Claude Giessner-Prettre's research while affiliated with UPMC and other places

Publications (43)

Article
Intermolecular interaction energy decompositions using the Constrained Space Orbital Variation (CSOV) method are carried out at the Hartree-Fock level on the one hand and using DFT with usual GGA functionals on the other for a number of model complexes to analyze the role of electron correlation in the intermolecular stabilization energy. In additi...
Article
The condensation of n-butyllithium on o-tolualdehyde in the presence of a chiral 3-aminopyrrolidine lithium amide led to the expected alcohol with ee strongly dependent on the solvent (THF, diethylether and toluene). A NMR and theoretical study of this effect was undertaken to rationalize these results. The addition of two equivalents of methyllith...
Article
To account for the distortion of the coordination sphere that takes place in complexes containing open-shell metal cations such as Cu(II), we implemented, in sum of interactions between fragments ab initio computed (SIBFA) molecular mechanics, an additional contribution to take into account the ligand field splitting of the metal d orbitals. This t...
Article
We have, within the framework of the molecular mechanics method SIBFA, improved the formulation of the Coulomb (electrostatic) energy contribution to the intermolecular interaction energy. This was done by integrating “overlap-like” terms into two components of the multipolar development used to calculate this contribution in SIBFA. The calibration...
Article
A set of high-field, low-temperature NMR experiments has been conducted on various mixtures of Me6Li and 6LiBr in toluene. All the 6Li and 1H signals of the (MeLi)n(LiBr)4-n aggregates were unambiguously assigned via one- and two- dimensional (HOESY and COSY) experiments. The influence of the MeLi/LiBr ratio on the concentration of these different...
Article
We have previously developed a new family of organometallic complexes targeting the HIV-1 protease, an enzyme that is essential for viral maturation. Among these, two Cu2+ complexes C1 and C2 were synthesized from flexible ligands L1, N1-(4-methyl-2-pyridyl)-2,3,6-trimethoxybenzamide and L2, N2-(2-methoxybenzyl)-2-quinolinecarboxamide, respectively...
Article
Full-text available
DFT calculations using the B3LYP functional are reported for a model of the (oxy)tyrosinase active site including the two copper cations, six imidazoles and dioxygen (in the oxy form), plus either phenol (taken as a model of tyrosine, the enzyme's natural substrate) or 2-aminophenol, a very efficient inhibitor. The results obtained suggest that (i)...
Article
The (1)J and (3)J(C-Li), (1)J(N-Li), and (2)J(Li-Li) NMR coupling constants have been calculated for various homogeneous and heterogeneous aggregates of methyllithium and lithium dimethylamide at the HF and MP2 levels of calculation. Ethereal solvation has also been taken into account either through a continuum model or through the explicit introdu...
Article
The complexes between methyllithium and chiral 3-aminopyrrolidine (3-AP) lithium amides bearing a second asymmetric center on their lateral amino group were studied using multinuclear ((1)H, (6)Li, (13)C, (15)N) low-temperature NMR spectroscopies in tetrahydrofuran-d(8). The results indicate that lithium chelation forces the pyrrolidine ring of the...
Article
SIBFA parametrization is extended to the closed-shell Cu(I) cation. This parametrization introduces the cation polarization up to quadrupolar effects and the metal−ligand charge transfer. The results obtained are compared to the corresponding ab initio quantum-chemical quantities given by intermolecular interaction energy decomposition and MP2 runs...
Article
A DFT analysis of the condensation of monomeric methyllithium and lithium dimethylamide (LMA), as well as their homo and hetero dimers, on formaldehyde and acetaldehyde is reported. A stable complex, exhibiting a directional interaction between a lone pair of the oxygen on the aldehyde and a lithium, is first found. At this stage, the aldehyde carb...
Article
In this study we compare the binding energies of polycoordinated complexes of Zn2+ within cavities composed of model “hard” (H2O, OH−) or “soft” (CH3SH, CH3S−) ligands. Ab initio supermolecule computations are performed at the HF and MP2 levels using extended basis sets to determine the binding energies and their components as a function of: the nu...
