scholarly journals Determination of the relative configuration of tropinone and granatanone aldols by using TBDMS ethers

2012 ◽  
Vol 8 ◽  
pp. 1877-1883 ◽  
Author(s):  
Ryszard Lazny ◽  
Aneta Nodzewska ◽  
Katarzyna Sidorowicz ◽  
Przemyslaw Kalicki
Keyword(s):  
Coupling Constants ◽  
Side Chain ◽  
X Ray Diffraction ◽  
Relative Configuration ◽  
X Ray ◽  
Vicinal Coupling Constants ◽  
Nmr Data ◽  
And Shifts ◽  
Solventless Reaction

The relative configurations oftert-butyldimethylsilyl (TBDMS) ethers of all four diastereomers of the aldols of tropinone (8-methyl-8-azabicyclo[3.2.1]octan-3-one), as well as of granatanone (9-methyl-9-azabicyclo[3.3.1]nonan-3-one), were determined from NMR data, and from the observed interconversion of the diastereomers (exo,antitoendo,synandexo,syntoendo,anti). Theexoforms invert toendoisomers in the presence of silica gel. The relative configuration of a new isomer of tropinone aldol accessible synthetically through the direct solventless reaction of tropinone and benzaldehyde in the presence of water was determined asexo,synby comparison of NMR data of the aldol isomers, in particular vicinal coupling constants and shifts corresponding to the side-chain CH group, with data of related TBDMS derivatives and confirmed by single-crystal X-ray diffraction.

scholarly journals NMR and X-ray studies of apetalic acid isolated from Calophyllum brasiliense and of its chiral amides

2021 ◽  
Author(s):  
Marie-Rose Van Calsteren ◽  
Ricardo Reyes-Chilpa ◽  
Chistopher K Jankowski ◽  
Fleur Gagnon ◽  
Simón Hernández-Ortega ◽  
...  
Keyword(s):  
Antimycobacterial Activity ◽  
Side Chain ◽  
Carboxyl Group ◽  
X Ray Diffraction ◽  
Rain Forests ◽  
X Ray ◽  
X Ray Crystallography ◽  
Calophyllum Brasiliense ◽  
Derivatives Of

The tropical tree Calophyllum brasiliense (Clusiaceae) grows in the rain forests from Brazil to Mexico. Its leaves, as well as those of other Calophyllum species, are rich sources of chromanone acids, such as apetalic acid, isoapetalic acid, and their derivatives. Apetalic acid has shown significant antimycobacterial activity. The biological activity of apetalic acid has been related to the configuration of three asymmetric centers and the stereochemistry of the molecule; however, the C-19 configuration in the acidic side chain has not been fully resolved. For this reason, the unequivocal determination of the absolute configuration by means of X-ray crystallography in a sample of unique homogeneous apetalic acid stereoisomer was the most important point to start this study. We prepared some chiral amides using the carboxyl group. We determined the C-19 stereochemistry of apetalic acid, and its specific chiral derivatives, using NMR, X-ray diffraction methods, and molecular mechanics. Finally, we observed that steric hindrance in the side chain of apetalic acid leads to restriction of rotation around the pivotal link C-10 and C-19 establishing chiral centers at C2(R), C3(S), and C19(R). We were able to separate derivatives of these two high-rotatory-barrier conformers of apetalic acid by forming diastereoisomeric amides with phenylglycine methyl ester having a chiral center at C-2’. Our results allowed the conclusion of the existence of atropisomerism in the apetalic acid molecule.

NMR Spectroscopy of Tetra(propyn- 1-yl)silane in the Solid State and in Solution

2003 ◽  
Vol 58 (8) ◽  
pp. 809-812 ◽  
Author(s):  
Bernd Wrackmeyer ◽  
Oleg L. Tok ◽  
Amin Badshah
Keyword(s):  
Solid State ◽  
Bulk Material ◽  
Point Group ◽  
Coupling Constants ◽  
Data Set ◽  
Tin Compounds ◽  
X Ray ◽  
Nmr Data ◽  
Solid State Structures

The crystal structure of tetra(propyn-1-yl)silane, Si(C≡CMe)4 1, has revealed a completely asymmetric molecule (point group C1). Since this finding concerns a single crystal, the bulk material of 1 was studied by solid-state 29Si and 13C MAS NMR. This confirmed the result of the X-ray analysis, and by comparison with previous NMR measurements of the tin analogue 1(Sn) it is concluded that 1 and 1(Sn) must have very similar solid-state structures which are in contrast to those known for other tetra(alkyn-1-yl)silicon and -tin compounds. The NMR data set of 1 in solution was completed by determination of the magnitude of coupling constants 1J(13C,13C).

