The Driving Mechanism Behind Attrition‐Enhanced Deracemization

Noorduin, Wim L.; Enckevort, W.J.P. van; Meekes, Hugo; Kaptein, Bernard; Kellogg, Richard M.; Tully, John C.; McBride, J. Michael; Vlieg, E.

doi:10.1002/anie.201002036

Cited by 153 publications

(167 citation statements)

References 35 publications

(32 reference statements)

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“…This result clearly shows that the majority in the solid phase is minority in the solution phase, in qualitative agreement to the experimental result. Therefore, this experiment [24] does not yet give a definitive answer about the correct scenario. Further exploration is necessary.…”

Section: Summary and Discussionmentioning

confidence: 79%

“…Thus summarized, we conclude that there are three different scenarios so far, and further experimental works are needed to decide which is the actual mechanism. Recently an experiment has been carried out on the measurement of enantiomeric excess in solution phase ee l as a function of that in solid phase ee s under the absence of racemization process in the solution [24]. It is found that ee l and ee s has the opposite sign, and the finding is explained in terms of Uwaha's scenario.…”

Section: Summary and Discussionmentioning

confidence: 95%

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Grinding-induced homochirality in crystal growth

Saitō

Hyuga

2011

Journal of Crystal Growth

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Section: Summary and Discussionmentioning

confidence: 79%

Section: Summary and Discussionmentioning

confidence: 95%

Grinding-induced homochirality in crystal growth

Saitō

Hyuga

2011

Journal of Crystal Growth

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“…!,! ) > 0, growth occurs, while the case of Similarly to previous models 18,39,51,52 , due to the Gibbs-Thomson effect, the cluster solubility ! "…”

Section: Growth and Dissolutionmentioning

confidence: 73%

“…The actual crystal size distributions (CSD) for each enantiomer of the conglomerate crystals are simplified by considering only two arbitrary groups of sizes: large crystals and small chiral clusters 39 . The large crystals in the initially present CSD correspond to the conglomerate seeds, typically of a single chirality, since they are used to control the deracemization outcome.…”

Section: Model Descriptionmentioning

confidence: 99%

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Coupling Viedma Ripening with Racemic Crystal Transformations: Mechanism of Deracemization

Xiouras

Horst

Gerven

et al. 2017

Crystal Growth & Design

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It has been recently observed that coupling Viedma ripening with a seeded in-situ metastable racemic crystal to conglomerate transformation leads to accelerated and complete deracemization: crystal transformation-enhanced deracemization. By means of a simple kinetic model, we show that the mechanistic pathway of this new process depends profoundly on the interplay between the crystal transformation and racemization processes, which in turn influence the nucleation process of the counter enantiomer. If the nucleation of the counter enantiomer is suppressed (e.g. by sufficiently fast racemization, low amount of racemic compound or gradual feed, low relative solubility between racemic compound and conglomerate), deracemization proceeds via a second order asymmetric transformation (SOAT) and is limited primarily by the dissolution rate of the racemic crystals and the growth rate of the preferred enantiomer crystals. Breakage and agglomeration accelerate the process, but contrary to conventional Viedma ripening, they are not essential ingredients to explain the observed enantiomeric enrichment. If the nucleation process of the counter enantiomer is not sufficiently suppressed, deracemization is initially controlled by the dissolution rate of the racemic crystals, but Viedma ripening is subsequently required to convert the conglomerate crystals of the counter enantiomer formed by nucleation, resulting in slower deracemization kinetics. In both cases, the combined process leads to faster deracemization kinetics compared to conventional Viedma ripening, while it autocorrects for the main disadvantage of SOAT, i.e. the accidental nucleation of the counter enantiomer. In addition, crystal transformation-enhanced deracemization extends the range of applicability of solid-state deracemization processes to compounds that form metastable racemic crystals. interplay between the crystal transformation and racemization processes, which in turn influence the nucleation process of the counter enantiomer. If the nucleation of the counter enantiomer is 3 suppressed (e.g. by sufficiently fast racemization, low amount of racemic compound or gradual feed, low relative solubility between racemic compound and conglomerate), deracemization proceeds via a second order asymmetric transformation (SOAT) and is limited primarily by the dissolution rate of the racemic crystals and the growth rate of the preferred enantiomer crystals.Breakage and agglomeration accelerate the process, but contrary to conventional Viedma ripening, they are not essential ingredients to explain the observed enantiomeric enrichment. If the nucleation process of the counter enantiomer is not sufficiently suppressed, deracemization is initially controlled by the dissolution rate of the racemic crystals, but Viedma ripening is subsequently required to convert the conglomerate crystals of the counter enantiomer formed by nucleation, resulting in slower deracemization kinetics. In both cases, the combined process leads to faster deracemization kinetics compared ...

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Rare, Neglected and Potential Synthetic Methods for the Separation of Enantiomers

Todd

2014

Separation of Enantiomers

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The Driving Mechanism Behind Attrition‐Enhanced Deracemization

Cited by 153 publications

References 35 publications

Grinding-induced homochirality in crystal growth

Grinding-induced homochirality in crystal growth

Coupling Viedma Ripening with Racemic Crystal Transformations: Mechanism of Deracemization

Rare, Neglected and Potential Synthetic Methods for the Separation of Enantiomers

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