Determination of the Absolute Configuration of 1,5-Diaza-cis-decalin by Comparison of Measured and Calculated CD-Spectra

1998 ◽  
Vol 53 (10-11) ◽  
pp. 896-902 ◽  
Author(s):  
Jörg Fleischhauer ◽  
Gerhard Raabe ◽  
A. G. Santos ◽  
Jan Schiffer ◽  
Axel Wollmer
Keyword(s):  
Absolute Configuration ◽  
Vibrational Energy ◽  
Zero Point ◽  
Equilibrium Mixture ◽  
Cotton Effect ◽  
Basis Set ◽  
Basis Sets ◽  
Cd Spectra ◽  
The Absolute

Abstract The absolute configurations of both 1,5-diaza-c/s-decalin enantiomers were determined by com-parison of measured and calculated CD spectra.CD spectra for both enantiomers were recorded. Theoretical CD spectra for one of the isomers were calculated by means of the semiempirical CNDO/2S method. Eight local minima on the energy hypersurface of the title compound were used to describe the conformer equilibrium mixture. The geometries of these conformers were calculated employing one-determinant ab initio calculations using the split valence 6-31G* basis set. Boltzmann factors were then obtained using relative energies calculated with three different basis sets and including correlation(MP2)-and zero point vibrational energy.Comparing the sign of the observed and calculated longest wavelength Cotton effect, we assign an absolute configuration to the compound. This assignment was verified by means of X-ray structure determination of one of the enantiomers’ α-methoxy-α-trifluoromethylphenyl aceticacid (MTPA, Mosher’s reagent) derivative.

Determination of the Absolute Configuration of Bis(tetrahydropyran2-yl)methane by Comparison of Measured and Calculated CD-spectra

1998 ◽  
Vol 53 (8) ◽  
pp. 704-710 ◽  
Author(s):  
Jörg Fleischhauer ◽  
Christoph Jansen ◽  
Axel Koslowski ◽  
Gerhard Raabe ◽  
Jan Schiffer ◽  
...  
Keyword(s):  
Force Field ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
Absolute Configuration ◽  
Vibrational Energy ◽  
Basis Set ◽  
Basis Sets ◽  
Am1 Method ◽  
Cd Spectra ◽  
The Absolute

Abstract The absolute configuration of bis(tetrahydropyran-2-yl)methane (1) was determined by comparison of measured and calculated CD spectra. The theoretical CD spectra were obtained by means of the CNDO/2S method. The five presumably lowest local minima on the energy hypersurface of the title compound were used to describe the conformer equilibrium mixture. The geometries of these conformers were calculated employing the MM3 force field, the semiempirical AM1 method and one-determinant ab initio calculations employing the 6-31G* basis set. Boltzmann factors were then obtained using relative energies calculated with three different basis sets and including correlation- and zero point vibrational energy. Based on the sign of the observed and calculated longest wavelength Cotton effect we assign an absolute configuration to the compound which is in keeping with the chirality expected from the assumed reaction mechanism. The results of force field and ab initio calculations converge to the point that the conformer equilibrium is dominated (85 -96%) by one single conformer which is energetically separated from the other conformers by about 2-3 kcal/mol. This result agrees with previous experimental data.

Ab initio Studies of Hydrazines: Equilibrium Structures of 1,1-Dimethylhydrazine and Transition Structures Connecting Them

1987 ◽  
Vol 40 (11) ◽  
pp. 1783 ◽  
Author(s):  
NV Riggs ◽  
L Radom
Keyword(s):  
Internal Rotation ◽  
Vibrational Energy ◽  
Zero Point ◽  
Basis Set ◽  
Basis Sets ◽  
Primary Amines ◽  
Rotational Angle ◽  
Small Rise ◽  
Equilibrium Structures ◽  
Anti Form

Optimization of the geometries of various stationary structures of 1,1-dimethylhydrazine has been carried out with the 3-21G and 3-21G(N*) basis sets, and the energies of each of the latter optimized structures have been evaluated with the 6.31G* basis set. The gauche form with a (mean) internal rotational angle near 80� (hydrazine, approx. 90�) is the lowest-energy form. After zero-point vibrational -energy corrections, the anti form lies in a shallow well 14kJ mol-1 higher on the potential-energy surface for internal rotation, and the transition structure connecting them lies approx. 1 kJ mol-1 higher still. The anti form is thus a true equilibrium species, unlike the case for hydrazine, but constitutes less than 0.5% of the molecules present at room temperature. It is estimated to have a half-life of less than 10 ps , so its observation by present physical methods may prove to be difficult. The barrier to internal rotation via the syn form (41kJ mol-1) coincides with that for hydrazine. gem-Dimethyl substitution in hydrazine leads to a small rise (1-2 kJ mol-1) in the barrier to inversion at the unsubstituted nitrogen atom, but to an unexpectedly high (by 8-9 kJ mol-1) calculated barrier to inversion at the substituted centre, whether the result be referred to the barrier in hydrazine or to that in dimethylamine. Calculated NH stretching frequencies for the gauche form show a spacing much larger than that for 'simple' primary amines, as is found experimentally.

