Search results for "ISOMER"

Conformational investigations of bis(α-aminoalkyl)phosphinic acids and studies of the stability of their complexes with Cu(II)

2008

Abstract Conformational investigations of a group of bis(α-aminoalkyl)phosphinic acids were performed by use of NMR spectroscopy and theoretical calculations. In the case of one of the studied compounds, substituted with aminobenzyl and amino(p-chlorobenzyl) moieties, a pH-dependent equilibrium between conformers, stabilized by intermolecular hydrogen bonds was observed. Potentiometric studies proved that these molecules formed stable complexes with copper(II) ions, where stoichiometry was 1:1 and 1:2 depending on pH of their aqueous solution.

Unusual oleanane-type saponins from Arenaria montana

2010

Three oleanane-type saponins, 3-O-β-d-glucopyranosylechinocystic acid 28-O-β-d-xylopyranosyl-(1→4)-[α-l-rhamnopyranosyl-(1→2)]-α-l-rhamnopyranosyl ester (1), 3-O-β-d-glucopyranosylechinocystic acid 28-O-α-l-arabinopyranosyl-(1→3)-β-d-xylopyranosyl-(1→4)-[α-l-rhamnopyranosyl-(1→2)]-α-l-rhamnopyranosyl ester (2), 3-O-β-d-glucopyranosylcaulophyllogenin 28-O-β-d-apiofuranosyl-(1→3)-β-d-xylopyranosyl-(1→4)-[β-d-apiofuranosyl-(1→3)]-α-l-rhamnopyranosyl-(1→2)-α-l-rhamnopyranosyl ester (3) were isolated from the whole plant of Arenaria montana. Their unusual structures for the Caryophyllaceae family were established mainly by 2D NMR techniques and mass spectrometry.

Light-induced opening and closing of the intramolecular hydrogen bond in glyoxylic acid.

2013

The isomerization process of glyoxylic acid (GA) conformers and their complexes with a water molecule were studied in a low temperature argon matrix. The research target was to understand how starting conformation and complexation affects the near-IR (NIR) induced conformer interconversion. The most stable GA conformer (Tc) is characterized by an intramolecular hydrogen bond, and it is found to undergo light-induced conformer interconversion slower than the open (Tt) conformer. Upon complexation with water, the isomerization processes slow down in the case of the Tc conformer, whereas for the Tt-based complex the influence of water is negligible on the isomerization process.

2019

Structural changes of glycolic acid (GA) complex with nitrogen induced by selective overtone excitation of the νOH mode were followed in argon matrices using FTIR spectroscopy. For the most stable SSC1 complex present in different trapping sites directly upon deposition site, selective changes in the νOH region were achieved upon near-infrared irradiation. Simultaneously, new conformers of the GA…N2 complex were formed, giving rise to several sets of bands in the νOH and νC=O regions of the spectra. Both position and intensity of new absorptions appeared to be highly sensitive on the wavelength of radiation used, as well as on the annealing of the matrix. Based on theoretical calculations a…

Raman spectroscopy and high-overtone driven isomerization of glyoxylic acid in solid argon

2013

High-overtone induced chemistry of glyoxylic acid isolated in a low-temperature argon matrix was investigated using Raman spectroscopy. The Raman spectra of two most stable conformers of glyoxylic acid are presented. Upon excitation in high overtone vibrational bands by 532 nm irradiation of the lowest energy conformer most abundant in neat deposited sample, the isomerization of glyoxylic acid was observed. The process most plausible proceeds via absorption into the fifth vibrational overtone state of the OH group or its combination with the torsional vibrational transition. The assignment of the fundamental vibrational spectra was assisted by quantum chemical harmonic and anharmonic vibrat…

Total Synthesis and Biological Investigation of (−)‐Artemisinin: The Antimalarial Activity of Artemisinin Is not Stereospecific

2018

Here, we describe an efficient and diversity-oriented entry to both (-)-artemisinin (1) and its natural antipode (+)-artemisinin, starting from commercially and readily available S-(+)- and R-(-)-citronellene, respectively. Subsequently, we answered the still open question regarding the specificity of artemisinins action. By using a drug-sensitive Plasmodium falciparum NF54 strain, we showed that the antimalarial activity of artemisinin is not stereospecific. Our straightforward and biomimetic approach to this natural endoperoxide enables the synthesis of artemisinin derivatives that are not accessible through applying current methods and may help to address the problem of emerging resistan…

Storage and release of false transmitters after infusion of (+)- and (?)-?-methyldopamine

1971

Rabbits were given an infusion of 10 mg/kg (−)- or 30 mg/kg (+)-α-methyldopamine and killed after 135 min. The noradrenaline content of the heart was decreased to 26±5 and 34±2%, respectively, of the control value. After infusion of the (+)-isomer the missing noradrenaline was replaced by (−)-α-methylnoradrenaline. Electrical stimulation of the sympathetic nerves or infusion of acetylcholine plus atropine caused an output of noradrenaline and (−)-α-methylnoradrenaline from the isolated heart. The two amines were released in the same proportion as they were stored in the heart and the total output of both amines equalled the output of noradrenaline from control hearts. Nerve stimulation caus…

l -Prolinoyl chiral picket iron porphyrins evaluated for the enantioselective epoxidation of alkenes

2003

International audience; Four atropisomers of an L-prolinoyl picket porphyrin were synthesised from tetra-o-aminophenyl porphyrin (TAPP) and were evaluated as alkene epoxidation catalysts after incorporation of iron in the porphyrin core. In the case of the aaaa atropisomer bearing the four amino groups on the same side, a bulky base was employed in order to suppress the eventual reaction on the non-functionalised side of the porphyrin.The resulting enantioselectivities were compared with either other chiral motifs or with the corresponding strapped porphyrins. The enantioselectivities obtained with picket porphyrins are as high as those for strapped porphryins, and in some cases, even highe…

Cytotoxic labdane diterpenes and bisflavonoid atropisomers from leaves of Araucaria bidwillii

2017

Abstract Chemical investigation of a methanolic extract of leaves from Araucaria bidwillii (Araucariaceae) from Egypt afforded four new labdane diterpenoidal metabolites (1–4) together with one known diterpene, 7-oxocallitrisic acid (5), two triterpenoidal metabolites, 2-O-acetyl-11-keto-boswellic acid (6) and β-sitosterol-3-O-glucopyranoside (7), phloretic acid (8), and two methylated bisflavonoids, agathisflavone-4′,7,7″-trimethyl ether (9) and cupressuflavone-4′,7,7″-trimethyl ether (10). The new metabolites 1–4 were unambiguously identified by applying extensive 1D and 2D NMR spectroscopic studies as well as HRESIMS. The relative and absolute configurations of 1–4 were determined using …

Microwave-Assisted Organocatalytic Enantioselective Intramolecular aza-Michael Reaction with α,β-Unsaturated Ketones

2011

An organocatalytic enantioselective intramolecular aza-Michael reaction of carbamates bearing conjugated ketones as Michael acceptors is described. By using 9-amino-9-deoxy-epi-hydroquinine as the catalyst and pentafluoropropionic acid as a co-catalyst, a series of piperidines, pyrrolidines, and the corresponding benzo-fused derivatives (indolines, isoindolines, tetrahydroquinolines, and tetrahydroisoquinolines) can be obtained in excellent yields and enantioselectivities. In addition, the use of microwave irradiation at 60 °C improves the efficiency of the process giving rise to the final products with comparable yields and enantiomeric excesses. Some mechanistic insights are also consider…