Diminished electron density in the Vaska-type rhodium(I) complextrans-[Rh(NCBH3)(CO)(PPh3)2]

2016 ◽  
Vol 72 (7) ◽  
pp. 514-517
Author(s):  
M. R. Galding ◽  
A. V. Virovets ◽  
I. V. Kazakov ◽  
M. Scheer ◽  
S. N. Smirnov ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Nmr Spectroscopy ◽  
Electron Density ◽  
Coupling Constants ◽  
X Ray Diffraction ◽  
Metathesis Reaction ◽  
Carbonyl Carbon ◽  
Carbonyl Ligand ◽  
X Ray ◽  
Nmr Data

Vaska-type complexes,i.e. trans-[RhX(CO)(PPh3)2] (Xis a halogen or pseudohalogen), undergo a range of reactions and exhibit considerable catalytic activity. The electron density on the RhIatom in these complexes plays an important role in their reactivity. Many cyanotrihydridoborate (BH3CN−) complexes of Group 6–8 transition metals have been synthesized and structurally characterized, an exception being the rhodium(I) complex. Carbonyl(cyanotrihydridoborato-κN)bis(triphenylphosphine-κP)rhodium(I), [Rh(NCBH3)(CO)(C18H15P)2], was prepared by the metathesis reaction of sodium cyanotrihydridoborate withtrans-[RhCl(CO)(PPh3)2], and was characterized by single-crystal X-ray diffraction analysis and IR,1H,13C and11B NMR spectroscopy. The X-ray diffraction data indicate that the cyanotrihydridoborate ligand coordinates to the RhIatom through the N atom in atransposition with respect to the carbonyl ligand; this was also confirmed by the IR and NMR data. The carbonyl stretching frequency ν(CO) and the carbonyl carbon1JC–Rhand1JC–Pcoupling constants of the Cipsoatoms of the triphenylphosphine groups reflect the diminished electron density on the central RhIatom compared to the parenttrans-[RhCl(CO)(PPh3)2] complex.

Darstellung und Kristallstruktur von endo-2-Dimethylphospliono-exo-2-liydroxy-(—)-camphan zur Bestimmung von 3J(CCCP)-Vicinalkopplungen / Synthesis and Crystal Structure of endo-2-Dimethylphosphono-exo-2-hydroxy-(—)-camphane for the Determination of 3J(CCCP) Vicinal Coupling Constants

1979 ◽  
Vol 34 (11) ◽  
pp. 1547-1551 ◽  
Author(s):  
Gunadi Adiwidjaja ◽  
Bernd Meyer ◽  
Joachim Thiem
Keyword(s):  
Coupling Constants ◽  
Coupling Constant ◽  
Nmr Spectrum ◽  
Synthesis And Crystal Structure ◽  
X Ray ◽  
Vicinal Coupling Constants ◽  
Complete Assignment ◽  
Hydroxy Phosphonates ◽  
C Nmr

endo-2-Dimethylphosphono-exo-2-hydroxy-(-)-camphane (2) is prepared and the structure confirmed by X-ray data. The complete assignment of the 13C NMR spectrum of this conformationally rigid derivative leads to a Karplus-type function for the vicinal 3J(CCCP) coupling constant in α-hydroxy phosphonates.

scholarly journals Absolute configuration of naturally occurring glabridin

2013 ◽  
Vol 69 (11) ◽  
pp. 1212-1216 ◽  
Author(s):  
Charlotte Simmler ◽  
Frank R. Fronczek ◽  
Guido F. Pauli ◽  
Bernard D. Santarsiero
Keyword(s):  
Absolute Configuration ◽  
X Ray Diffraction ◽  
Data Set ◽  
X Ray ◽  
Naturally Occurring ◽  
Nmr Data ◽  
Stereochemical Analysis ◽  
Medium Pressure Liquid Chromatography ◽  
Species Specific

The title compound {systematic name: 4-[(3R)-8,8-dimethyl-3,4-dihydro-2H-pyrano[2,3-f]chromen-3-yl]benzene-1,3-diol, commonly named glabridin}, C20H20O4, is a species-specific biomarker from the rootsGlycyrrhiza glabraL. (European licorice, Fabaceae). In the present study, this prenylated isoflavan has been purified from an enriched CHCl3fraction of the extract of the root, using three steps of medium-pressure liquid chromatography (MPLC) by employing HW-40F, Sephadex LH-20 and LiChroCN as adsorbents. Pure glabridin was crystallized from an MeOH–H2O mixture (95:5 v/v) to yield colorless crystals containing one molecule per asymmetric unit (Z′ = 1) in the space groupP212121. Although the crystal structure has been reported before, the determination of the absolute configuration remained uncertain. Stereochemical analysis, including circular dichroism, NMR data and an X-ray diffraction data set with Bijvoet differences, confirms that glabridin, purified from its natural source, is found only in a C3Rconfiguration. These results can therefore be used as a reference for the assignment of the configuration and enantiopurity of any isolated or synthetic glabridin sample.

