Evidence of Conglomerate with Partial Solid Solutions in Ethylammonium Chlocyphos

Mbodji, Aliou; Gbabode, Gabin; Sanselme, Morgane; Cartigny, Yohann; Couvrat, Nicolas; Leeman, Michel; Dupray, Valérie; Kellogg, Richard M.; Coquerel, G.

doi:10.1021/acs.cgd.9b01699

Cited by 11 publications

(13 citation statements)

References 26 publications

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“…Similar behavior was observed in the solid solution of racemic salt. [28] These observations in the phase diagram and PXRD measurements indicate that both the SL and RL were In order to quantitatively design the chiral resolution process by crystallization using this complete solid solution system, a quasi-ternary phase diagram, SL/RL/methanol, was constructed. After the solubility tests with various solvents, methanol was selected for phase diagram construction and chiral resolution study due to the moderate solubility of 1.…”

Section: Main Textmentioning

confidence: 95%

Overcoming a Solid Solution System on Chiral Resolution: Combining Thermodynamics of Crystallization and Kinetics of Enantioselective Dissolution

Oketani

Shiohara

Hisaki

2023

Preprint

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We have successfully performed chiral resolution of a key synthetic intermediate of ozanimod, rac-4-cyano-1-aminoindane, by combining crystallization and enantioselective dissolution. 4-Cyano-1-aminoindane forms a diastereomeric salt with di-p-toluoyl-L-tartaric acid, however the single crystallization gave moderate enantiomeric excess, which indicated the formation of solid solution. The formation of solid solution is typical trouble in chiral resolution, and the limitation of enrichment by the crystallization was indicated by the construction of binary and ternary phase diagrams. Thorough phase diagram study revealed the solid-state landscape of the diastereomeric salt and determined the condition for chiral resolution. Additionally, further enrichment was achieved by following enantioselective dissolution using the difference in dissolution rates of the diastereomeric pairs. This combination of crystallization and dissolution demonstrated chiral resolution of 4-cyano-1-aminoindane up to 96%, and proposed a new solution to the solid solution formation which is typical trouble of chiral resolution for the first time.

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Section: Main Textmentioning

confidence: 95%

Overcoming a Solid Solution System on Chiral Resolution: Combining Thermodynamics of Crystallization and Kinetics of Enantioselective Dissolution

Oketani

Shiohara

Hisaki

2023

Preprint

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“…Partial solid solutions between enantiomers are also well known [5,18]. Those cases are intermediate between conglomerates without solid solution and with complete solid solution.…”

Section: Chiral Discrimination Between Pairs Of Enantiomers In the So...mentioning

confidence: 99%

“…Symmetry 2020, 12, x FOR PEER REVIEW 3 of 18 cooling (i.e., quenching) can lead to amorphous material without any kind of macroscopic chiral recognition [17]. Partial solid solutions between enantiomers are also well known [5,18]. Those cases are intermediate between conglomerates without solid solution and with complete solid solution.…”

Section: Equilibrium In Solutionmentioning

confidence: 99%

Spontaneous and Controlled Macroscopic Chiral Symmetry Breaking by Means of Crystallization

Coquerel

Hoquante

2020

Symmetry

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In this paper, macroscopic chiral symmetry breaking refers to as the process in which a mixture of enantiomers departs from 50–50 symmetry to favor one chirality, resulting in either a scalemic mixture or a pure enantiomer. In this domain, crystallization offers various possibilities, from the classical Viedma ripening or Temperature Cycle-Induced Deracemization to the famous Kondepudi experiment and then to so-called Preferential Enrichment. These processes, together with some variants, will be depicted in terms of thermodynamic pathways, departure from equilibrium and operating conditions. Influential parameters on the final state will be reviewed as well as the impact of kinetics of the R ⇔ S equilibrium in solution on chiral symmetry breaking. How one can control the outcome of symmetry breaking is examined. Several open questions are detailed and different interpretations are discussed.

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“…In two cases (QAKTAB 52 and DAJYUM 53 ), a cocrystallization strategy was employed. In the remaining three examples (EMUZEU, 54 GUPBOL, 55 and IGIXII 56 ) the substrates were transformed into an organic salt. Notably, all examples presented in Figure 5 use an achiral agent to form the required cocrystal or salt in the engineered crystal.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Figure 5. Chiral conglomerates crystals formed by crystal engineering.The conglomerate structures are labeled with their associated CSD Refcodes: QAKTAB,52 DAJYUM,53 EMUZEU,54 GUPBOL,55 IGIXII 56. …”

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confidence: 99%

Conglomerate Crystallization in the Cambridge Structural Database (2020–2021)

Walsh¹,

Barclay

Begg

et al. 2023

Crystal Growth & Design

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Conglomerate crystals are materials capable of undergoing spontaneous resolution and were responsible for the discovery of molecular chirality. Their relevance to modern chemical and crystallographic sciences has been hindered by the difficulty in identifying and searching materials with this characteristic ability to spontaneously bias their own enantioenrichment. With the release of the November 2021 distribution of the Cambridge Structural Database (CSD) (version 5.43), a fresh quantity of chiral conglomerate crystals is expected to have been published in the CSD without identification. Indeed, no crystals in the CSD have been identified as a spontaneously resolving conglomerate crystal in their crystallographic information file since the 2019 release, despite the deposition of over 108,000 new crystal structures into the database over the same time period. A manual inspection of crystals deposited between 2020 and 2021 was conducted to identify 343 new chiral materials which exhibit conglomerate crystallization behavior. It is hoped that the continued manual curation of this list will aid those in the crystallographic and synthetic communities to study and exploit this spontaneous enantioenrichment behavior.

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Evidence of Conglomerate with Partial Solid Solutions in Ethylammonium Chlocyphos

Cited by 11 publications

References 26 publications

Overcoming a Solid Solution System on Chiral Resolution: Combining Thermodynamics of Crystallization and Kinetics of Enantioselective Dissolution

Overcoming a Solid Solution System on Chiral Resolution: Combining Thermodynamics of Crystallization and Kinetics of Enantioselective Dissolution

Spontaneous and Controlled Macroscopic Chiral Symmetry Breaking by Means of Crystallization

Conglomerate Crystallization in the Cambridge Structural Database (2020–2021)

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