Article
DFT (B3PW91) calculations have been carried out to discuss the role of the ancillary ligand X on the transformations of ethylene and vinyl ether by RuHX(PH3)2q+ (X = Cl, q = 0; X = CO, q = 1). This study follows the experimental results presented in the preceding paper. The energy of isomerization of the vinyl ether adduct into an alkoxy-stabilized...
Article
A quantitative analysis of the intermolecular forces responsible for the formation of aggregates/complexes involving organolithium compounds has been undertaken using the Restricted Variational Space (RVS) decomposition scheme of the intermolecular interaction energy. Two series of RVS computations have been carried out for every complex. The first...
Article
DFT computations on 3-N-methylamino-N-methylpyrrolidine lithium amide and its complex with methyllithium are reported. The results obtained fully support the norbornyl-like folding adopted by the pyrrolidine ring that has been inferred from experimental NMR data. The 6Li and 13C theoretical nuclear magnetic shielding constants are in reasonable agr...
Article
Molecular mechanics (SIBFA)/continuum reaction field computations have been performed on 2-furfuryl fumarates (1). The results show that the presence of a methyl or gem-dimethyl substituent on the diene−dienophile linker and also polar solvents such as DMSO stabilize the folded conformation precursor of the transition state in the intramolecular Di...
Article
A method giving simple access to various 1-(phenylthio)-4-substituted-1,3-dienes (5−10) is described. The influence of the different functionalizations introduced on the dienic systems has been tested in a set of classical [4 + 2] cycloaddition reactions. Both the endo/exo and regio selectivities have been investigated. While the endo compound is,...
Article
Semiempirical and ab initio calculations on (di)allylic alcohols indicate that the efficiency of their acid-catalyzed condensation with dienol ethers depends on their protonation-dehydration energies.
Article
The conformations of several substituted cyclohexyl esters involved in highly diastereoselective organic reactions that have been rationalized by intramolecular a-stacking were investigated by resorting to the semiempirical SIBFA procedure. Different cases, for which experimental results featuring a large set of chiral auxiliaries are available, we...
Article
The variation of the nuclear magnetic shielding constant of the different protons and carbons of trans HCO-L-Pro-NH2 with the value of the angle psi is calculated by a non-empirical method for three conformations of the proline ring. The results concerning the CH protons show that the chemical shift of the alpha, beta and gamma endo hydrogens can v...
Article
The magnetic shielding constant of the 31P nucleus of the dimethylphosphate anion is calculated by an ab initio method for different values of the torsion angles about the PO ester bond and different orientations of the methyl groups. The results obtained tend to show that both types of conformational parameters contribute to the value of σ31P. The...
Article
The magnetic shielding constants of the different atoms of formamide, hydrated formamide and N-methylformamide are calculated by anab initio method. For the protons of formamide the measured differences between their chemical shifts are correctly reproduced by theory, provided that the molecular geometry used as input is carefully chosen. The diffe...
Article
Both 1H and 13C resonances of purine have been investigated. In D2O solution, pH 7.0, 25°C, the concentration range of purine studied was from 0.001 to 1.04 M for 1H resonances and 0.02 to 1.01 M for 13C resonances. All 1H and 13C resonances have been assigned unambiguously together with the determination of all hetero 13C-1H coupling constants. Th...
Article
The variation of the chemical shift of the protons of 5′-UMP and 5′-AMP is calculated as a function of χCN, ψ and ϕ torsion angles. The shift of H8 of 5′-AMP and H6 of 5′-UMP is found to be very sensitive to the value of χCN. For the anti conformations the shift of these protons is more sensitive to the value of the rotation about CS′-05′ than abou...
Chapter
The knowledge of the conformational dependence of the chemical shifts of orotons of the nucleic acid constituents is of increasing interest for the development of the study of the conformation of polynucleotides in solution [1]–[6] (and references therein) by nuclear magnetic resonance spectroscopy since a number of experimental evidences obtained...
Article
Computations are performed on the proton chemical shifts due to hydrogen bonding between the purine and pyrimidine bases of the nucleic acids and water molecules of their first hydration shell. The water molecules should produce measurable shifts essentially for protons of the bases located close to the site of interaction. For the imino protons of...