Total assignment of the 13C spectrum of taraxasteryl acetate by 13C–13C connectivity experiments and determination of the stereochemistry of taraxasterol by X-ray diffraction

1985 ◽  
Vol 63 (5) ◽  
pp. 1048-1054 ◽  
Author(s):  
William F. Reynolds ◽  
Jeffery F. Sawyer ◽  
Raúl G. Enriquez ◽  
Laura I. Escobar ◽  
Marco A. Chavez ◽  
...  
Keyword(s):  
Coupling Constants ◽  
Boat Conformation ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Chair Form ◽  
X Ray ◽  
Ethanol Solvate ◽  
Similar Conformation ◽  
Spectral Assignment

13C–13C connectivity (INADEQUATE) experiments have been used to reassign the 13C spectrum of taraxasteryl acetate. This shows that there were ten errors in an earlier 13C spectral assignment for this compound. An X-ray diffraction investigation of taraxasterol shows that ring E adopts a slightly distorted boat conformation. It is suggested that severe steric interactions in the chair form force it to adopt this unusual conformation. On the basis of the 1H–1H coupling constants, it is concluded that taraxasteryl acetate adopts a very similar conformation in solution. Crystals of taraxasterol–ethanol solvate are orthorhombic, space group P21,21,21, wih a = 7.447(1) Å, b = 17.637(2) Å, c = 22.269(4) Å, U = 2925 Å3, and Dcalc = 1.07 g cm−3 for Z = 4.

Sesquiterpenic lactones of the Inula caspica BLUME species

1990 ◽  
Vol 55 (6) ◽  
pp. 1568-1579 ◽  
Author(s):  
Sergazy M. Adekenov ◽  
Miloš Buděšínský ◽  
Metram A. Abdikalikov ◽  
Coblandy M. Turdybekov ◽  
David Šaman ◽  
...  
Keyword(s):  
Absolute Configuration ◽  
Cd Spectroscopy ◽  
X Ray Diffraction ◽  
Relative Configuration ◽  
X Ray

From Inula caspica BLUME (Compositae) were isolated 3β-hydroxy-2α-senecioyloxyisoalantolactone (I), whose structure was confirmed by X-ray diffraction and completed by determination of its absolute configuration, and britannin (II) whose relative configuration was determined by X-ray diffraction and absolute configuration by CD spectroscopy.

Sem and X-Ray Analysis of Renal and Biliary Calculi

1976 ◽  
Vol 34 ◽  
pp. 306-307
Author(s):  
R. J. Narconis ◽  
G. L. Johnson
Keyword(s):  
Chemical Constituents ◽  
Natural State ◽  
X Ray Diffraction ◽  
Chemical Methods ◽  
X Ray ◽  
Additional Dimension ◽  
Biliary Calculi ◽  
Calculus Formation ◽  
Scanning Electron

Analysis of the constituents of renal and biliary calculi may be of help in the management of patients with calculous disease. Several methods of analysis are available for identifying these constituents. Most common are chemical methods, optical crystallography, x-ray diffraction, and infrared spectroscopy. The application of a SEM with x-ray analysis capabilities should be considered as an additional alternative.A scanning electron microscope equipped with an x-ray “mapping” attachment offers an additional dimension in its ability to locate elemental constituents geographically, and thus, provide a clue in determination of possible metabolic etiology in calculus formation. The ability of this method to give an undisturbed view of adjacent layers of elements in their natural state is of advantage in determining the sequence of formation of subsequent layers of chemical constituents.

New Coordination Compounds of Fe(III) with Organic Ligands

2009 ◽  
Vol 59 (12) ◽  
Author(s):  
Mihaela Flondor ◽  
Ioan Rosca ◽  
Doina Sibiescu ◽  
Mihaela-Aurelia Vizitiu ◽  
Daniel-Mircea Sutiman ◽  
...  
Keyword(s):  
Chemical Analysis ◽  
Complex Compounds ◽  
Organic Ligands ◽  
X Ray Diffraction ◽  
X Ray ◽  
Elemental Chemical Analysis ◽  
Structural Formulae ◽  
Paramagnetic Properties

In this paper the synthesis and the study of some complex compounds of Fe(III) with ligands derived from: 2-(4-chloro-phenylsulfanyl)-1-(2-hydroxy-3,5-diiodo-phenyl)-ethanone (HL1), 1-(3,5-dibromo-2-hydroxy-phenyl)-2-phenylsulfanyl-ethanone(HL2), and 2-(4-chloro-phenylsulfanyl)-1-(3,5-dibromo-2-hydroxy-phenyl)-ethanone (HL3) is presented. The characterization of these complexes is based on method as: the elemental chemical analysis, IR and ESR spectroscopy, M�ssbauer, the thermogravimetric analysis and X-ray diffraction. Study of the IR and chemical analysis has evidenced that the precipitates form are a complexes and the combination ratio of M:L is 1:2. The central atoms of Fe(III) presented paramagnetic properties and a octaedric hybridization. Starting from this precipitation reactions, a method for the gravimetric determination of Fe(III) with this organic ligands has been possible. Based on the experimental data on literature indications, the structural formulae of the complex compounds are assigned.

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