Enantioseparation of racemic bupivacaine via ultrasonic-assisted diastereomeric crystallization using 12,14-dinitrodehydroabietic acid

Ge, Li; Zhu, Yi; Qi, Y. Q.; Chen, Yande; Yang, Kang

doi:10.1016/j.ultsonch.2019.01.020

Cited by 8 publications

(4 citation statements)

References 38 publications

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“…6,8 L-lysine exhibits more robust binding affinity with (S)-ibuprofen than its antipode. 7 Similar results were reported for 12,14-dinitrodehydroabietic acid toward enantiopure bupivacaine 11 and (S)-mandelic acid toward (S)-2-(2-oxopyrrolidin-1-yl)butanamide. 12 Furthermore, there are also reports on transforming racemic compounds into conglomerates based on achiral coformers.…”

Section: ■ Introductionsupporting

confidence: 72%

Thermodynamic and Molecular Recognition Mechanism of Diastereomeric Salt/Cocrystal-Induced Chiral Separation

Sui

Wang

et al. 2022

Crystal Growth & Design

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To better understand the thermodynamics and molecular self-assembly mechanism of diastereomeric salt/cocrystalinduced chiral separation, a series of 1:1 cocrystals and salts consisting of chiral valines (VAL) and tartaric acid derivatives were synthesized via different methods. Powders of these as-screened cocrystals/salts were characterized by PXRD, TGA, DSC, FT-IR, and Raman spectroscopy. The crystal structures of the five cocrystals/salts were determined and analyzed. It was found that both DBTA and DTTA form diastereomeric salt pairs with VAL enantiomers. Interestingly, L-DMTA cocrystallizes with D-VAL and L-VAL via hydrogen bonding and proton transfer, respectively. Considering this particularity, the differential isothermal (10 °C) ternary phase diagrams (TPDs) of D-DMTA and L-VAL (D-VAL) cocrystals (salt) were constructed in the mixed solvent of MeOH/ H 2 O. Moreover, a pure L-VAL:D-DMTA cocrystal and D-VAL:D-DMTA:0.5CH 4 O:0.25H 2 O salt were prepared via equimolar slurry conversion at 10 °C. In situ Raman spectroscopy was applied to monitor the molecular assembly process during the incubation of the cocrystal/salt. Molecular dynamics simulation was employed to rationalize the molecular recognition mechanism, demonstrating the excellent chirality preference of L-DMTA toward L-VAL instead of D-VAL. Calculations of density functional theory approved the synergistic instead of antagonistic effects of binding energy and solvation free energy toward chiral separation.

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Section: ■ Introductionsupporting

confidence: 72%

Thermodynamic and Molecular Recognition Mechanism of Diastereomeric Salt/Cocrystal-Induced Chiral Separation

Sui

Wang

et al. 2022

Crystal Growth & Design

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“… 216 Similarly, Ge et al successfully enantio-separated ( R , S )-bupivacaine via an ultrasonic-assisted CCR process by adopting 12,4-dinitrodehydroabietic acid (12,14-dinitroDHAA) as the resolving agent. 217 After utilizing a Box–Behnken design with response surface methodology, the optimal conditions were obtained to prepare the ( S )-enantiomer with 69.8% ee and 87.5% yield. In addition, PBMs encompassing simplified crystallization kinetics and objective functions can also be applied to CCR for the prediction of temperature, concentration, or particle size distribution in the system.…”

Section: Crystallization-based Methods For Chiral Separationmentioning

confidence: 99%

Strategies for chiral separation: from racemate to enantiomer

Sui,

Wang,

Wang

et al. 2023

Chem. Sci.

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“…The exact mechanisms of sonocrystallization and sonofragmentation are still rather unclear; however, it is believed that most effects arise from mechanical effects, which include the generation, growth, and implosive collapse of micrometer-sized cavitation bubbles when ultrasound waves propagate in a liquid medium. 905,906 In the last decade, resolution procedures by crystallization have been also reported for chiral metal nanoclusters and nanocrystals (Figure 74). 907 The interest in the enantioseparation of nanomaterials is related to the evidence that chiral nanocrystals may interact enantioselectively with biomolecules and biological tissues.…”

Section: Enantioselective Adsorption and Permeationmentioning

confidence: 99%

“…The application of ultrasound to stereoselective crystallization processes (sonocrystallization) has been shown to have several beneficial effects on the process in order to determine some properties of the product, such as size, shape and polymorphic modification. The exact mechanisms of sonocrystallization and sonofragmentation are still rather unclear; however, it is believed that most effects arise from mechanical effects, which include the generation, growth, and implosive collapse of micrometer-sized cavitation bubbles when ultrasound waves propagate in a liquid medium. , …”

Section: Trends In Enantioselective Recognition In Natural and Synthe...mentioning

confidence: 99%

Recognition in the Domain of Molecular Chirality: From Noncovalent Interactions to Separation of Enantiomers

2022

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It is not a coincidence that both chirality and noncovalent interactions are ubiquitous in nature and synthetic molecular systems. Noncovalent interactivity between chiral molecules underlies enantioselective recognition as a fundamental phenomenon regulating life and human activities. Thus, noncovalent interactions represent the narrative thread of a fascinating story which goes across several disciplines of medical, chemical, physical, biological, and other natural sciences. This review has been conceived with the awareness that a modern attitude toward molecular chirality and its consequences needs to be founded on multidisciplinary approaches to disclose the molecular basis of essential enantioselective phenomena in the domain of chemical, physical, and life sciences. With the primary aim of discussing this topic in an integrated way, a comprehensive pool of rational and systematic multidisciplinary information is provided, which concerns the fundamentals of chirality, a description of noncovalent interactions, and their implications in enantioselective processes occurring in different contexts. A specific focus is devoted to enantioselection in chromatography and electromigration techniques because of their unique feature as “multistep” processes. A second motivation for writing this review is to make a clear statement about the state of the art, the tools we have at our disposal, and what is still missing to fully understand the mechanisms underlying enantioselective recognition.

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Enantioseparation of racemic bupivacaine via ultrasonic-assisted diastereomeric crystallization using 12,14-dinitrodehydroabietic acid

Cited by 8 publications

References 38 publications

Thermodynamic and Molecular Recognition Mechanism of Diastereomeric Salt/Cocrystal-Induced Chiral Separation

Thermodynamic and Molecular Recognition Mechanism of Diastereomeric Salt/Cocrystal-Induced Chiral Separation

Strategies for chiral separation: from racemate to enantiomer

Recognition in the Domain of Molecular Chirality: From Noncovalent Interactions to Separation of Enantiomers

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