51 research outputs found
Joint ITC and DFT Study of the Affinity of Some Lewis Bases to HIFP in Solution
HFIP, i.e. 1,1,1,3,3,3-hexafluoropropan-2-ol, was found to be an exceptional medium,[1] either as solvent or co-solvent, that allows many reactions to occur.[2-5] However, the exact role and mode of action of HFIP in various chemical transformations still remains elusive. Despite many reports dealing with water/HFIP complexes, little has been published on other molecular complexes of HFIP as well as on thermochemistry of the formation of such complexes.[6]
Within this study the affinity of a series of eight different Lewis bases (3 sulfoxides, 3 Nsp2 pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) to HFIP (as Lewis acid) is investigated
experimentally by Isothermal Titration Calorimetry (ITC) and theoretically using static DFT-D calculations. Measured ITC association enthalpy values ÎHaITC spanned -9.3 kcal/mol - -14
kcal/mol. Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems - ÎHa values ranging -8.5 â -12.7 kcal/mol. In general, most of interaction energy is due to the hydrogen bonding and not due to formation of significantly strong halogen bonds. An additional set of calculations combining implicit and explicit solvation by chlorobenzene of the reactants, pointed out the relatively low interference of the solvent with the HFIPbase complexation, which main effect is to slightly enhance the Gibbs energy of the HFIP-Lewis base association. It is speculated that the interactions of bulk HFIP with Lewis bases therefore may significantly intervene in catalytic processes not only via the dynamic miscrostructuration of the medium but also more explicitly by affecting bondsâ polarization at the Lewis bases
Supplementary data for the article: MilovanoviÄ, M. R.; Dherbassy, Q.; WencelâDelord, J.; Colobert, F.; ZariÄ, S. D.; ÄukiÄ, J.-P. The Affinity of Some Lewis Bases for Hexafluoroisopropanol as a Reference Lewis Acid: An ITC/DFT Study. ChemPhysChem 2020, 21 (18), 2136â2142. https://doi.org/10.1002/cphc.202000560.
Supplementary material for: [https://doi.org/10.1002/cphc.202000560]Related to published version: [https://cherry.chem.bg.ac.rs/handle/123456789/4337]Related to accepted version: [https://cherry.chem.bg.ac.rs/handle/123456789/4339
Dissymmetrically Substituted Diphosphines with Two Atropisomeric Axes and Their Application in Asymmetric Hydrogenation of Imines
Stereoselective Metal-Catalyzed CâC Bond Coupling Reactions by Stereoconvergence, Dynamic Kinetic Asymmetric Transformation, or Dynamic Kinetic Resolution
International audienc
SynthÚse des ligands chiraux DiPPAM et évaluation de leurs complexes métalliques pour la formation de liaison C-C
De nouveaux ligands chiraux tridentates P,N,O, les sels de phosphinoazométhinylate (les DiPPAMs), ont été développés. Une chimiothÚque de 8 ligands a été synthétisée en une seule étape, sans aucune purification et avec des rendements quantitatifs. Des applications des DiPPAMs pour les réactions de couplages C-C ont été développées. De hautes énantiosélectivités ont été obtenues pour des additions conjuguées-1,4 et -1,6 catalysées au cuivre. Par ailleurs, un complexe Pd/DiPPAM a été isolé et évalué pour la réaction de Tsuji-Trostsur des substrats symétriques et dissymétriques. Des bons ee ont été obtenus dans le premier cas et un dédoublement cinétique a été observé lors d applications sur des substrats portant deux substituants différents sur les carbones allyliques terminaux.New chiral P,N,O ligands, the phosphinoazomethinaylate salts (DiPPAMs) were developed. A library of 8 DiPPAM ligands was prepared in one-step synthesis, without any purification and in quantitative yields. Applications of DiPPAMs for C-C bond formations were investigated. High enantioselectivities were obtained for 1,4- and 1,6-copper catalyzed conjugate additions. Furthermore, an original Pd/DiPPAM complex was synthesized and evaluated for Tsuji-Trost reaction on symmetric and dissymmetric substrates. Good ee s were obtained in the first case and a kinetic resolution was observed in the case of substrates bearing two different substituents on the external allylic carbones.RENNES1-BU Sciences Philo (352382102) / SudocSudocFranceF
Highlights from the 54th EUCHEM BĂŒrgenstock Conference on Stereochemistry, Brunnen, Switzerland, May 2019
International audienc
Diastereoselective Substrate-Controlled Transition-Metal-Catalyzed CâH Activation: An Old Solution to a Modern Synthetic Challenge
CâH bond activation enables the rapid construction and late-stage diversification of functional molecules
International audienc
Diastereoselective Substrate-Controlled Transition-Metal-Catalyzed CâH Activation: An Old Solution to a Modern Synthetic Challenge
International audienc
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