2404-44-6Relevant academic research and scientific papers
A PALLADIUM CATALYZED CONVERSION OF HALOHYDRINS TO KETONES
Tsuji, Jiro,Nagashima, Hideo,Sato, Koji
, p. 3085 - 3088 (1982)
Pd(OAc)2 combined with P(o-Tol)3 catalyzes the conversion of halohydrins to ketones in the presence of K2CO3.Various halohydrins, which are easily available from olefins, can be converted to ketones in high yields.
Metalloporphyrinic framework containing multiple pores for highly efficient and selective epoxidation
Yang, Xiu-Li,Wu, Chuan-De
, p. 4797 - 4799 (2014)
Metalloporphyrin MnIIICl-5,10,15,20-tetrakis(3,5- biscarboxylphenyl)porphyrin, having eight carboxylate groups in multiple coordination modes, connects with paddle-wheel Zn2(COO)4 units for the construction of an interesting porous porphyrinic framework that demonstrates high efficiency and stability upon epoxidation of olefins with excellent substrate size selectivity.
Direct oxidative carboxylation of terminal olefins to cyclic carbonates by tungstate assisted-tandem catalysis
Calmanti, Roberto,Perosa, Alvise,Selva, Maurizio
, p. 7609 - 7619 (2021/10/12)
Tungstate catalysts are well established for olefin epoxidation reactions, while their catalytic activity for CO2 insertion in epoxides is a more recent discovery. This dual reactivity of tungstate prompted the present development of a catalytic tandem process for the direct conversion of olefins into the corresponding cyclic organic carbonates (COCs). Each of the two steps was studied in the presence of the ammonium tungstate ionic liquid catalyst-[N8,8,8,1]2[WO4]-obtained via a benign procedure starting from ammonium methylcarbonate ionic liquids. The catalytic epoxidation first step was optimised on 1-decene as model substrate, using H2O2 as benign oxidant, [N8,8,8,1]2[WO4] as catalyst and phosphoric acid as promoter affording quantitative conversion with 92% selectivity towards decene oxide. Unfortunately, the addition of CO2 from the start (auto-tandem catalysis) gave low yields of decene carbonate (10%). On the contrary, the addition of 1 atm CO2 and tetrabutyl ammonium iodide after completion of the epoxidation first step without any intermediate work-up (assisted-tandem catalysis) afforded a 94% yield in decene carbonate. The protocol could be scaled up to a 10 gram scale. The scope of the reaction was demonstrated for primary aliphatic olefins with different alkyl chain lengths (C6-C16), while cyclic and aromatic activated olefins such as cyclohexene and styrene suffered from the formation of undesired overoxidation products in the first step.
Preparation of flavin-containing mesoporous network polymers and their catalysis
Arakawa, Yukihiro,Sato, Fumiaki,Ariki, Kenta,Minagawa, Keiji,Imada, Yasushi
supporting information, (2020/02/15)
Riboflavin tetramethacrylate (RFlTMA) was prepared as a flavin monomer and copolymerized with ethylene glycol dimethacrylate (EGDMA) under polymerization-induced phase separation conditions. The resulting flavin-containing mesoporous network polymer, poly(RFlTMA-co-EGDMA), was found to be a more effective catalyst than riboflavin tetraacetate (RFlTA), a soluble analogue, for aerobic hydrogenation of olefins despite its heterogeneity, which allowed for its multiple recovery and reuse through simple filtrations and washings without loss in catalytic activity. In addition, the polymeric flavin was demonstrated to be utilized also as an effective photocatalyst in the oxidation of benzyl alcohols.
Copper based coordination polymers based on metalloligands: Utilization as heterogeneous oxidation catalysts
Kumar, Gulshan,Hussain, Firasat,Gupta, Rajeev
, p. 16985 - 16994 (2019/01/03)
This work presents the synthesis and characterization of two Cu(ii)-based coordination polymers prepared by utilizing two different Co(iii)-based metalloligands offering appended arylcarboxylic acid groups. Both coordination polymers are three-dimensional in nature and present pores and channels filled with water molecules. Both coordination polymers function as heterogeneous catalysts for the epoxidation of various olefins using O2 while employing isobutyraldehyde as the coreductor and for peroxide-mediated oxidation of assorted benzyl alcohols. The catalytic results illustrate efficient oxidation reactions, whereas the hot-fltration test and leaching experiments indicate the true heterogeneous nature of the catalysis.
Mechanistically Driven Development of an Iron Catalyst for Selective Syn-Dihydroxylation of Alkenes with Aqueous Hydrogen Peroxide
Borrell, Margarida,Costas, Miquel
supporting information, p. 12821 - 12829 (2017/09/25)
Product release is the rate-determining step in the arene syn-dihydroxylation reaction taking place at Rieske oxygenase enzymes and is regarded as a difficult problem to be resolved in the design of iron catalysts for olefin syn-dihydroxylation with potential utility in organic synthesis. Toward this end, in this work a novel catalyst bearing a sterically encumbered tetradentate ligand based in the tpa (tpa = tris(2-methylpyridyl)amine) scaffold, [FeII(CF3SO3)2(5-tips3tpa)], 1 has been designed. The steric demand of the ligand was envisioned as a key element to support a high catalytic activity by isolating the metal center, preventing bimolecular decomposition paths and facilitating product release. In synergistic combination with a Lewis acid that helps sequestering the product, 1 provides good to excellent yields of diol products (up to 97% isolated yield), in short reaction times under mild experimental conditions using a slight excess (1.5 equiv) of aqueous hydrogen peroxide, from the oxidation of a broad range of olefins. Predictable site selective syn-dihydroxylation of diolefins is shown. The encumbered nature of the ligand also provides a unique tool that has been used in combination with isotopic analysis to define the nature of the active species and the mechanism of activation of H2O2. Furthermore, 1 is shown to be a competent synthetic tool for preparing O-labeled diols using water as oxygen source.
