73 research outputs found
Les normes, comment?
La description normalisée des ressources d’enseignement et d’apprentissage requiert l’utilisation d’outils d’implantation conformes aux conventions d’un standard ou d’une norme internationale et un réseau d’entraide et d’accompagnement
1,6,7-Trigermabicyclo[4.1.0]hept-3-en-7-yl: The Isolable Bicyclic Germyl Radical
The one-electron oxidation reaction of potassium 3,4-dimethyl-1,6,7-tris(tri-tert-butylsilyl)-1,6,7-trigermabicyclo[4.1.0]hept-3-en-7-ide (2-·K+) with tris(pentafluorophenyl)borane in THF
results in the formation of stable 3,4-dimethyl-1,6,7-tris(tri-tert-butylsilyl)-1,6,7-trigermabicyclo[4.1.0]hept-3-en-7-yl (3•), representing the first bicyclic germyl radical with the bicyclo[4.1.0]hept-3-ene skeleton. The germyl radical 3• was characterized by X-ray crystallographic
analysis as well as ESR spectroscopy, showing that it has a near-planar Ge-radical center
1,6,7-Trigermabicyclo[4.1.0]hept-3-en-7-yl: The Isolable Bicyclic Germyl Radical
The one-electron oxidation reaction of potassium 3,4-dimethyl-1,6,7-tris(tri-tert-butylsilyl)-1,6,7-trigermabicyclo[4.1.0]hept-3-en-7-ide (2-·K+) with tris(pentafluorophenyl)borane in THF
results in the formation of stable 3,4-dimethyl-1,6,7-tris(tri-tert-butylsilyl)-1,6,7-trigermabicyclo[4.1.0]hept-3-en-7-yl (3•), representing the first bicyclic germyl radical with the bicyclo[4.1.0]hept-3-ene skeleton. The germyl radical 3• was characterized by X-ray crystallographic
analysis as well as ESR spectroscopy, showing that it has a near-planar Ge-radical center
Theoretical Mechanistic Investigation of the Dynamic Kinetic Resolution of N‑Protected Amino Acid Esters using Phase-Transfer Catalysts
A detailed theoretical mechanistic investigation on the
dynamic
kinetic resolution of N-protected amino acid esters using phase-transfer
catalysts is described. Semiautomatic exhaustive conformation search
of transition state (TS)-like structures were carried out using the
ConFinder program and the pseudo-TS conformational search (PTSCS)
method. This conformational search method successfully provided reasonable
TS structures for determining the stereoselectivity in the asymmetric
base hydrolysis of hexafluoroisopropyl (HFIP) esters as well as the
racemization mechanism. Furthermore, the independent gradient model
(IGM) analysis of the TS structures suggested that the H-bonding interactions
with the oxyanion hole and π-stacking interactions are the common
important features of the proposed TS structures that determine the
stereoselectivity
Comparison of fixation variability and average gaze deviations from fixation target among the DEF, N-DEF, and BF conditions.
Comparison of fixation variability and average gaze deviations from fixation target among the DEF, N-DEF, and BF conditions.</p
Theoretical Mechanistic Investigation of the Dynamic Kinetic Resolution of N‑Protected Amino Acid Esters using Phase-Transfer Catalysts
A detailed theoretical mechanistic investigation on the
dynamic
kinetic resolution of N-protected amino acid esters using phase-transfer
catalysts is described. Semiautomatic exhaustive conformation search
of transition state (TS)-like structures were carried out using the
ConFinder program and the pseudo-TS conformational search (PTSCS)
method. This conformational search method successfully provided reasonable
TS structures for determining the stereoselectivity in the asymmetric
base hydrolysis of hexafluoroisopropyl (HFIP) esters as well as the
racemization mechanism. Furthermore, the independent gradient model
(IGM) analysis of the TS structures suggested that the H-bonding interactions
with the oxyanion hole and π-stacking interactions are the common
important features of the proposed TS structures that determine the
stereoselectivity
Typical examples of fixation variability.
Smooth scatter plots show typical examples of fixation variability during foveal threshold (upper) and visual field (lower) measurement in dominant eye fixation (DEF), non-dominant eye fixation (N-DEF), and binocular fixation (BF) conditions. Fixation variability of the visual field within 30° (upper) and 10° (magnified; lower) in visual field measurement. BCEA, bivariate contour ellipse area.</p
Participant demographic and ocular characteristics.
Participant demographic and ocular characteristics.</p
Comparison of standard automated perimetry findings among the DEF, N-DEF, and BF conditions.
Comparison of standard automated perimetry findings among the DEF, N-DEF, and BF conditions.</p
Dynamic Kinetic Resolution of N‑Protected Amino Acid Esters via Phase-Transfer Catalytic Base Hydrolysis
Asymmetric
base hydrolysis of α-chiral esters with synthetic
small-molecule catalysts is described. Quaternary ammonium salts derived
from quinine were used as chiral phase-transfer catalysts to promote
the base hydrolysis of N-protected amino acid hexafluoroisopropyl
esters in a CHCl<sub>3</sub>/NaOH (aq) via dynamic kinetic resolution,
providing the corresponding products in moderate to good yields (up
to 99%) with up to 96:4 er. Experimental and computational mechanistic
studies using DFT calculation and pseudotransition state (pseudo-TS)
conformational search afforded a TS model accounting for the origin
of the stereoselectivity. The model suggested π-stacking and
H-bonding interactions play essential roles in stabilizing the TS
structures
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