Search results for "Selectivity"
showing 10 items of 1148 documents
CO2 as a C1-organic building block: Electrocarboxylation of aromatic ketones. A quantitative study of the effect of the concentration of substrate an…
2006
The purpose of this work is to establish and discuss quantitative relationships between the selectivity in preparative scale electrolysis and intrinsic and operational parameters for the electrocarboxylation of aromatic ketones. For the investigated ketones, under appopriate experimental conditions the selectivity of the process is mainly determined by the competition between carboxylation and protonation, de-halogenation reactions (when an halogenated ketone is involved), and possibly dimerizations involving the electrogenerated radical anion. A simple model was proposed to account for these unwanted side paths which allows to predict the dependence of the selectivity as a function of the …
A new model for C–C bond formation processes derived from the Molecular Electron Density Theory in the study of the mechanism of [3+2] cycloaddition …
2016
Abstract The [3+2] cycloaddition (32CA) reactions of the nitrile ylide (NY) with ethylene and with dicyanoethylene (DCE) have been studied using the Molecular Electron Density Theory through DFT calculations at the MPWB1K/6-31G(d) level. The analysis of the electronic structure of NY indicates that it presents a carbenoid structure with an sp 2 lone pair at the carbon atom. While the 32CA reaction with ethylene presents a low activation energy, 6.1 kcal mol −1 , the transition state structure associated with the 32CA reaction of NY with DCE is located 7.5 kcal mol −1 below the reagents, the reaction being completely regioselective. The topological analysis of the Electron Localisation Funct…
Peptide mapping by reversed-phase high-performance liquid chromatography employing silica rod monoliths.
2003
In this paper, a general procedure is described for the generation of peptide maps of proteins with monolithic silica-based columns. The peptide fragments were obtained by tryptic digestion of various cytochrome c species with purification of the tryptic fragments achieved by reversed-phase high-performance liquid chromatographic methods. Peak assignment of the various peptides was based on evaluation of the biophysical properties of the individual peptides and via mass spectrometric identification. The performance of several different monolithic sorbents prepared as columns of identical cross-sectional dimensions were investigated as part of these peptide mapping studies and the data evalu…
ChemInform Abstract: Lithium Enediolates and Dienediolates of Carboxylic Acids in Synthesis: Alkylation with Secondary Halides.
2010
Abstract High yields in the alkylation of dianions of α,β-unsaturated carboxylic acids with secondary halides can be obtained despite elimination reactions occurring. α-Regioselectivity for the alkylation of but-2-enoic acids ( 1–4 ) is seldom obtained. Although double bond stereoselectivity is higher than 99% for γ-alkylated products, stereoselectivity is rather poor for most of the α-alkylated products.
ChemInform Abstract: Stereoselective Synthesis of 7,11-Guaien-8,12-olides from Santonin. Synthesis of Podoandin and (+)-Zedolactone A.
2001
Photochemical rearrangement of hydroxy ester 2, easily obtained from santonin (1), afforded butenolide 4, a good starting material for the synthesis of 7,11-guaien-8,12-olides. Compound 4 has been transformed into compound 10, which has been used for the synthesis of podoandin (5) and (+)-zedolactone A (ent-6). Regioselective elimination of the acetyl group on C10 afforded directly podoandin (5). For the synthesis of ent-6, a hydroxyl group has been regio- and stereoselectively introduced at the 4α-position through the 3α,4α-epoxide 15. The basic hydrolysis of the 10-acetyl group in compound 18 took place with concomitant intramolecular conjugated addition of the alkoxide to the butenolide …
Synthesis of 1,3,5-Trisubstituted Hydantoins by Regiospecific Domino Condensation/Aza-Michael/O→N Acyl Migration of Carbodiimides with Activated α,β-…
2005
[reaction: see text] Carbodiimides and suitably activated alpha,beta-unsaturated carboxylic acids react effectively to afford a vast array of 1,3,5-trisubstituted hydantoins by means of a regiospecific domino condensation/aza-Michael/N--O acyl migration. The reaction works well in very mild conditions (20 degrees C, dichloromethane) with fumaric acid derivatives bearing an electron-withdrawing group in the beta position. Good results have been obtained also with less activated substrates bearing only one electron-withdrawing group in the beta position, using more polar solvents (acetonitrile, DMF), and in the presence of a base (2,4,6-trimethylpyridine). Reactions with asymmetric carbodiimi…
Partial oxidation of aromatic alcohols via TiO2 photocatalysis: the influence of substituent groups on the activity and selectivity
2012
Aromatic alcohols with substituent groups in different positions have been partially oxidised to the corresponding aldehydes in a photocatalytic system in order to investigate the influence of the substituents on reactivity and selectivity to aldehyde. To this aim benzyl alcohol, 2-methoxybenzyl alcohol, 3-methoxybenzyl alcohol, 4-methoxybenzyl alcohol, 2,4-dimethoxybenzyl alcohol, 4-hydroxybenzyl alcohol and 4-hydroxy-3-methoxybenzyl alcohol have been photocatalytically oxidised to their corresponding aldehydes in aqueous TiO2 suspensions under near-UV irradiation. Home-made and commercial rutile TiO2 samples were used as photocatalysts. The catalysts were characterized by XRD, BET, SEM, T…
Enzymatic glycosylation of o-glycopeptides
1992
Abstract O-Glycosylation of serine derivatives carried out with N-urethane protected glucosamine yields O-glycopeptides which are regio- and stereoselectively galactosylated with the aid of β-1,4-galactosyltransferase (EC 2.4.1.22).
Environmentally Friendly Photocatalytic Oxidation of Aromatic Alcohol to Aldehyde in Aqueous Suspension of Brookite TiO(2)
2008
WOS: 000260509000008
Non-classical CH⋯O hydrogen-bond determining the regio- and stereoselectivity in the [3 + 2] cycloaddition reaction of (Z)-C-phenyl-N-methylnitrone w…
2015
The role of the ester groups in the regio- and stereoselectivities of the zw-type [3 + 2] cycloaddition (32CA) reaction of C-phenyl-N-methylnitrone with dimethyl 2-benzylidenecyclopropane-1,1-dicarboxylate (BCPC) has been studied using DFT methods at the MPWB1K/6-31G(d) level. The possible ortho/meta regioisomeric channels and the endo/exo stereoselective approach modes were explored and characterized. Analysis of the relative energies associated with the different reaction pathways indicates that the presence of the two CO2Me groups in the cyclopropane ring has a remarkable effect on selectivities favouring the ortho/endo path, in good agreement with the experimental data. Inclusion of sol…