2270-57-7Relevant articles and documents
Naves
, (1951)
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.
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.
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.