Asymmetric Synthesis Involving Dynamic Enantioselective Crystallization

Sakamoto, Masami

doi:10.1007/978-981-15-5085-0_21

Cited by 11 publications

(7 citation statements)

References 54 publications

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“…894 If preferential crystallization is applied under conditions in which fast racemization proceeds in the mother liquor, it becomes possible to direct the entire system to the desired single-handed enantiomer. 895 As a racemic mixture of a conglomerate is dynamically crystallized from a supersaturated solution, the molecule repeatedly aggregates and dissolves until the first chiral crystal nucleus is formed. Under these conditions, the crystals grow through molecules of the same enantiomer, whereas the crystallized enantiomer decreases in the mother liquor, and as a consequence, it is restored in solution through racemization in order to maintain the equilibrium state.…”

Section: Enantioselective Adsorption and Permeationmentioning

confidence: 99%

“…If preferential crystallization is applied under conditions in which fast racemization proceeds in the mother liquor, it becomes possible to direct the entire system to the desired single-handed enantiomer . As a racemic mixture of a conglomerate is dynamically crystallized from a supersaturated solution, the molecule repeatedly aggregates and dissolves until the first chiral crystal nucleus is formed.…”

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

confidence: 99%

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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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Section: Enantioselective Adsorption and Permeationmentioning

confidence: 99%

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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“…versus time can also evolve linearly [27]. Viedma ripening can be implemented directly during the synthesis; this method is called asymmetric synthesis, involving dynamic enantioselective crystallization [28].…”

Section: Deracemization Induced By a Flux Of Energy Crossing The Susp...mentioning

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 either method, the products must crystallize as a conglomerate, and rapid racemization must proceed under the conditions of crystal growth. It has been reported that the racemization of the products can be carried out directly via an achiral intermediate, such as an enolate anion, − using a reversible reaction such as the Michael addition reaction − or the Diels–Alder reaction. , Various new reaction systems are actively under development. − …”

Section: Introductionmentioning

confidence: 99%

Asymmetric Anisoin Synthesis Involving Benzoin Condensation Followed by Deracemization

Washio

Hosaka

Uemura

et al. 2021

Crystal Growth & Design

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The highly enantioselective synthesis of p-anisoin was achieved via the benzoin condensation of a prochiral p-anisaldehyde using achiral NHC catalysts such as vitamin B1. In this reaction, p-anisoin crystallized as a conglomerate, and the deracemization of racemic p-anisoin under basic conditions was efficiently performed by Viedma ripening. Although the handedness of the enantioselective crystallization could not be controlled by spontaneous crystallization, it could be controlled by the coexistence of a catalytic amount of optically active valine. It was clarified that this is due to the asymmetric transformation of p-anisoin with enantiomeric valine in the mother liquor.

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Asymmetric Synthesis Involving Dynamic Enantioselective Crystallization

Cited by 11 publications

References 54 publications

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

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

Spontaneous and Controlled Macroscopic Chiral Symmetry Breaking by Means of Crystallization

Asymmetric Anisoin Synthesis Involving Benzoin Condensation Followed by Deracemization

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