Synthesis of Four Stereoisomers of 1,4-Thiazane-3-carboxylic Acid 1-Oxide<i>via</i>the Asymmetric Transformation (combined isomerization-preferential crystallization) of 1,4-Thiazane-3-carboxylic Acid

Shiraiwa, Tadashi; Tadokoro, Kohya; Ishikawa, Joji; Tanaka, Haruyuki; Masaki, Tooru; Kurokawa, Hidemoto

doi:10.1271/bbb.64.341

Cited by 4 publications

(2 citation statements)

References 12 publications

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“…The same group described a number of similar CIDT for histidine, 104 4-thiazolidinecarboxylic acid, 105 and 2,2-dimethyl-4-thiazolidinecarboxylic acid 106 (the latter two are precursors to cysteine) as well as for 1,3-thiazane-3-carboxylic acid 107 (a precursor to homocysteine) and 1,4-thiazane-3carboxylic acid 108 (a precursor to the natural product chondrine). In each case the amino acid is heated with a tartaric acid in the presence of salicylaldehyde in a carboxylic acid solvent at an elevated temperature and the diastereomerically pure salt is obtained in high yield and purity.…”

Section: Amino Acids and Related Compoundsmentioning

confidence: 99%

Crystallization-Induced Diastereomer Transformations

2006

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Section: Amino Acids and Related Compoundsmentioning

confidence: 99%

Crystallization-Induced Diastereomer Transformations

2006

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“…In this case, the α-carbon of the methyl phenylglycinate is the equilibrating center while the chiral centers of L -tartaric acid act as nonequilibrating centers. Since then, tartaric acid and its derivatives have been widely used in CIDT of amino acid derivatives either as a chiral resolution step or as an intermediate step in asymmetric synthesis. − In addition, the use of covalent diastereomers (as opposed to diastereomeric salts) in CIDT has been demonstrated by Cannata et al for the enantiopurification of an anti-inflammatory drug, naproxen. In this process, they treated the racemic naproxen mixture with an aminoalcohol to produce diastereomeric amides, which was then followed by acid hydrolysis to recover optically pure naproxen.…”

Section: Introductionmentioning

confidence: 99%

Enantiopurification of Mandelic Acid by Crystallization-Induced Diastereomer Transformation: An Experimental and Computational Study

Lerdwiriyanupap

Cedeno

Nalaoh

et al. 2023

Crystal Growth & Design

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Chiral purification is crucial in the pharmaceutical industry due to the dramatic differences in biological activity of the two enantiomers of most chiral drugs. In this work, we demonstrate a new enantiopurification route for an important drug precursor, mandelic acid, by forming a diastereomeric amide with enantiopure 1-phenylethylamine. We show that in the presence of a strong base, the resulting diastereomeric system not only undergoes a reversible epimerization reaction but also exhibits a surprising difference in crystallization behavior, i.e., at room temperature, one epimer forms a metastable gel phase, only converting to a more stable crystal over several days, while the other forms a stable crystalline phase. Exploiting these properties, a facile purification technique via crystallization-induced diastereomer transformation (CIDT) was achieved enabling good product yield (>70%) and excellent optical purity (>92%). Enantiopure mandelic acid (∼91% e.e.) can then be recovered via acid hydrolysis. This work highlights that for compounds that are neither conveniently racemizable nor conglomerate-forming such as mandelic acid, CIDT is a powerful alternative to the deracemization technique, capable of yields greater than the 50% in contrast to traditional resolution techniques.

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Optical resolution methods

et al. 2006

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Despite the large number of elaborate enantioselective syntheses for the preparation of a single enantiomer to achieve industrial and scientific goals, the separation and purification of enantiomers (components of racemic compounds) is also necessary. Hence, we present the most often used thought-provoking modern methods based on momentous recognitions (e.g. spontaneous resolution, induced crystallization, resolution by formation of diastereomers, resolution by formation of non-covalent diastereomers, resolution by diastereomeric salt formation, resolution by diastereomeric complex formation, "half equivalent" methods of resolution, separation by crystallization, separation by distillation, separation by supercritical fluid extraction, resolution with mixtures of resolving agents, resolution with a derivative of the target compound, enantioselective chromatography, resolution by formation of covalent diastereomers, resolution by substrate selective reaction, kinetic resolution without enzymes, kinetic resolution by enzyme catalysis, hydrolytic and redox enzymes, kinetic and thermodynamic control, resolutions combined with 2nd order asymmetric transformations, enrichment of partially resolved mixtures, role of the solvent and methods of optimization in the separation of diastereoisomers, non-linear effects and selected examples of resolution on an industrial scale).

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Synthesis of Four Stereoisomers of 1,4-Thiazane-3-carboxylic Acid 1-Oxideviathe Asymmetric Transformation (combined isomerization-preferential crystallization) of 1,4-Thiazane-3-carboxylic Acid

Cited by 4 publications

References 12 publications

Crystallization-Induced Diastereomer Transformations

Crystallization-Induced Diastereomer Transformations

Enantiopurification of Mandelic Acid by Crystallization-Induced Diastereomer Transformation: An Experimental and Computational Study

Optical resolution methods

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