Gambarotti, Cristian,Pierini, Monica,Galimberti, Laura
, p. 2203 - 2205 (2004)
Primary benzylic alcohols are selectively oxidized to the corresponding aromatic aldehydes by molecular oxygen at atmospheric pressure, under Br 2-HNO3 catalysis in a biphasic medium (1,2-dichloroethane- water, 5:1) at 60 °C. Under paragonable experimental conditions the aliphatic alcohols are oxidized to esters.
4CzIPN catalyzed photochemical oxidation of benzylic alcohols
Zhang, Heng,Guo, Tianyun,Wu, Mingzhong,Huo, Xing,Tang, Shouchu,Wang, Xiaolei,Liu, Jian
, (2021)
A green photoredox oxidation of benzylic primary and secondary alcohols to aldehydes and ketones with air as an oxidant was reported. The oxidation shows broad substrate scope and excellent selectivity over benzylic alcohols to the aliphatic alcohols. Further mechanistic studies revealed a quinuclidine mediated HAT process, and blue LEDs promoted 4CzlPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene) photoredox cycle were involved in our oxidation.
Efficient and Highly Selective Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Bucky Nanodiamond
Lin, Yangming,Wu, Kuang-Hsu Tim,Yu, Linhui,Heumann, Saskia,Su, Dang Sheng
, p. 3497 - 3505 (2017)
Selective oxidation of alcohols to aldehydes is widely applicable to the synthesis of various green chemicals. The poor chemoselectivity for complicated primary aldehydes over state-of-the-art metal-free or metal-based catalysts represents a major obstacle for industrial application. Bucky nanodiamond is a potential green catalyst that exhibits excellent chemoselectivity and cycling stability for the selective oxidation of primary alcohols in diverse structures (22 examples, including aromatic, substituted aromatic, unsaturated, heterocyclic, and linear chain alcohols) to their corresponding aldehydes. The results are comparable to reported transition-metal catalysts including conventional Pt/C and Ru/C catalysts for certain substrates under solvent-free conditions. The possible activation process of the oxidant and substrates by the surface oxygen groups and defect species are revealed with model catalysts, ex situ electrochemical measurements, and ex situ attenuated total reflectance. The zigzag edges of sp2 carbon planes are shown to play a key role in these reactions.
One-pot oxidant-free dehydrogenation-Knoevenagel tandem reaction catalyzed by a recyclable magnetic base-metal bifunctional catalyst
Yuan, Xiaofeng,Wan, Zijuan,Ning, Jinfeng,Zhang, Qiang,Luo, Jun
, (2020)
A new base-metal bifunctional catalyst NH-Pd(0)@MNP was prepared via a facile procedure and fully characterized. The as-prepared catalyst was used as an efficient relay catalyst for the one-pot oxidant-free dehydrogenation-Knoevenagel condensation tandem reaction from benzyl alcohol in H2O under mild conditions and generated benzalmalononitriles with yield up to 96%. Meanwhile, the catalyst could be easily recovered from the reaction system by an external magnetic field, and is reusable with little loss of activity up to 6 runs (5%).
Candida parapsilosis ATCC 7330 mediated oxidation of aromatic (activated) primary alcohols to aldehydes
Sivakumari, Thakkellapati,Chadha, Anju
, p. 91594 - 91600 (2015)
A green, simple and high yielding [up to 86% yield] procedure is developed for the oxidation of aromatic (activated) primary alcohols to aldehydes using whole cells of Candida parapsilosis ATCC 7330. The biotransformation is carried out under mild conditions at 25 °C, in hexane: water (48 : 2) (v/v).
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Mowry
, (1945)
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Highly Productive Oxidative Biocatalysis in Continuous Flow by Enhancing the Aqueous Equilibrium Solubility of Oxygen
Chapman, Michael R.,Cosgrove, Sebastian C.,Turner, Nicholas J.,Kapur, Nikil,Blacker, A. John
, p. 10535 - 10539 (2018)
We report a simple, mild, and synthetically clean approach to accelerate the rate of enzymatic oxidation reactions by a factor of up to 100 when compared to conventional batch gas/liquid systems. Biocatalytic decomposition of H2O2 is used to produce a soluble source of O2 directly in reaction media, thereby enabling the concentration of aqueous O2 to be increased beyond equilibrium solubility under safe and practical conditions. To best exploit this method, a novel flow reactor was developed to maximize productivity (g product L?1 h?1). This scalable benchtop method provides a distinct advantage over conventional bio-oxidation in that no pressurized gas or specialist equipment is employed. The method is general across different oxidase enzymes and compatible with a variety of functional groups. These results culminate in record space-time yields for bio-oxidation.
Selective oxidation of alcohols using ferrocene-labeled Merrifield resin-supported ionic liquid phase catalysts
Kurane, Rajanikant,Bansode, Prakash,Khanapure, Sharanabasappa,Salunkhe, Rajashri,Rashinkar, Gajanan
, p. 7807 - 7821 (2016)
Abstract: A novel ferrocene-labeled Merrifield resin-supported ionic liquid phase catalysts has been synthesized and successfully utilized for the selective oxidation of primary alcohols into corresponding aldehydes. The catalysts were recovered by simple filtration which greatly simplified the purification step and allowed successive reuse for multiple times without significant loss in activity. Graphical Abstract: [Figure not available: see fulltext.]