Selective oxidation of hydrocarbons under air using recoverable silver ferrite-graphene (AgFeO2-G) nanocomposite: A good catalyst for green chemistry
Hosseini, Seyed Majid,Hosseini-Monfared, Hassan,Abbasi, Vahideh,Khoshroo, Mohammad Reza
, p. 72 - 79 (2016/04/10)
The selective oxidation of hydrocarbons is a main academic and industrial research challenge. A lot of researches have been done about this issue, but till now relatively little attention has been paid to graphene-complex oxide nanocomposites. Herein, we report our studies on a new catalyst. Silver ferrite-graphene (AgFeO2-G) as a separable nanocomposite from the reaction solution, was used as an effective oxidizing agent for the oxidation of various hydrocarbons (1- decene, cyclohexene, cis-cycloctene, cyclohexane, cyclooctane etc.) under mild conditions (55 °C, 8 h) with high conversion and selectivity using air, that is proper for 'green' chemistry. Metal or metal oxide nanoparticles assembled on graphene sheets revealed high electrocatalytic activity. Indeed, AgFeO2 with graphene due to low band gap and graphene oxide with large amounts of oxygen-containing groups, provide facility catalytic activity of catalyst-supported system. We also found that, with this catalyst, selective oxidation could be achieved without the need for the addition of solvent, which is appropriate in particular for 'green' chemistry. The catalysts showed little deactivation and maintained their conversion and selectivity levels duration of the measurements.
Unique Chemoselective Hydrogenation using a Palladium Catalyst Immobilized on Ceramic
Monguchi, Yasunari,Marumoto, Takahisa,Ichikawa, Tomohiro,Miyake, Yutaka,Nagae, Yoshiyuki,Yoshida, Michiyuki,Oumi, Yasunori,Sawama, Yoshinari,Sajiki, Hironao
, p. 2155 - 2160 (2015/11/24)
A heterogeneous palladium catalyst supported on a ceramic (5 % Pd/ceramic) was developed. The catalyst exhibited a specific chemoselectivity for hydrogenation that has never been achieved by other palladium-catalyzed methods. Either aliphatic or aromatic N-Cbz groups could be deprotected to the corresponding free-amines, while the hydrogenolysis of benzyl esters and ethers did not proceed. Furthermore, aryl chlorides and epoxides were tolerant under the Pd/ceramic-catalyzed hydrogenation conditions. 5 % Pd/ceramic could be reused without any loss of catalyst activity, as no palladium leaching was detected in the reaction media.
Development of chelate resin-supported palladium catalysts for chemoselective hydrogenation
Monguchi, Yasunari,Ichikawa, Tomohiro,Nozaki, Kei,Kihara, Kensuke,Yamada, Yuuko,Miyake, Yutaka,Sawama, Yoshinari,Sajiki, Hironao
supporting information, p. 6499 - 6505 (2015/08/18)
Abstract Two kinds of palladium catalysts immobilized on a chelate resin bearing diiminoacetate or polyamine moieties on the polystyrene-divinylbenzene polymer were newly prepared by the adsorption of palladium (II) ions on these resins followed by the reduction to palladium (0) with hydrazine monohydrate. Both catalysts showed a similar activity for hydrogenation. A variety of reducible functionalities, except for benzylic alcohol, alkyl benzyl ether, silyl ether, and epoxide, could be reduced under the hydrogenation conditions using either catalyst. Since the palladium metal elution from the immobilized catalysts was never observed, the catalysts could be reused without any decrease in the catalyst activity for at least 5 runs.
Solvent-Free Aerobic Epoxidation of Dec-1-ene Using Gold/Graphite as a Catalyst
Gupta, Upendra Nath,Dummer, Nicholas F.,Pattisson, Samuel,Jenkins, Robert L.,Knight, David W.,Bethell, Donald,Hutchings, Graham J.
, p. 689 - 696 (2015/08/04)
The oxidation of dec-1-ene has been investigated using gold nanoparticles supported on graphite in the presence of a radical initiator (α,α-azobisisobutyronitrile) using oxygen from air as oxidant. We have investigated the influence of the reaction temperature (70-100 °C), catalyst mass and reaction time on the epoxide yield. In the absence of a radical initiator the reaction does not proceed, although auto-oxidation can occur at higher temperatures in the range studied. However, in the presence of an initiator, selective oxidation occurs and the initiator propagates the reaction through the formation of a peroxy-radical at the allylic C3 position. Graphite enhances the formation of the allylic products dec-1-en-3-ol, dec-1-en-3-one, and dec-2-en-1-ol; however, the addition of gold nanoparticles to the graphite, enhances formation of 1,2-epoxydecane. It is suggested that gold suppresses the formation of allylic products via a Russell termination. Graphical Abstract: [Figure not available: see fulltext.]
