Refine
Has Fulltext
- no (35)
Year of publication
Document Type
- Article (35) (remove)
Language
- English (35)
Is part of the Bibliography
- yes (35)
Keywords
- Conformational analysis (5)
- DFT calculations (4)
- NMR spectroscopy (4)
- Leguminosae (3)
- conformational analysis (3)
- Cytotoxicity (2)
- NMR (2)
- Plasmodium falciparum (2)
- Theoretical calculations (2)
- cytotoxicity (2)
- modified Mannich reaction (2)
- (+)-Tephrodin (1)
- 3,4-Dihydroisoquinoline (1)
- 4-Substituted cyclohexanones (1)
- 4-methylene-cyclohexyl pivalate (1)
- 6 alpha-Hydroxy-alpha-toxicarol (1)
- ALTONA equation (1)
- Alkenyl cyclohexanone (1)
- Alkenyl cyclohexenone (1)
- Aminonaphthol (1)
- Aminonaphthols (1)
- Anti-inflammatory (1)
- Antimicrobial (1)
- Benzazepine (1)
- Coumaronochromone (1)
- Coumestan (1)
- DFT structural study (1)
- Dynamic NMR (1)
- Dynamic NMR spectroscopy (1)
- Hammett-Brown plots (1)
- Isoflavone (1)
- Lannea rivae (1)
- Lannea schweinfurthii (1)
- Lonchocarpus bussei (1)
- Lonchocarpus eriocalyx (1)
- Millettia dura (1)
- Millettia lasiantha (1)
- Millettia micans (1)
- Modified Mannich reaction (1)
- Naphthoxazines (1)
- Naphthoxazinoquinazolines (1)
- Naphthoxazinoquinazolinones (1)
- Pterocarpan (1)
- Quantum chemical calculations (1)
- Quinazolines (1)
- Ring current effect (1)
- Simulation of H-1 NMR spectra (1)
- Stereochemistry (1)
- Tephrosia purpurea (1)
- Tephrosia subtriflora (1)
- Tephrosia villosa (1)
- Thienopyridine (1)
- [4+2] cycloaddition (1)
- antiplasmodial (1)
- cyclic imines (1)
- cycloaddition (1)
- dynamic NMR spectroscopy (1)
- exo-methylene conformational effect at cyclohexane (1)
- isoflavone (1)
- ortho-quinone methide (o-QMs) (1)
- prenylated flavanonol (1)
- pterocarpan (1)
- quantum chemical calculations (1)
- spectroscopy (1)
- subtriflavanonol (1)
Institute
The esters of 4-hydroxy-cyclohexanone and a series of carboxylic acids R-COOH with R of different electronic and steric influence (R=Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, sec-Bu, t-Bu, CF3, CH2Cl, CHCl2, CCl3, CH2Br, CHBr2, and CBr3) were synthesized and the conformational equilibria studied by 1H and 13C NMR spectroscopy at 103 K and at 295 K, respectively. The geometry of optimized structures of the axial/equatorial chair conformers was computed at the ab initio MO and DFT levels of theory. Only one preferred conformation was obtained for the axial and the equatorial conformer as well. When comparing the conformational equilibria of the cyclohexanone esters with those of the corresponding cyclohexyl esters a certain polarity contribution of the cyclohexanone framework was revealed, which is independent of the substituent effects and increases the stability of the axial conformers by a constant amount.
Configuration and stereodynamics of exo/endoisomeric push-pull alkenes of pentadiene structure
(1998)
NMR spectroscopic and theoretical structural analysis of 5,5-disubstituted hydantoins in solution
(1997)
The esters of 4-hydroxy-cyclohexanone and a series of carboxylic acids R-COOH with R of different electronic and steric influence (R=Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, sec-Bu, t-Bu, CF3, CH2Cl, CHCl2, CCl3, CH2Br, CHBr2, and CBr3) were synthesized and the conformational equilibria studied by H-1 and C-13 NMR spectroscopy at 103 K and at 295 K, respectively. The geometry of optimized structures of the axial 'equatorial chair conformers was computed at the ab initio MO and DFT levels of theory. Only one preferred conformation was obtained for the axial and the equatorial conformer as well. When comparing the conformational equilibria of the cyclohexanone esters with those of the corresponding cyclohexyl esters a certain polarity contribution of the cyclohexanone framework was revealed, which is independent of the substituent effects and increases the stability of the axial conformers by a constant amount.
