2270-57-7Relevant articles and documents
Rethinking Basic Concepts-Hydrogenation of Alkenes Catalyzed by Bench-Stable Alkyl Mn(I) Complexes
Weber, Stefan,St?ger, Berthold,Veiros, Luis F.,Kirchner, Karl
, p. 9715 - 9720 (2019/10/14)
An efficient additive-free manganese-catalyzed hydrogenation of alkenes to alkanes with molecular hydrogen is described. This reaction is atom economic, implementing an inexpensive, earth-abundant nonprecious metal catalyst. The most efficient precatalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe)(CO)3(CH2CH2CH3)]. The catalytic process is initiated by migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate which undergoes rapid hydrogenolysis to form the active 16e Mn(I) hydride catalyst [Mn(dippe)(CO)2(H)]. A range of mono- A nd disubstituted alkenes were efficiently converted into alkanes in good to excellent yields. The hydrogenation of 1-alkenes and 1,1-disubstituted alkenes proceeds at 25 °C, while 1,2-disubstituted alkenes require a reaction temperature of 60 °C. In all cases, a catalyst loading of 2 mol % and a hydrogen pressure of 50 bar were applied. A mechanism based on DFT calculations is presented, which is supported by preliminary experimental studies.
Regio- and Chemoselective Hydrogenation of Dienes to Monoenes Governed by a Well-Structured Bimetallic Surface
Miyazaki, Masayoshi,Furukawa, Shinya,Komatsu, Takayuki
, p. 18231 - 18239 (2017/12/27)
Unprecedented surface chemistry, governed by specific atomic arrangements and the steric effect of ordered alloys, is reported. Rh-based ordered alloys supported on SiO2 (RhxMy/SiO2, M = Bi, Cu, Fe, Ga, In, Pb, Sn, and Zn) were prepared and tested as catalysts for selective hydrogenation of trans-1,4-hexadiene to trans-2-hexene. RhBi/SiO2 exhibited excellent regioselectivity for the terminal C=C bond and chemoselective hydrogenation to the monoene, not to the overhydrogenated alkane, resulting in a high trans-2-hexene yield. Various asymmetric dienes, including terpenoids, were converted into the corresponding inner monoenes in high yields. This is the first example of a regio- and chemoselective hydrogenation of dienes using heterogeneous catalysts. Kinetic studies and density functional theory calculations revealed the origin of the high selectivity: (1) one-dimensionally aligned Rh arrays geometrically limit hydrogen diffusion and attack to alkenyl carbons from one direction and (2) adsorption of the inner C=C moiety to Rh is inhibited by steric repulsion from the large Bi atoms. The combination of these effects preferentially hydrogenates the terminal C=C bond and prevents overhydrogenation to the alkane.
Flavin-functionalized gold nanoparticles as an efficient catalyst for aerobic organic transformations
Imada, Yasushi,Osaki, Motonari,Noguchi, Mikiko,Maeda, Takatoshi,Fujiki, Misa,Kawamorita, Soichiro,Komiya, Naruyoshi,Naota, Takeshi
, p. 99 - 106 (2015/03/04)
Monolayer-protected gold clusters functionalized with synthetic flavins were synthesized and their catalytic activity in aerobic organic transformations investigated. Gold nanoparticles with 5-ethyl-3-(8-thiooctyl)lumiflavinium perchlorate acts as an efficient catalyst for the aerobic oxidation of organic sulfides to the corresponding sulfoxides upon treatment with hydrazine at room temperature and under atmospheric pressure in oxygen. With a catalytic amount of gold nanoparticles with 3-(8-thiooctyl)lumiflavin, diimide reduction of various olefins can be performed with hydrazine at room temperature under atmospheric pressure in air with greater yields of product alkanes than with non-supported 3-methyllumiflavin catalyst under the same conditions. Kinetic studies revealed that the mono-layer-protected gold cluster-catalyzed reactions proceeded faster than those with non-supported catalysts over the full substrate concentration range for the hydrogenation of olefins and at lower substrate concentrations for sulfoxidation. This positive effect was rationalized by assuming a Michaelis-Menten-type mechanism in which the specific inclusion of substrates into the enzyme-like reaction cavities was a key factor in the high efficiency of the supported flavin catalysts.
Palladium nanoparticles in situ generated in metal-organic films for catalytic applications
Gao, Shuiying,Cao, Minna,Li, Weijin,Cao, Rong
, p. 12185 - 12193 (2014/08/05)
Palladium nanoparticles were first in situ generated in metal-organic films for catalytic applications. Layer-by-layer assembly of metal-organic films consisting of rigid-rod chromophores connected by terminal pyridine moieties to palladium centers on solid substrates was presented. Bipyridyl and polypyridyl ligands were used as building blocks to explore the influence of different ligand structures on catalytic properties. Metal-organic films were characterized by UV-Vis spectra, atomic force microscopy (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results show that the deposition mechanism of metal-organic films is perfect layer-by-layer self-assembling with complete surface coverage and regular growth. Moreover, the catalytic activity toward the hydrogenation of olefin was investigated. Based on XPS and TEM, the catalytic activity toward the hydrogenation of olefin was ascribed to the in situ formation of Pd nanoparticles from Pd ions in metal-organic films. This film material is an active catalyst for the hydrogenation of olefin under mild conditions. Furthermore, catalytic results indicated that monodentate bipyridyl ligands exhibited superior catalytic activity than tridentate polypyridyl ligands. Catalytic activity is related to the loading amount of catalysts and permeability. More importantly, this study points toward the potential application of metal-organic films as heterogeneous catalysts with easy separation and good recyclability. This journal is the Partner Organisations 2014.
