Ring Conformation (ring + conformation)

Distribution by Scientific Domains

Selected Abstracts

Structure,Catalytic Activity Relationship in Bridging Silacycloalkyl Ring Conformations of Constrained Geometry Titanium Complexes

Eugene Kang
Abstract A series of cyclic silylene-bridged (amidocyclopentadienyl)dichlorotitanium(IV) complexes [TiCl2{,5 -1-(CySitBuN- ,N)-2,3,4,5-R4 -C5}] was prepared, where CySi = silacyclobutyl (a), silacyclopentenyl (b), silacyclopentyl (c), and silacyclohexyl (d); R = H (4), Me (5). The starting silane, dichlorosilacycloalkane CySiCl2 (1), was treated with NaCp (LiCp*), followed by LiNHtBu to yield the cyclic silylene-bridged ligands (R4C5)CySi(NHtBu) [R = H (2); Me (3)]. Subsequent deprotonation with n -butyllithium, followed by transmetalation with TiCl4 yielded the desired constrained geometry complexes (CGCs) (CpCySiNtBu)TiCl2 (4) and (Cp*CySiNtBu)TiCl2 (5). The structures of the resulting cyclopentadienyl- (4b and 4c) and tetramethylcyclopentadienyl(silacycloalkyl)amidotitanium(IV) dichloride (5a, 5c, and 5d) species were studied by using X-ray crystallography to obtain geometrical information on cyclic silylene-modified CGCs. The ethylene polymerization by the cyclic silylene-bridged CGCs 4 and 5 was examined to verify the structure,catalytic activity relationship derived from variation of the size of a cyclic silylene ring. Indeed, the size of the cyclic silylene ring at the 1,1,-position of 4 and 5 affected the catalytic activities through the ethylene polymerization. Systematic increase in the catalytic activities was observed as the cyclic silylene-bridging unit was expanded from a four- to six-membered ring. In the present study, we found that CGCs of TiIV with a six-membered silylene-bridged ligand (5d) produced active catalytic species for the formation of polyethylene with Mw = 42.7,×,10,4 g,mol,1 and Mw/Mn = 2.1 with excellent catalytic activities (20.9 kg,polymer per mmol of Ti). When titanium(IV) dimethyl complex (6d) was applied in continuous polymerization process, impressive high catalytic activity on copolymerization with 1-octene was observed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

Ring conformations and intermolecular interactions in two fused dibenzoazocines

Andrés F. Yepes
5-Acetyl-2-chloro-8,11-dimethyl-5,6,11,12-tetrahydrodibenzo[b,f]azocine, C19H20ClNO, (I), crystallizes as a single fully ordered isomer, but 14-acetyl-8,11-dimethyl-7,8,13,14-tetrahydrobenzo[f]naphtho[1,2- b]azocine,14-acetyl-8,9-dimethyl-7,8,13,14-tetrahydrobenzo[f]naphtho[1,2- b]azocine (74/26), C23H23NO, (II), exhibits threefold whole-molecule disorder involving both configurational and structural isomers. In (I) and in the predominant form of (II), the azocine rings adopt very similar conformations, forming boat-shaped rings having approximate twofold rotational symmetry. There are no direction-specific intermolecular interactions in the crystal structure of (I), but the molecules of (II) are weakly linked into chains by an aromatic ,,, stacking interaction. The compounds were made under green conditions using an acid-catalysed cyclization process having very high atom utilization. [source]

Mycobacterium tuberculosis Thymidine Monophosphate Kinase Inhibitors: Biological Evaluation and Conformational Analysis of 2,- and 3,-Modified Thymidine Analogues

