Insights into halogen bond-driven enantioseparations

Peluso, Paola; Mamane, Victor; Aubert, Emmanuel; Dessì, Alessandro; Dallocchio, Roberto; Dore, Antonio; Pale, Patrick; Cossu, Sergio

doi:10.1016/j.chroma.2016.06.007

Cited by 41 publications

(57 citation statements)

References 58 publications

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“…Therefore, a mixed enantioseparation mechanism controlled by halogen‐dependent interactions as well as analyte steric fit seemed to be active on the amylose‐based CSP, with chromatographic outcomes depending on both volume and XBD ability of the analyte. Differently, on CDMPC the σ‐hole on halogens were shown to control enantioseparation exclusively . The occurrence of two different mechanisms as the polysaccharide backbone changes was supported by the following remarks: (i) ΔΔ S values determined for 1–3 on CDMPC (–5.36 ( 1 ) > –19.78 ( 2 ) > –27.47 ( 3 ) J/(mol K)) ranged following an opposite order compared to ADMPC (–5.95 ( 1 ) < –2.38 ( 2 ) < –0.55 ( 3 ) J/(mol K)); (ii) by enhancing MP polarity with mix B on CDMPC retention increased (0.51 ≤ k 1 ≤ 8.11), whereas selectivity decreased (1.00 ≤ α ≤ 1.67), keeping again the order Cl < Br < I.…”

Section: Resultsmentioning

confidence: 89%

“…Indeed, MeOH is able to destabilize XBs by penetrating inside the chiral cavity and forming HBs with the carbonyl oxygens better than IPA due to its stereoelectronic properties (SI). Meanwhile, MeOH favors hydrophobic contacts .…”

Section: Resultsmentioning

confidence: 99%

“…Therefore, a mixed enantioseparation mechanism controlled by halogen-dependent interactions as well as analyte steric fit seemed to be active on the amylose-based CSP, with chromatographic outcomes depending on both volume and XBD ability of the analyte. Differently, on CDMPC the σ-hole on halogens were shown to control enantioseparation exclusively [21]. The occurrence of two different mechanisms as the polysaccharide backbone changes was supported by the following remarks: order Cl < Br < I.…”

Section: Hplc Halogen Bond-driven Enantioseparations: Cellulose Versumentioning

confidence: 87%

“…Differently, for the 3,3 ′ -diiodo 7 α decreased as compared to 5. In this case, the comparison of the ΔΔS values derived from the van't Hoff plots and associated with the enantiodiscriminations ([J/(mol⋅K], 5: -10.92; 7: -0.71) proved that entropic factors, caused by the larger 2,2 ′ -bromines close to the 3,3 ′iodines, exert a detrimental effect on selectivity [21]. Differently, on ADMPC-mix A, iodine at position 5,5 ′ seemed to be detrimental for enantioseparation.…”

Section: Hplc Halogen Bond-driven Enantioseparations: Cellulose Versumentioning

confidence: 89%

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Polysaccharide‐based chiral stationary phases as halogen bond acceptors: A novel strategy for detection of stereoselective σ‐hole bonds in solution

Peluso

Mamane

Dallocchio

et al. 2018

J of Separation Science

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In the last few years, halogen bonds have been exploited in a variety of research areas both in the solid state and in solution. Nevertheless, several factors make formation and detection of halogen bonds in solution challenging. Moreover, to date, few chiral molecules containing electrophilic halogens as recognition sites have been reported. Recently, we described the first series of halogen-bond-driven enantioseparations performed on cellulose tris(3,5-dimethylphenylcarbamate) by high-performance liquid chromatography. Herein the performances of amylose tris(3,5-dimethylphenylcarbamate) as halogen bond acceptor were also investigated and compared with respect to cellulose tris(3,5-dimethylphenylcarbamate). With the aim to explore the effect of polysaccharide backbone on the enantioseparations, the thermodynamic parameters governing the halogen-dependent enantioseparations on both cellulose and amylose polymers were determined by a study at variable temperature and compared. Molecular dynamics were performed to model the halogen bond in polysaccharide-analyte complexes. Chiral halogenated 4,4'-bipyridines were used as test compounds (halogen bond donors). On this basis, a practical method for detection of stereoselective halogen bonds in solution was developed, which is based on the unprecedented use of high-performance liquid chromatography as technical tool with polysaccharide polymers as molecular probes (halogen bond acceptors). The analytical strategy showed higher sensitivity for the detection of weak halogen bonds.

