17733-68-5Relevant academic research and scientific papers
Activation of C-C Bonds via σ-Bond Metathesis: Hydroborenium-Catalyzed Hydrogenolysis of Cyclopropanes
Su, Bo,Li, Yawei,Li, Zhen Hua,Hou, Jun-Li,Wang, Huadong
supporting information, p. 4159 - 4163 (2020/04/10)
High-valent transition metal or main group complex mediated σ-bond metathesis plays an important role in the activation of covalent H-E bonds. However, its involvement in the activation of C-C bonds has remained elusive. Here we describe direct hydroboration of the C-C bonds of cyclopropanes by a hydroborenium complex. Our mechanism study suggests this reaction operates through a σ-bond metathesis pathway. With this hydroborenium complex as a catalyst, hydrogenolysis of unfunctionalized cyclopropanes was achieved, which is unprecedented for homogeneous catalysts and provides an unconventional approach for C-C bond functionalization in the absence of metals.
Heteroatom-free arene-cobalt and arene-iron catalysts for hydrogenations
Gaertner, Dominik,Welther, Alice,Rad, Babak Rezaei,Wolf, Robert,Von Wangelin, Axel Jacobi
supporting information, p. 3722 - 3726 (2014/04/17)
75 years after the discovery of hydroformylation, cobalt catalysts are now undergoing a renaissance in hydrogenation reactions. We have evaluated arene metalates in which the low-valent metal species is - conceptually different from heteroatom-based ligands - stabilized by π coordination to hydrocarbons. Potassium bis(anthracene)cobaltate 1 and -ferrate 2 can be viewed as synthetic precursors of quasi-"naked" anionic metal species; their aggregation is effectively impeded by (labile) coordination to the various π acceptors present in the hydrogenation reactions of unsaturated molecules (alkenes, arenes, carbonyl compounds). Kinetic studies, NMR spectroscopy, and poisoning studies of alkene hydrogenations support the formation of a homogeneous catalyst derived from 1 which is stabilized by the coordination of alkenes. This catalyst concept complements the use of complexes with heteroatom donor ligands for reductive processes. Especially high selectivities were observed in the hydrogenation of various alkenes, ketones, and imines with bis(anthracene) cobaltate(-I) [K(dme)2{Co(C14H10)2}] under mild conditions (1-5 mol% cat., 1-10 bar H2, 20-60°C). Mechanistic studies indicate the operation in alkene hydrogenations of a homogeneous catalyst formed by initial ligand exchange and stabilized by the coordination of π-acidic alkenes or arenes.
Organolanthanide catalyzed hydrogenation and hydrosilylation of substituted methylenecycloalkanes
Molander, Gary A.,Winterfeld, Joern
, p. 275 - 279 (2007/10/03)
This communication presents a study of the scope of the catalytic hydrogenation and hydrosilylation of chiral exomethylene-substituted cyclopentanes and cyclohexanes utilizing the organolanthanide precatalysts Cp2* LnCH(SiMe3)2 (Cp* = C5Me5; Ln = Sm, Yb). Both reaction types are sterically driven and lead to the cis-diastereomer as the major product. Additionally, the hydrosilylation is regiospecific, the silane being placed exclusively at the terminal position of the double bond.
ALKYLATION OF BENZENE WITH 4-METHYLCYCLOHEXANOL IN THE PRESENCE OF SULFURIC ACID
Lipovich, V. G.,Zemskov, V. V.,Ratovskii, G. V.,Burlakova, O. V.
, p. 109 - 112 (2007/10/02)
Alkylation of benzene with 4-methylcyclohexanol in the presence of methylcyclohexane and 96, 88, and 80percent H2SO4 has been studied.It was established that depending on the solubility of the starting components in sulfuric acid, alkylation occurs in the inorganic phase or on the interface between the organic and inorganic phases.The yield and composition of the catalysate are determined to a significant degree by the extent of the alkylation process and intramolecular hydride transfers.
REACTION OF 1-CHLORO-1-METHYLCYCLOHEXANE WITH PHENYL- AND BENZYL- TRIMETHYLSILANES IN THE PRESENCE OF ALUMINIUM CHLORIDE
Bolestova, G. I.,Parnes, Z. N.,Vol'pin, M. E.
, p. 967 - 971 (2007/10/02)
In the reaction of 1-chloro-1-methylcyclohexane with phenyltrimethylsilane and benzyltrimethylsilane in the presence of aluminum chloride the chlorine atom is substituted by a phenyl or benzyl group with the formation of 1-methyl-1-phenyl- and 1-methyl-1-benzylcyclohexane, respectively.In the case of benzyltrimethylsilane the products from alkylation of the benzene ring of the benzyltrimethylsilane by the 1-methylcyclohexyl carbocation in the Friedel-Crafts reaction are formed in addition to 1-methyl-1-benzylcyclohexane.
PHOTOCHEMISTRY OF N-ACYLAZOLES. VI). PHOTOREACTIVITIES OF 1-ACYL-1,2,4-TRIAZOLES AND OF 2-ACYLTETRAZOLES
Murato, Kazuo,Yatsunami, Takashi,Iwasaki, Shigeo
, p. 588 - 605 (2007/10/02)
Contrary to the findings in the photolysis of N-acylimidazoles (2) irradiation of 1-acyl-1,2,4-triazoles afforded no photo-Fries product, but instead products formed via the corresponding acyl radicals and aldehydes.Photolysis of 2-acyltetrazoles gave in part the same products as those obtained from the irradiation of the corresponding acyl-triazoles as well as 2-alkyl-1,3,4-oxadiazoles.N-Acyltetrazoles didn't give any photo-Fries product neither.
