50417-78-2Relevant academic research and scientific papers
Solvent-Dependent Reaction Pathways Operating in Copper(II) Tetrafluoroborate Promoted Oxidative Ring-Opening Reactions of Cyclopropyl Silyl Ethers
Hasegawa, Eietsu,Nemoto, Kazuki,Nagumo, Ryosuke,Tayama, Eiji,Iwamoto, Hajime
, p. 2692 - 2703 (2016/04/26)
(Figure Presented) Oxidative ring-opening reactions of benzene-fused bicyclic cyclopropyl silyl ethers, promoted by copper(II) tetrafluoroborate, were investigated. The regioselectivity of cyclopropane ring-opening as well as product distributions were found to be highly dependent on the nature of the solvent. In alcohols, dimeric substances arising from external bond cleavage are major products. Radical rearrangement products are also formed in solvents such as ether and ethyl acetate. On the contrary, nucleophile addition to carbocation intermediates, generated by internal bond cleavage, occurs mainly in reactions taking place in acetonitrile. It is proposed that the observed solvent effects that govern the reaction pathways followed are a consequence of varying solvation of copper intermediates, which governs their reactivity and redox properties. In addition, the influence of counteranions of the copper salts, organonitriles, cyclic dienes, and substrate structures on the pathways followed in these reactions was also examined.
MCl2(ampy)(dppf) (M = Ru, Os): Multitasking catalysts for carbonyl compound/alcohol interconversion reactions
Putignano, Elisabetta,Bossi, Gianluca,Rigo, Pierluigi,Baratta, Walter
, p. 1133 - 1142 (2012/04/04)
The easily accessible complexes [MCl2(dppf)(ampy)] (M = Ru (cis-1), Os (trans-2); dppf = 1,1′-bis(diphenylphosphino)ferrocene; ampy = 2-aminomethylpyridine) in the presence of base (NaOiPr, KOtBu) are efficient catalysts for several reactions involving carbonyl compounds and alcohols. The derivatives 1 and 2 catalyze the selective transfer hydrogenation of aldehydes and ketones to alcohols with 2-propanol using 0.1-0.005 mol % of catalyst at 82 °C with TOF values up to 3.0 × 105 h-1. These compounds (0.1-0.02 mol %) promote the hydrogenation of aldehydes and ketones in EtOH or a MeOH/EtOH mixture at 30-90 °C (5 atm of H2) and the acceptorless dehydrogenation of alcohols to ketones in tBuOH at 130-145 °C (0.4 mol %). Complexes 1 and 2 (0.5 mol %) catalyze the racemization of chiral alcohols at 70 °C in 2-propanol and the isomerization of allylic alcohols to ketones in tBuOH at 70-120 °C (1 mol %). In addition, 1 and 2 (0.5 mol %) promote the α alkylation of α-tetralone with primary alcohols (EtOH, nPrOH, and nBuOH) at 120 °C in a tBuOH/toluene mixture (1/2 v/v). Complex 2 is easily obtained in 93% yield from [OsCl2(PPh3) 3], dppf, and ampy in toluene.
Catalytic asymmetric protonation of lithium enolates using amino acid derivatives as chiral proton sources
Mitsuhashi, Kaori,Ito, Rie,Arai, Takayoshi,Yanagisawa, Akira
, p. 1721 - 1724 (2007/10/03)
Asymmetric protonation of lithium enolates was examined using commercially available amino acid derivatives as chiral proton sources. Among the amino acid derivatives tested, Nβ-L-aspartyl-L-phenylalanine methyl ester was found to cause significant asymmetric induction in the protonation of lithium enolates. The enantiomeric excess (up to 88% ee) of the products obtained in the presence of a catalytic amount of the chiral proton source was higher than those obtained in the stoichiometric reaction.
Synthesis of Biological Markers in Fossil Fuels. 2. Synthesis and 13C NMR Studies of Substituted Indans and Tetralins
Adamczyk, Maciej,Watt, David S.,Netzel, Daniel A.
, p. 4226 - 4237 (2007/10/02)
Unambiguous syntheses of all possible methyl, ethyl, n-propyl, and n-butyl derivatives of indan and tetralin were developed using the Kumada coupling procedure involving the reaction of aryl or vinyl halides with Grignard reagents in the presence of nickel(II) chloride.An analysis of the 13C NMR spectra of these compounds was also completed.