Article
The variations of the ring current, the local diamagnetic susceptibility anisotropy and the polarization contributions to the chemical shift of the non exchangeable protons of the ribose ring of purine nucleosides are computed as a function of the torsion angle about the glycosyl bond, χCN. The results show that the ring current effect is relativel...
Article
Molecular orbital computations are performed on the different contributions to the variation of the chemical shifts of the non-exchangeable protons of the ribose ring in pyrimidine nucleosides as a function of the torsion angle XCN about the glycosyl bond. They show that the ring current effects are negligible, that the contribution of the atomic d...
Article
The variation of the proton chemical shifts due to the formation of intermolecular hydrogen bonds is computed for a number of complexes which can be formed between the bases of the nucleic acids. The shifts expected for the isolated base pairs, in particular for the G-N1 H, T(or U)-N3 H protons and the protons of the amino groups of A, G and C, whe...
Article
The spatial dependence of the ring-current magnetic anisotropy of nucleic acid bases is presented in a series of graphs in cylindrical coordinates. The curves may be used to calculate the ring-current shift at a point in a cylinder of radius 10Å extending 8 Å above and below each ring of the base. These distance effects are found to influence consi...
Article
The various approximations proposed for computing molecular potentials with CNDO wave functions are tested on the case of guanine and shown to be unable to reproduce correctly the essential fine features of theab initio potential.
Article
Molecular orbital calculations of 31P–13C and 31P–1H spin-spin coupling constants are carried out for ethyl phosphate taken as model compound for nucleotides. The calculations are in good agreement with the conformational dependence of vicinal PC and PH couplings found experimentally. It is found that the two bonds POC coupling constant is determin...
Article
Molecular orbital calculations of proton-proton coupling constants are carried out for a number of nucleosides as a function of conformational characteristics of these compounds. The study of the role of the ring puckering and of the orientation of the exocyclic CH2OH group on the vicinal coupling constants of the ribose indicates the existence, in...
Article
The chemical shifts of protons due to ring currents in neighbouring aromatic amino acids of proteins and in porphin are evaluated for several planes parallel to the conjugated rings of these compounds. The calculated values reproduce correctly the order of magnitude of the measured shifts as well as the variations of the effect with the structure o...
Article
The effect (on the energy of the different states) of including doubly excited configurations in a - plus -configuration interaction treatment, is studied within the CNDO/2 framework. For moderately large molecules the problem of the choice of the type ( or ) of configurations taken into account is examined. When possible, comparison is made with s...
Article
Im Rahmen der CNDO/ 2 Methode wird der Einfluß (auf die Energien verschiedener Zustände) des Einschlusses doppelt angeregter Konfigurationen in einer 0- und π-Konfigurationswechselwirkungs-Behandlung studiert.
Article
The association of aromatic molecules through vertical stacking produces an upfield shift of the proton resonance lines of these compounds with respect to the isolated molecules. This increase of the proton shielding is due mainly to the additional magnetic field created by the ring currents of the neighbours. This paper presents the results of cal...
Article
The CNDO/2 and INDO approximations (with their original parametrization) are utilized for the calculation of transition energies. The effect of including all ( and ) singly excited configurations is assessed in C2H4, H2CO, HCOOH and HCONH2, and the results are compared to experimental transitions and to the available non-empirical calculations. The...
Article
The approximation made in the calculation of molecular dipole moments by including only the point charges and the atomic dipoles is evaluated in different all-valence (or all)-electrons MO procedures. In the CNDO method, the use of the exact formula after retransformation of the atomic basis into Slater orbitals gives poorer values than the Pople-S...
Article
A semi-empirical self-consistent field calculation has been carried out for the purine and pyrimidine bases of the nucleic acids after an appropriate optimization of the integral values using reference compounds. Special emphasis has been laid upon results concerned with the ionization potentials, electron affinities, spectral transitions, triplet...

Citations

... Such drastic and restricted reaction conditions limit the interest for this chemistry. For our concern, we have tried to develop a methodology involving chiral ligands able to afford high induction levels in "classical" cryogenic conditions, that is to say, in one single solvent (THF, Et 2 O, toluene) and not below À78 C (Fressigné et al., unpublished results) [96][97][98][99][100][101][102][103][104][105][106][107][108][109][110][111][112][113][114][115]. For organometallic reactants, the ligand can be a σ-donor coordinating entity (chiral amines and polyamines, ethers, aminoethers, phosphines) [28][29][30][31][32][33][34][35] or a second dipolar species (chiral lithium or magnesium alkoxide, lithium or magnesium amide) [115]. ...