Philippe Van Rompaey
Abstract Mycobacterium tuberculosis thymidine monophosphate kinase (TMPKmt) has recently been introduced as a potential target for the structure-based design of anti-tuberculosis drugs. Based on the TMPKmt X-ray structure and previous S.A.R. studies, we synthesised the nucleoside analogues 3a,b, 6a,b, 7a,b, and 8a,b, modified in 2,- and 3,-position of the ribofuranose ring moiety. To our surprise, these analogues showed only moderate binding affinity (i.e. Ki between 118 and 1260 ,M). This prompted us to investigate the conformational features of these nucleosides. We concluded that compounds of this series, especially 8a,b, are strongly biased towards the "Northern" furanose ring conformation, whereas X-ray crystallography reveals a preference of TMPKmt for the opposite "Southern" conformers. This paper covers the synthesis, biological evaluation and conformational features (i.e. preferred ring puckering) of the 2,- and 3,-modified dT analogues. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

Gas-phase acidity of proline from density functional computations

T. Marino
Abstract Density functional computations using the B3LYP hybrid potential coupled with the extended 6-311++G** basis set were performed to evaluate gas-phase acidity of proline ,-amino acid. The computed value of gas-phase acidity is 1403.8 kJ/mol in good agreement with the experimental counterpart (1395.0±13.8 kJ/mol) and is referred to the deprotonated species deriving from the first relative minimum of neutral proline characterized by the exo ring conformation with the carboxyl group in cis position. The most stable neutral proline isomer gives rise to a species for which the gas-phase acidity value (1384.5 kJ/mol) is also close to the experimental data. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem 84: 264,268, 2001 [source]

A new GROMOS force field for hexopyranose-based carbohydrates

Roberto D. Lins
Abstract A new parameter set (referred to as 45A4) is developed for the explicit-solvent simulation of hexopyranose-based carbohydrates. This set is compatible with the most recent version of the GROMOS force field for proteins, nucleic acids, and lipids, and the SPC water model. The parametrization procedure relies on: (1) reassigning the atomic partial charges based on a fit to the quantum-mechanical electrostatic potential around a trisaccharide; (2) refining the torsional potential parameters associated with the rotations of the hydroxymethyl, hydroxyl, and anomeric alkoxy groups by fitting to corresponding quantum-mechanical profiles for hexopyranosides; (3) adapting the torsional potential parameters determining the ring conformation so as to stabilize the (experimentally predominant) 4C1 chair conformation. The other (van der Waals and nontorsional covalent) parameters and the rules for third and excluded neighbors are taken directly from the most recent version of the GROMOS force field (except for one additional exclusion). The new set is general enough to define parameters for any (unbranched) hexopyranose-based mono-, di-, oligo- or polysaccharide. In the present article, this force field is validated for a limited set of monosaccharides (,- and ,-D-glucose, ,- and ,-D-galactose) and disaccharides (trehalose, maltose, and cellobiose) in solution, by comparing the results of simulations to available experimental data. More extensive validation will be the scope of a forthcoming article. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 1400,1412, 2005 [source]

Proton affinity ladder for uridine and analogs: influence of the hydroxyl group on the sugar ring conformation

S. Mezzache
Abstract A ladder of relative proton affinities (PA) for a series of modified uridines (e.g. araU, ddU, 5BrU, 5BrdU and 5IU) was established from competitive dissociations of proton-bound heterodimers using Cooks and co-workers' kinetic method. The studied heterodimers are constituted of a modified nucleoside and either an amino acid or a nucleoside with known PA value. These non-covalent heterodimers were prepared under electrospray conditions to be selected and dissociated into the ion-trap analyzer. These results allowed our PA ladder of uridine and deoxyuridine analogs substituted at the C-5 position in the uracil ring to be extended. From this scale, it was showed that the substitution of hydrogen atom at the C-2, position in the sugar ring by a hydroxyl group involves a decrease of about 7 kJ mol,1. The experimental values for U, 5MeU, dU, 5MedU, ddU and araU are consistent with those obtained by DFT calculations (B3P86/6,31+G*//B3LYP/6,31G*). Several neutral and protonated conformations of these compounds were considered, in particular the ring conformation of furanose and the orientation of the base with respect to the sugar ring. These calculated results showed the influence of sugar substituent on the conformation of the neutral form of theses nucleosides. However, the most stable protonated structure is the same for all the studied nucleosides except for araU, where the position of the anti 2,-OH group imposes a specific conformation. Copyright © 2005 John Wiley & Sons, Ltd. [source]