Mechanisms of the Aerobic Oxidation of Alcohols to Aldehydes and Ketones, Catalysed under Mild Conditions by Persistent and Non-Persistent Nitroxyl Radicals and Transition Metal Salts - Polar, Enthalpic, and Captodative Effects
Minisci, Francesco,Recupero, Francesco,Cecchetto, Andrea,Gambarotti, Cristian,Punta, Carlo,Faletti, Roberta,Paganelli, Roberto,Pedulli, Gian Franco
, p. 109 - 119 (2004)
The oxidation of alcohols to aldehydes and ketones by air or oxygen under mild conditions (room temperature and atmospheric pressure), catalysed by persistent and non-persistent nitroxyl radicals in combination with transition metal salts, appears to be the most convenient of the numerous processes developed for these purposes. The thermochemistry, the kinetics, and the Hammett correlations have allowed us to establish, on a quantitative basis, the fundamental difference between the oxidation catalysed by persistent and non-persistent nitroxyl catalysts. In the latter case, an interesting significant captodative effect is displayed for the first time for the oxidation of substituted benzyl alcohols; the importance of enthalpic and polar effects is emphasised.
Convenient oxidation of benzylic and allylic halides to aldehydes and ketones
Chen, David X.,Ho, Chi M.,Rudy Wu,Wu, Peter R.,Wong, Freeman M.,Wu, Weiming
, p. 4147 - 4148 (2008)
Benzylic and allylic halides were conveniently oxidized to aldehydes and ketones by pyridine N-oxide in the presence of silver oxide under mild conditions.
The Room-Temperature Palladium-Catalyzed Cyanation of Aryl Bromides and Iodides with Tri-t-butylphosphine as Ligand
Ramnauth, Jailall,Bhardwaj, Namrta,Renton, Paul,Rakhit, Suman,Maddaford, Shawn P.
, p. 2237 - 2239 (2003)
The palladium-catalyzed cyanation of aryl bromides and iodides to the corresponding nitriles occurs at room temperature when tri-t-butylphosphine is used as ligand, Zn(CN)2 as the cyanide source and Zn dust as a co-catalyst in DMF as solvent. A variety of aromatic halides, including electron-withdrawing and electron-donating, can be efficiently cyanated under these conditions. The reactions are completed in less than 1 hour and products are produced in good to excellent yield.
Oxidant free dehydrogenation of alcohols using chitosan/polyacrylamide entrapped Ag nanoparticles
Kurhe, Deepak K.,Fernandes, Thomson A.,Deore, Tushar S.,Jayaram, Radha V.
, p. 46443 - 46447 (2015)
Silver nanoparticles encaged in a nanoporous chitosan/polyacrylamide interpenetrating polymer network (Ag@IPN) were synthesized and characterized by various techniques such as Fourier Transform Infra Red (FTIR), X-ray Diffraction (XRD), Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy (SEM-EDX), Transmission Electron Microscopy (TEM), Thermogravimetric Analysis (TGA) and ICP-AES. This material exhibits good catalytic activity for the oxidant free dehydrogenation of alcohols to the corresponding carbonyl compounds. The reusability of Ag@IPN for this reaction was compared with a chitosan-silver complex under the same reaction conditions. It was found that encaging silver nanoparticles in interpenetrating polymer networks (IPN) has improved their stability by avoiding leaching and aggregation.
C- vsN-Oxidations of Benzyltriazanes: Selective Access to Triazones, Azimines, and Triazenes
Glowacki, Aurore,Jeux, Victorien,Gasnier, Gwéna?l,Joucla, Lionel,Jacob, Guy,Lac?te, Emmanuel
, p. 566 - 570 (2018)
The oxidation of several benzyltriazanes has been studied. Routes to the selective formation of triazenes, azimines, and triazones via C- or N-oxidation (and rearrangement) were devised. The rich reactivity of triazanes shows that trinitrogen chains are interesting functions, whose reactivity has been overlooked despite their interest as 3-N building blocks.
Radical induced disproportionation of alcohols assisted by iodide under acidic conditions
Huang, Yang,Jiang, Haiwei,Li, Teng,Peng, Yang,Rong, Nianxin,Shi, Hexian,Yang, Weiran
supporting information, p. 8108 - 8115 (2021/10/29)
The disproportionation of alcohols without an additional reductant and oxidant to simultaneously form alkanes and aldehydes/ketones represents an atom-economical transformation. However, only limited methodologies have been reported, and they suffer from a narrow substrate scope or harsh reaction conditions. Herein, we report that alcohol disproportionation can proceed with high efficiency catalyzed by iodide under acidic conditions. This method exhibits high functional group tolerance including aryl alcohol derivatives with both electron-withdrawing and electron-donating groups, furan ring alcohol derivatives, allyl alcohol derivatives, and dihydric alcohols. Under the optimized reaction conditions, a 49% yield of 5-methyl furfural and a 49% yield of 2,5-diformylfuran were obtained simultaneously from 5-hydroxymethylfurfural. An initial mechanistic study suggested that the hydrogen transfer during this redox disproportionation occurred through the inter-transformation of HI and I2. Radical intermediates were involved during this reaction.
One-Pot Direct Oxidation of Primary Amines to Carboxylic Acids through Tandem ortho-Naphthoquinone-Catalyzed and TBHP-Promoted Oxidation Sequence
Kim, Hun Young,Oh, Kyungsoo,Si, Tengda
supporting information, p. 18150 - 18155 (2021/12/09)
Biomimetic oxidation of primary amines to carboxylic acids has been developed where the copper-containing amine oxidase (CuAO)-like o-NQ-catalyzed aerobic oxidation was combined with the aldehyde dehydrogenase (ALDH)-like TBHP-mediated imine oxidation protocol. Notably, the current tandem oxidation strategy provides a new mechanistic insight into the imine intermediate and the seemingly simple TBHP-mediated oxidation pathways of imines. The developed metal-free amine oxidation protocol allows the use of molecular oxygen and TBHP, safe forms of oxidant that may appeal to the industrial application.
