Search results for "Catalysis"

Metal-Free Diastereo- and Enantioselective Dearomative Formal [3 + 2] Cycloaddition of 2-Nitrobenzofurans and Isocyanoacetate Esters

2022

The diastereo- and enantioselective dearomative formal [3 + 2] cycloaddition of 2-nitrobenzofurans and α-aryl-α-isocyanoacetate esters provides tricyclic compounds bearing the 3a,8b-dihydro-1H-benzofuro[2,3-c]pyrrole framework with three consecutive stereogenic centers. The reaction was enabled by a cupreine-ether organocatalyst. The reaction products were obtained with almost full diastereoselectivity and with excellent enantiomeric excesses for a number of substituted 2-nitrobenzofurans and isocyanoacetates.

Gold(I)-Catalyzed Intermolecular Cycloaddition of Allenamides with α,β-Unsaturated Hydrazones: Efficient Access to Highly Substituted Cyclobutanes

2014

α,β-Unsaturated N,N-dialkyl hydrazones undergo a mild [2 + 2] cycloaddition to allenamides when treated with a suitable gold catalyst. The method, which represents the first application of N,N-dialkyl hydrazones in gold catalysis, is compatible with a wide variety of substituents at the alkenyl moiety of the hydrazone component, proceeds with excellent levels of regio- and diastereoselectivity, and provides densely substituted cyclobutanes with good to excellent yields.

Catalytic properties of Ag-PolyaminoβCD NPs for reduction of nitroarenes

2014

The reduction of nitroarenes is a key reaction involved in the synthesis of several compounds such as drugs, pesticides or dyes. During the last years Pd and Ag NPs have been used as catalysts to carry out this reaction with NaBH4. However several mechanistic aspects of the process are still unclear; in particular there is not agreement about the kinetic order of these reactions, whether 0-th or 1-st order in the substrate[1]. The aim of this work is to use a novel catalytic systems constituted by Ag-NPs coated with different polyamino-βCDs (Figure 1)[2], to carry out the reduction of some aromatic nitrocompounds using NaBH4 as the reducing agent, and to determine the kinetic features of th…

Olefin metathesis reactions with fluorinated substrates, catalysts, and solvents.

2014

Catalytic Oxidation of Alkanes and Alkenes by H 2 O 2 with a μ‐Oxido Diiron(III) Complex as Catalyst/Catalyst Precursor

2015

A new mu-oxo diiron(III) complex of the lithium salt of the pyridine-based unsymmetrical ligand 3-[(3-{[bis(pyridin-2-ylmethyl)amino]methyl}-2-hydroxy-5-methylbenzyl)(pyridin2-ylmethyl)amino] propanoate (LiDPCPMPP), [Fe-2(mu-O)(LiDPCPMPP)(2)](ClO4)(2), has been synthesized and characterized. The ability of the complex to catalyze oxidation of several alkanes and alkenes has been investigated by using CH3COOH/H2O2 (1:1) as an oxidative system. Moderate activity in cyclohexane oxidation (TOF = 33 h(-1)) and good activity in cyclohexene oxidation (TOF = 72 h(-1)) were detected. Partial retention of configuration (RC = 53%) in cis- and trans-1,2-dimethylcyclohexane oxidation, moderate 3 degrees…

Spectroscopic and DFT Characterization of a Highly Reactive Nonheme FeV–Oxo Intermediate

2018

The reaction of [(PyNMe3)FeII(CF3SO3)2], 1, with excess peracetic acid at −40 °C generates a highly reactive intermediate, 2b(PAA), that has the fastest rate to date for oxidizing cyclohexane by a nonheme iron species. It exhibits an intense 490 nm chromophore associated with an S = 1/2 EPR signal having g-values at 2.07, 2.01, and 1.94. This species was shown to be in a fast equilibrium with a second S = 1/2 species, 2a(PAA), assigned to a low-spin acylperoxoiron(III) center. Unfortunately, contaminants accompanying the 2(PAA) samples prevented determination of the iron oxidation state by Mossbauer spectroscopy. Use of MeO-PyNMe3 (an electron-enriched version of PyNMe3) and cyclohexyl pero…

Enantioselective sensing of dicarboxylates. Influence of the stoichiometry of the complexes on the sensing mechanism

2009

Two new cyclohexane-based thiourea chiral ligands have been synthesized in their enantiomerically pure forms. Both the ability of these ligands in the complexation of chiral dicarboxylates and their sensing properties have been studied. The influence of the stoichiometry of the formed complexes on the fluorescent properties of the systems has been established. The effect of additional substitution in the cyclohexyl moiety was considered by comparing the properties of the newly prepared ligands with those of similar compounds previously described.

From Hexaphenylbenzene to 1,2,3,4,5,6-Hexacyclohexylcyclohexane

2020

The hydrogenation of hexaphenylbenzene was studied, affording novel partially hydrogenated hexacyclohexylbenzene (HCB) as well as fully hydrogenated 1,2,3,4,5,6-hexacyclohexylcyclohexane (HCC) as an unprecedented “oligocyclohexyl” molecule. The reaction process was analyzed by mass spectrometry with atmospheric pressure chemical ionization and high-performance liquid chromatography. From a crude product mixture, two different crystals with flake- and block-shapes could be grown and analyzed by X-ray crystallography, revealing their structures as HCB and HCC. While a geared arrangement of cyclohexyl substitutes was found in HCB, two isomeric structures were identified in HCC crystal with cha…

New Molecular Topologies by Fourfold Metathesis Reactions within a Hydrogen-Bonded Calix[4]arene Dimer

2003

A calix[4]arene tetrapentyl ether in the cone conformation substituted at its wide rim by four m-(omega-octenyloxy)phenyl urea groups forms hydrogen-bonded dimeric capsules in dichloromethane/benzene (95:5). Metathesis reaction with Grubbs' catalyst under high-dilution conditions (1.1 x 10(-4) M) followed by hydrogenation leads to a covalent connection of all the urea groups within a dimer. Three topologically different products may be expected in such a reaction: a bis[2]catenane, a doubly bridged monocatenane and a tetrabridged capsule. All three possible reaction products could be isolated in an overall yield up to 60 % for the separated and purified compounds. Their identification was b…

Fluorescent Sensing of Maleate versus Fumarate by a Neutral Cyclohexane Based Thiourea Receptor.

2006

A new cyclohexyl based fluorescent anion receptor, is able to recognize maleate versus fumarate both as their TMA salts. Costero Nieto, Ana Maria, Ana.Costero@uv.es ; Colera Llavata, Manuel, Manuel.Colera@uv.es ; Gaviña Costero, Pablo, Pablo.Gavina@uv.es ; Gil Grau, Salvador, Salvador.Gil@uv.es