... The integrated SEBFA/Continuum procedure has very recently been applied to an investigation of the intramolecular Diels-Alder reaction of 2-furfuryl derivatives, as occurring in an apolar solvent, CHCl3, and a polar one, DMSO (130). In both solvents, the energy differences between the folded and extended conformations were computed for a series of 2-furfuryl fumarates, and found in agreement with experimental data. ...
... The reason for the increase in the CueCu distance from 3.32 Å to 3.5 Å and 3.72 Å during the interaction of catechol with mettyrosinase in explicit water and ethanol/water mixtures, respectively (Fig. 5), is the location of the substrate between those two coppers [54], which provides easy coordination between catechol and met-tyrosinase. In the presence of explicit water (Fig. 5a), bond formation with the distance of 1.34 Å was observed between the H atom in the hydroxyl group of the catechol (H 138 ) and the O atom in the hydroxyl group of met-tyrosinase (O 62 *). ...
... This decrease can be linked to a deformation of the tetramer, as suggested previously for (Me 6 Li) 4Àn ( 6 LiBr) n mixed aggregates. 8 To check this hypothesis, we measured lithium scalar coupling constants for mixtures, in THF-d 8 , of tetrameric alkyllithiums with different chain lengths. ...
... The first term V NN i is the neural network contribution that accounts for short-range interactions that we introduced in section II B. We model the electrostatic interaction V elec,CP ij via a Coulomb potential with fluctuating charges and the Piquemal charge penetration model [50]: ...
... Some investigations have indicated that proteasome inhibition is involved in the apoptosis of cancer cells induced by copper complexes (15,16,18,104). Copper complexes have been designed as human immunodeficiency virus type 1 (HIV-1) protease inhibitors (56,57). Thus, cellular proteins are possible targets of therapeutic copper complexes. ...
... [26] Complexes of Cu(I) with O-, S-, and N-containing ligands were compared with the SIBFA molecular mechanism versus ab initio methods. [27] Finally, the complexes of CuF with π systems were studied at CCSD(T) showing the importance of the distortion of the interacting units. [28] Finally, some studies have considered derivatives of the three noble metals. ...
... In addition to the O=C · · · NR 3 interaction discussed above it has been argued that the second point of anchorage between cinchonidine and MP results from some kind ofinteraction between the system of the quinoline ring and the system of MP [8]. This kind of interaction has been interpreted in terms of -stacking effect [22], where both systems are polarized due to the presence of the second unity, and in terms of charge transfer complex [8], where HOMO-LUMO interactions take place with charge transfer from the aromatic ring system to the conjugated double bond system of MP. -Stacking inter- actions are weak and have been observed mainly in solid state [23], although they have been supposed to originate stereoselective reaction in homogeneous liquid-phase catalytic processes [24]. Charge transfer complexes, in contrast, are usually more stable and have been observed in a set of reactions, for example leading to aromatic substitution [25]. ...
... It was shown already more than 40 years ago that purines associate much better than pyrimidines [13]; regarding nucleotides, the situation was less clear for many years [14][15][16]. Today it is generally accepted that self-association of all these species occurs via nucleobase stacking [14,17,18], that it proceeds beyond the dimer stage and that oligomers are formed [14,16,[18][19][20][21][22][23][24]. ...
... Such drastic and restricted reaction conditions limit the interest for this chemistry. For our concern, we have tried to develop a methodology involving chiral ligands able to afford high induction levels in "classical" cryogenic conditions, that is to say, in one single solvent (THF, Et 2 O, toluene) and not below À78 C (Fressigné et al., unpublished results) [96][97][98][99][100][101][102][103][104][105][106][107][108][109][110][111][112][113][114][115]. For organometallic reactants, the ligand can be a σ-donor coordinating entity (chiral amines and polyamines, ethers, aminoethers, phosphines) [28][29][30][31][32][33][34][35] or a second dipolar species (chiral lithium or magnesium alkoxide, lithium or magnesium amide) [115]. ...