Chiral Discrimination at the Solid State of Methyl 2-(Diphenylmethylsulfinyl)acetate

Renou, Ludovic; Morelli, Thomas; Coste, Servane; Petit, Marie‐Noëlle; Berton, Benjamin; Malandain, Jean‐Jacques; Coquerel, Gérard

doi:10.1021/cg070075f

Cited by 34 publications

(37 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Despite progress in the solid‐state characterisation of chiral systems in recent decades, the mechanisms of chiral selectivity in crystalline architectures are insufficiently understood. For instance, the prevalence of racemic compounds (depicted in ca.…”

Section: Introductionmentioning

confidence: 99%

Prenucleation Self‐Assembly and Chiral Discrimination Mechanisms during Solution Crystallisation of Racemic Diprophylline

Brandel

Cartigny

Coquerel

et al. 2016

Chemistry A European J

View full text Add to dashboard Cite

This version is available at https://strathprints.strath.ac.uk/58510/ Strathprints is designed to allow users to access the research output of the University of Strathclyde. Unless otherwise explicitly stated on the manuscript, Copyright © and Moral Rights for the papers on this site are retained by the individual authors and/or other copyright owners. Please check the manuscript for details of any other licences that may have been applied. You may not engage in further distribution of the material for any profitmaking activities or any commercial gain. You may freely distribute both the url (https://strathprints.strath.ac.uk/) and the content of this paper for research or private study, educational, or not-for-profit purposes without prior permission or charge.Any correspondence concerning this service should be sent to the Strathprints administrator: strathprints@strath.ac.ukThe Strathprints institutional repository (https://strathprints.strath.ac.uk) is a digital archive of University of Strathclyde research outputs. It has been developed to disseminate open access research outputs, expose data about those outputs, and enable the management and persistent access to Strathclyde's intellectual output. FULL PAPER Pre-Nucleation Self-Assembly and Chiral Discrimination Mechanisms during Solution Crystallization of Racemic DiprophyllineClément Brandel,* [a] Yohann Cartigny, [a] Gérard Coquerel, [a] Joop H. ter Horst, [b] and Samuel Petit [a] Abstract: The crystallization behavior of (RS)-Diprophylline (DPL) in two different solvents is investigated in order to assess the incidence of solvated pre-associations on nucleation, crystal growth and chiral discrimination. In the solvated state, Raman spectroscopy shows that dimeric associations similar to those depicted in the crystalline solid solution (ssRII) predominate in isopropyl alcohol (IPA), which may account for the systematic spontaneous nucleation of this crystal form from this solvent. By contrast, spontaneous nucleation in dimethylformamide yields the stable racemic compound RI, consistently with the distinct features of the Raman spectrum collected in this solvent. A crystal growth study of ssRII in IPA reveals that the crystal habitus is impacted by the solution enantiomeric excess which is explained by an increased competition between homo and heterochiral pre-associations. This is supported by a molecular modelling study on the enantiomeric selectivity of the DPL crystal lattices. The combination of assessment methods on solution chemistry, nucleation and chiral discrimination provides methodological tools from which the occurrence of solid solutions can be rationalized.

show abstract

Section: Introductionmentioning

confidence: 99%

Prenucleation Self‐Assembly and Chiral Discrimination Mechanisms during Solution Crystallisation of Racemic Diprophylline

Brandel

Cartigny

Coquerel

et al. 2016

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Owing to the chemical similarities between C-HDMAPP 2-and C-ethylPP 2- (Figure 1), one can easily envisage the replacement of C-HDMAPP 2-by C-ethylPP 2-in the crystal lattice of C-HDMAPP 3 Na 2 3 H 2 O, that is, a solid solution of substitution type. [14][15][16][17] Crystallization is an out-of-equilibrium process involving a balance between thermodynamic (stability, solubility, etc.) and kinetic (supersaturation, diffusion in solution, etc.)…”

Section: Methodsmentioning

confidence: 99%

Structural and Physicochemical Characterization of a Solid Solution Produced by Antisolvent Crystallization of a New Phosphoantigen

Descamps

Cartigny

Sanselme

et al. 2009

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

During the crystallization of the monohydrated disodium salt of hydroxydimethylallyl pyrophosphonate (C-HDMAPP 3 Na 2 3 H 2 O) induced by addition of ethanol to an aqueous solution, a synthesis impurity (C-ethylPP 2-) can be incorporated into the crystal lattice. Owing to the chemical similarity between the two anionic molecular entities, a solid solution of substitution type is produced and has been characterized by X-ray powder diffraction (XRPD), thermal analysis, and dynamic vapor sorption (DVS). Besides the incidence of the solid solution on diffraction peak positions caused by expansion/ contraction of the lattice, XRPD revealed that a distinct crystalline phase is obtained when the proportion of impurity is higher than ca. 20 wt %. The crystal structure of both C-HDMAPP 3 Na 2 3 H 2 O and C-ethylPP 3 Na 2 phases were determined, which allowed molecular modeling investigations. A mechanism has been proposed to explain the substitution at a molecular level and is consistent with the correlation observed between the actual water content (nonstoichiometry) and the proportion of impurity in the solid solution of global formula C-HDMAPP 1-x 3 C-ethylPP x 3 Na 2 3 (H 2 O) 1þ2x , (0 e x e 0.26).

show abstract

“…Conglomerates with partial solid solution are rare, but interesting from a fundamental point of view. [15][16][17][18] corresponds to that case. A synthetic precursor of the API Timolol.…”

Section: Solubility Of System Without Racemic Compoundmentioning

confidence: 97%

“…In Figure , a mix between situations depicted in Figure and in Figure is presented. Conglomerates with partial solid solution are rare, but interesting from a fundamental point of view [15–18]. corresponds to that case.…”

Section: Nonracemizable Enantiomersmentioning

confidence: 99%

Solubility of chiral species as function of the enantiomeric excess

Coquerel

2015

Journal of Pharmacy and Pharmacology

Self Cite

View full text Add to dashboard Cite

show abstract

Chiral Discrimination at the Solid State of Methyl 2-(Diphenylmethylsulfinyl)acetate

Cited by 34 publications

References 30 publications

Prenucleation Self‐Assembly and Chiral Discrimination Mechanisms during Solution Crystallisation of Racemic Diprophylline

Prenucleation Self‐Assembly and Chiral Discrimination Mechanisms during Solution Crystallisation of Racemic Diprophylline

Structural and Physicochemical Characterization of a Solid Solution Produced by Antisolvent Crystallization of a New Phosphoantigen

Solubility of chiral species as function of the enantiomeric excess

Contact Info

Product

Resources

About