CD-Spectroscopic Investigations for the Determination of the Absolute Configuration of α-Alkylated 1,4-CycIohexanedione Derivatives

2000 ◽  
Vol 55 (11) ◽  
pp. 1011-1014 ◽  
Author(s):  
Jörg Fleischhauer ◽  
Sven Gabriel ◽  
Dieter Ender ◽  
Anja Nühring ◽  
Axel Wollmer
Keyword(s):  
Absolute Configuration ◽  
Membered Ring ◽  
Cd Spectra ◽  
Pure Material ◽  
Enantiomerically Pure ◽  
System 2 ◽  
The Absolute ◽  
Stereogenic Center ◽  
Rotational Strengths

The absolute configuration of the conformationally flexible six membered ring system 2-methyl- and 2,6-dimethyl-l,4-cyclohexanedione monoethylene acetal was determined by comparison of measured and calculated CD spectra. The rotational strengths were calculated by means of the CNDO/S-method assuming R at the stereogenic center. The results were compared with the predictions made by the octant rule. The enantiomerically pure material was synthesized via the corresponding SAMP- and RAMP-hydrazones.

An ab initio Study of the Equilibrium Structures of Prop-2-ynamine (Propargylamine) and the Transition Structures Connecting Them

1987 ◽  
Vol 40 (3) ◽  
pp. 435 ◽  
Author(s):  
NV Riggs
Keyword(s):  
Ab Initio ◽  
Internal Rotation ◽  
Vibrational Energy ◽  
Vibrational Analysis ◽  
Zero Point ◽  
Basis Set ◽  
Basis Sets ◽  
Experimental Result ◽  
Transition Structure ◽  
Equilibrium Structures

Optimization with the 3-21G and 3-21G(N*) basis sets finds, in agreement with previous ab initio studies and the experimental result, the anti conformation of prop-2-ynamine to be of lowest energy and, after zero-point vibrational -energy ( Ezpv ) corrections, the gauche form to lie 11 kJ mol-l higher; by vibrational analysis, both are confirmed as equilibrium structures. The synform was not able to be optimized with the 3.21G basis set but, with the 3-21G(N*) basis set, is found to lie 8.6 kJ mol-1 (after Ezpv corrections) above the gauche form, and is shown by vibrational analysis to be a transition structure connecting enantiomeric gauche forms by internal rotation about the N-C bond. The transition structure connecting gauche and anti forms by internal rotation lies 6.3 kJ mol-1 (after Ezpv corrections) above the gauche form, and the transition structure for inversion at the nitrogen atom lies 31.1 kJ mol- l (after Ezpvcorrections) above the anti form.

scholarly journals 6-Methoxy-3,3’,3’-Trimethylspiro[2H-1-Benzopyran-2,1’[2]Oxaindan]: Separation Of Enantiomers, Circular Dichroism Measurements And Determination Of The Absolute Configuration

2003 ◽  
Vol 58 (7-8) ◽  
pp. 443-450 ◽  
Author(s):  
Elena N. Voloshina ◽  
Yuekui Wang ◽  
Nikolai A. Voloshina ◽  
Gerhard Raabe ◽  
Hans-Joachim Gais ◽  
...  
Keyword(s):  
High Pressure ◽  
Optical Properties ◽  
Liquid Chromatography ◽  
Absolute Configuration ◽  
Quantum Chemical ◽  
Cd Spectra ◽  
Chromatography Method ◽  
The Absolute ◽  
Liquid Chromatography Method

The enantiomers of 6-methoxy-3,3’,3’-trimethylspiro[2H-1-benzopyran-2,1’[2]oxaindan] were separated with the high-pressure liquid chromatography method. Their optical properties were studied experimentally and by quantum-chemical calculations. The absolute configurations of the compounds were determined by comparison of the measured and calculated CD spectra.

Evaluation of Different Synthetic Routes to (2R,3R)-3-Hydroxymethyl-2-(4-hydroxy- 3-methoxyphenyl)-1,4-Benzodioxane-6-Carbaldehyde

2020 ◽  
Vol 23 (26) ◽  
pp. 2960-2968
Author(s):  
Renáta Kertiné Ferenczi ◽  
Tünde-Zita Illyés ◽  
Sándor Balázs Király ◽  
Gyula Hoffka ◽  
László Szilágyi ◽  
...  
Keyword(s):  
Absolute Configuration ◽  
Stereoselective Synthesis ◽  
Cotton Effect ◽  
Enantioselective Synthesis ◽  
Aryl Group ◽  
Target Molecule ◽  
Synthetic Routes ◽  
The Absolute

The reported enantioselective synthesis for the preparation of (+)-(2R,3R)-2-(4- hydroxy-3-methoxyphenyl)-3-hydroxymethyl-1,4-benzodioxane-6-carbaldehyde, precursor for the stereoselective synthesis of bioactive flavanolignans, could not be reproduced. Thus, the target molecule was prepared via the synthesis and separation of diastereomeric O-glucosides. TDDFT-ECD calculations and the 1,4-benzodioxane helicity rule were utilized to determine the absolute configuration. ECD calculations also confirmed that the 1Lb Cotton effect is governed by the helicity of the heteroring, while the higher-energy ECD transitions reflect mainly the orientation of the equatorial C-2 aryl group.

scholarly journals Rapid Organocatalytic Chirality Analysis of Amines, Amino Acids, Alcohols, Amino Alcohols and Diols with Achiral Iso(thio)cyanate Probes

2021 ◽  
Author(s):  
Eryn Nelson ◽  
Jeffrey S. S. K. Formen ◽  
Christian Wolf
Keyword(s):  
Amino Acids ◽  
Absolute Configuration ◽  
Rapid Determination ◽  
Amino Alcohols ◽  
Enantioselective Synthesis ◽  
Widespread Occurrence ◽  
Chiral Compounds ◽  
New Methods ◽  
The Absolute

The widespread occurrence and significance of chiral compounds does not only require new methods for their enantioselective synthesis but also efficient tools that allow rapid determination of the absolute configuration,...

Sign in / Sign up

Export Citation Format

Share Document