Metal-ligand core-shell nanocomposite catalysts for the selective semihydrogenation of alkynes
Mitsudome, Takato,Takahashi, Yusuke,Ichikawa, Satoshi,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
supporting information, p. 1481 - 1485 (2013/04/10)
Catalysts with a sheltered upbringing: Novel core-shell nanocomposite catalysts consisting of active metal nanoparticles encapsulated by macroligands have been prepared. They have Pd nanoparticles (PdNPs) as an active core and shell ligands having sulfoxide moieties coordinated to the PdNPs. The shell protects the catalyst from coordination by alkenes and allows the lead-free selective semihydrogenation of a wide range of alkynes without any additives (see scheme). Copyright
Selective reduction of dienes/polyenes using sodium borohydride/catalytic ruthenium(III) in various liquid amide aqueous mixtures
Babler, James H.,Ziemke, David W.,Hamer, Robert M.
, p. 1754 - 1757 (2013/04/10)
An efficient method to effect selective reduction of several structurally diverse dienes and an unsymmetrical triene is reported. The reduction is facile at 0 °C in a liquid amide aqueous solution containing sodium borohydride in the presence of 15 mol % ruthenium(III) chloride. The chemoselectivity of the reaction is controlled by proper choice of the liquid amide solvent.
Iron(III) chloride-catalysed aerobic reduction of olefins using aqueous hydrazine at ambient temperature
Lamani, Manjunath,Ravikumara, Guralamata S.,Prabhu, Kandikere Ramaiah
supporting information; experimental part, p. 1437 - 1442 (2012/07/03)
A chemoselective reduction of olefins and acetylenes is demonstrated by employing catalytic amounts of ferric chloride hexahydrate (FeCl 3·6 H2O) and aqueous hydrazine (NH 2NH2·H2O) as hydrogen source at room temperature. The reduction is chemoselective and tolerates a variety of reducible functional groups. Unlike other metal-catalysed reduction methods, the present method employs a minimum amount of aqueous hydrazine (1.5-2 equiv.). Also, the scope of this method is demonstrated in the synthesis of ibuprofen in aqueous medium. Copyright
Guanidine catalyzed aerobic reduction: A selective aerobic hydrogenation of olefins using aqueous hydrazine
Lamani, Manjunath,Guralamata, Ravikumara Siddappa,Prabhu, Kandikere Ramaiah
supporting information; experimental part, p. 6583 - 6585 (2012/07/14)
An efficient aerobic reduction of olefins, internal as well as terminal, is developed using guanidine as an organocatalyst. A remarkable chemoselectivity in reduction has been demonstrated in the presence of a variety of functional groups and protective groups and a selective reduction of a terminal olefin in the presence of an internal olefin is revealed.
Aerobic reduction of olefins by in situ generation of diimide with synthetic flavin catalysts
Imada, Yasushi,Iida, Hiroki,Kitagawa, Takahiro,Naota, Takeshi
supporting information; experimental part, p. 5908 - 5920 (2011/07/07)
A versatile reducing agent, diimide, can be generated efficiently by the aerobic oxidation of hydrazine with neutral and cationic synthetic flavin catalysts 1 and 2. This technique provides a convenient and safe method for the aerobic reduction of olefins, which proceeds with 1 equiv of hydrazine under an atmosphere of O2 or air. The synthetic advantage over the conventional gas-based method has been illustrated through high hydrazine efficiency, easy and safe handling, and characteristic chemoselectivity. Vitamin B2 derivative 6 acts as a highly practical, robust catalyst for this purpose because of its high availability and recyclability. Association complexes of 1b with dendritic 2,5-bis(acylamino)pyridine 15 exhibit unprecedented catalytic activities, with the reduction of aromatic and hydroxy olefins proceeding significantly faster when a higher-generation dendrimer is used as a host pair for the association catalysts. Contrasting retardation is observed upon similar treatment of non-aromatic or non-hydroxy olefins with the dendrimer catalysts. Control experiments and kinetic studies revealed that these catalytic reactions include two independent, anaerobic and aerobic, processes for the generation of diimide from hydrazine. Positive and negative dendrimer effects on the catalytic reactions have been ascribed to the specific inclusion of hydrazine and olefinic substrates into the enzyme-like reaction cavities of the association complex catalysts. Copyright
Neutral flavins: Green and robust organocatalysts for aerobic hydrogenation of olefins
Imada, Yasushi,Kitagawa, Takahiro,Ohno, Takashi,Iida, Hiroki,Naota, Takeshi
supporting information; experimental part, p. 32 - 35 (2010/03/04)
"Chemical Equation Presented" Various olefins can be hydrogenated quantitatively with neutral flavin 2 catalysts in the presence of 1 -2 equiv of hydrazine under 1 atm of O2. Vitamin B2 derivative 2g acts as a highly efficient and robust catalyst for the present environmentally benign process producing water and nitrogen gas as the only waste products