Density functional and vibrational spectroscopic analysis of ,-carotene

S. Schlücker
Abstract We report a computational study on the structural, energetic and vibrational spectroscopic characteristics of ,-carotene employing density functional theory (DFT). The optimized geometry and the complete vibrational spectrum calculated at the BPW91/6,31G* level, including infrared (IR) intensities and Raman activities, are presented. The centrosymmetric structure of ,-carotene is verified both theoretically and experimentally, by identifying a stable calculated structure with Ci symmetry and the mutually exclusive occurrence of bands in the experimental Fourier transform IR and Raman spectrum, respectively. The calculated vibrational spectra reflect the major characteristic features observed experimentally. Differences in the calculated IR intensities and Raman activities for a few dominant modes of two ,-carotene configuration isomers, the all- trans and the natural abundant (C6,C7) s- cis form, are explained qualitatively by the corresponding eigenvectors. At the level of theory employed, s- cis -,-carotene was found to be 8.8 kJ mol,1 more stable than the all- trans form. Calculations on ,-carotene model systems were performed to separate electronic from steric contributions. The higher stability of s- cis -,-carotene is explained by an energetically favored ,-ionone ring conformation, compensating for its shorter conjugation length in comparison with the all- trans form. Copyright © 2003 John Wiley & Sons, Ltd. [source]

A 13C solid-state NMR analysis of steroid compounds

Jen-Hsien Yang
Abstract 13C CP/MAS solid-state NMR spectroscopy has been utilized to analyze six steroid compounds, namely testosterone (Tes), hydrocortisone (Cor), trans -dehydroandrosterone (Adr), prednisolone (Prd), prednisone (Pre) and estradiol (Est). Among them, Tes displays a doublet pattern for all residues, whereas Prd, Pre and Est, exhibit exclusively singlets. For Cor and Adr, the 13C spectra contain both doublet and singlet patterns. The 13C doublet signal, with splittings of 0.2,1.5 ppm, are ascribed to local differences in the ring conformations associated with polymorphism. We have assigned all of the 13C resonances to the different residues in these steroid compounds on the basis of solution NMR data. The C-7, C-8, C-10, C-15 and C-16 residues of Tes, Cor and Adr consistently give rise to singlets or doublets with splittings of less than 0.5 ppm, indicating similar local conformations. Accompanying hydration and dehydration processes, a reversible phase transformation between ,- and ,-crystal forms has been observed in Tes, corresponding to singlet and doublet13C patterns, respectively. To further characterize the ring conformations in the ,-form, we have successfully extracted chemical shift tensor elements for the 13C doublets. It is demonstrated that 13C solid-state NMR spectroscopy provides a reliable and sensitive means of characterizing polymorphism in steroids. Copyright © 2008 John Wiley & Sons, Ltd. [source]

Structures of furanosides: geometrical analysis of low-temperature X-ray and neutron crystal ­structures of five crystalline methyl ­pentofuranosides

Artem Evdokimov
Crystal structures of all five crystalline methyl d -pentofuranosides, methyl ,- d -arabinofuranoside (1), methyl ,- d -arabinofuranoside (2), methyl ,- d -lyxofuranoside (3), methyl ,- d -ribofuranoside (4) and methyl ,- d -xylofuranoside (5) have been determined by means of cryogenic X-ray and neutron crystallography. The neutron diffraction experiments provide accurate, unbiased H-atom positions which are especially important because of the critical role of hydrogen bonding in these systems. This paper summarizes the geometrical and conformational parameters of the structures of all five crystalline methyl pentofuranosides, several of them reported here for the first time. The methyl pentofuranoside structures are compared with the structures of the five crystalline methyl hexopyranosides for which accurate X-ray and neutron structures have been determined. Unlike the methyl hexopyranosides, which crystallize exclusively in the C1 chair conformation, the five crystalline methyl pentofuranosides represent a very wide range of ring conformations. [source]