To synthesize functionalized Mannich bases that can serve two different types of ortho-quinone methide (o-QM) intermediates, 2-naphthol and 6-hydroxyquinoline were reacted with salicylic aldehyde in the presence of morpholine. The Mannich bases that can form o-QM and aza-o-QM were also synthesized by mixing 2-naphthol, 2-nitrobenzaldehyde, and morpholine followed by reduction of the nitro group. The highly functionalized aminonaphthol derivatives were then tested in [4+2] cycloaddition with different cyclic imines. The reaction proved to be both regio- and diastereoselective. In all cases, only one reaction product was obtained. Detailed structural analyses of the new polyheterocycles as well as conformational studies including DFT modelling were performed. The relative stability of o-QMs/aza-o-QM were also calculated, and the regioselectivity of the reactions could be explained only when the cycloaddition started from aminodiol 4. It was summarized that starting from diaminonaphthol 25, the regioselectivity of the reaction is driven by the higher nucleophilicity of the amino group compared with the hydroxy group. 12H-benzo[a]xanthen-12-one (11), formed via o-QM formation, was isolated as a side product. The proton NMR spectrum of 11 proved to be very unique from NMR point of view. The reason for the extreme low-field position of proton H-1 could be accounted for by theoretical calculation of structure and spatial magnetic properties of the compound in combination of ring current effects of the aromatic moieties and steric compression within the heavily hindered H(1)-C(1)-C(12b)-C(12a)-C(12)=O structural fragment.
The cyclizations of tetrahydroisoquinoline 1,2-amino alcohols with phenylphosphonic dichloride, bis(2- chloroethyl)phosphoramidic dichloride, thionyl chloride and sulfuryl chloride were utilized to synthesize 1,5,6,10b- tetrahydro-1,3,2-oxazaphospholo[4,3-a]isoquinolines (2, 3), 1,5,10,10a-tetrahydro-1,3,2-oxazaphospholo[3,4- b]isoquinolines (8, 9), 1,5,6,10b-tetrahydro-1,2,3-oxathiazolo[4,3-a]isoquinolines (4-6) anda 1,5,10,10a-tetrahydro- 1,2,3-oxathiazolo[3,4-b]isoquinoline (11), which are the first representatives of these ring systems. NMR spectroscopic analysis revealed the existence of conformational equilibria that are fast on the NMR timescale. Theoretical DFT calculations pointed to the participation of generally two preferred conformers in the conformational equilibria; the positions of the equilibria were indicated by the experimental NMR spectroscopic parameters, and they are in good agreement with the theoretically calculated energy differences of the participating conformers. For two compounds, which could be not isolated (10, 12), both the preferred conformers and the stereochemistry could be concluded from the DFT calculation results.
Through the cyclization of 1-(;-hydroxynaphthyl)-1,2,3,4-tetrahydroisoquinoline and 1-(;- hydroxynaphthyl)-1,2,3,4-tetrahydroisoquinoline with formaldehyde, phosgene, p-nitrobenzaldehyde or p-chlorophenyl isothiocyanate, 8-substituted 10,11-dihydro-8H,15bH-naphth[1,2-e][1,3]oxazino[4,3-a]isoquinolines (3 and 4) and 10,11- dihydro-8H,15bH-naphth[2,1-e][1,3]oxazino[4,3-a]isoquinolines (15 and 16) were prepared. Conformational analysis of both the piperidine and the 1,3-oxazine moieties of these heterocycles by NMR spectroscopy and an accompanying theoretical study revealed that these two conformationally flexible six-membered ring moieties prefer twisted chair conformers.
A new functional group, the hydroxy group, was inserted into a Betti base by reaction with salicylaldehyde, and the naphthoxazine derivatives thus obtained were converted by ring-closure reactions with formaldehyde, acetaldehyde, propionaldehyde or phosgene to the corresponding naphth[1',2':5,6][1,3]oxazino[3,2-c][1,3]benzoxazine derivatives. Further, the conformational analysis of these polycyclic compounds by NMR spectroscopy and an accompanying molecular modelling are reported; especially, both quantitative anisotropic ring current effects of the aromatic moieties in these compounds and steric substituent effects were employed to determine the stereochemistry of the naphthoxazinobenzoxazine derivatives.