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Section: Resultsmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Section: Hplc Halogen Bond-driven Enantioseparations: Cellulose Versumentioning

confidence: 87%

Section: Hplc Halogen Bond-driven Enantioseparations: Cellulose Versumentioning

confidence: 89%

See 2 more Smart Citations

Polysaccharide‐based chiral stationary phases as halogen bond acceptors: A novel strategy for detection of stereoselective σ‐hole bonds in solution

Peluso

Mamane

Dallocchio

et al. 2018

J of Separation Science

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“…Despite the huge number of papers published in these fields, the understanding of the stereoselective interaction process is still an open issue. Indeed, multiple noncovalent interactions along with other effects can promote retention and enantioseparation : i) strong long‐range interactions involved in the primary non‐stereoselective binding, ii) non‐stereoselective adsorption of analytes to the solid support, iii) short‐range directional noncovalent interactions , underlying the stereoselective binding, which are governed by complementarity of functional groups, like hydrogen bond (HB), π‐π interactions, dipole‐dipole stacking and the emergent halogen bond (XB) , iv) steric factors deriving from the spatial arrangement of selector binding site, v) conformational changes of selector induced by selectand binding, vi) hydrophobic effects, and vii) solvation effects. This high level of complexity concerns in particular high‐molecular weight selectors such as polysaccharide derivatives.…”

Section: Introductionmentioning

confidence: 99%

Recent studies of docking and molecular dynamics simulation for liquid‐phase enantioseparations

et al. 2019

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Liquid‐phase enantioseparations have been fruitfully applied in several fields of science. Various applications along with technical and theoretical advancements contributed to increase significantly the knowledge in this area. Nowadays, chromatographic techniques, in particular HPLC on chiral stationary phase, are considered as mature technologies. In the last thirty years, CE has been also recognized as one of the most versatile technique for analytical scale separation of enantiomers. Despite the huge number of papers published in these fields, understanding mechanistic details of the stereoselective interaction between selector and selectand is still an open issue, in particular for high‐molecular weight chiral selectors like polysaccharide derivatives. With the ever growing improvement of computer facilities, hardware and software, computational techniques have become a basic tool in enantioseparation science. In this field, molecular docking and dynamics simulations proved to be extremely adaptable to model and visualize at molecular level the spatial proximity of interacting molecules in order to predict retention, selectivity, enantiomer elution order, and profile noncovalent interaction patterns underlying the recognition process. On this basis, topics and trends in using docking and molecular dynamics as theoretical complement of experimental LC and CE chiral separations are described herein. The basic concepts of these computational strategies and seminal studies performed over time are presented, with a specific focus on literature published between 2015 and November 2018. A systematic compilation of all published literature has not been attempted.

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Synthesis and Characterisation of Chiral Triazole‐Based Halogen‐Bond Donors: Halogen Bonds in the Solid State and in Solution

Kaasik

Kaabel

Kriis

et al. 2017

Chemistry A European J

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A general platform for the synthesis of various chiral halogen-bond (XB) donors based on the triazole core and the characterisation of factors that influence the strength of the halogen bond in the solid state and in solution are reported. The characterisation of XB donors in the solid state by X-ray crystallography and in solution by H NMR titration can be used to aid the design of new XB donors. We describe the first example of a XB between iodotriazoles and thioureas in solution. In addition, the enantiodiscrimination of acceptors in solution through halogen-bond participation is described.

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Insights into halogen bond-driven enantioseparations

Cited by 41 publications

References 58 publications

Polysaccharide‐based chiral stationary phases as halogen bond acceptors: A novel strategy for detection of stereoselective σ‐hole bonds in solution

Polysaccharide‐based chiral stationary phases as halogen bond acceptors: A novel strategy for detection of stereoselective σ‐hole bonds in solution

Recent studies of docking and molecular dynamics simulation for liquid‐phase enantioseparations

Synthesis and Characterisation of Chiral Triazole‐Based Halogen‐Bond Donors: Halogen Bonds in the Solid State and in Solution

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