• Journal of the Korean Chemical Society
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• v.52 no.3
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• pp.338-340
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• 2008

• Journal of the Society of Cosmetic Scientists of Korea
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• v.49 no.2
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• pp.141-146
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• 2023

The efficient use of a chiral shift agent (3) containing bifunctional group (thiourea and tertiary amine) for the determination of the enantiomeric purity of racemic mixture (Hemiesters) has been studied. The diastereomeric complexes derived from a chiral shift agent (3) with various hemiesters gave rise to well separate signals of the methoxy protons of hemiesters. Good splitting signals for enantiomers of hemiesters in ¹H NMR are originated form the hydrogen bonds between carbonyl groups of hemiester and bifunctional groups of a chiral shift agent (3) such as thiourea moiety and tertiary amine. This study provides a quick and simple way to determine the chiral purity of hemiester using chiral transfer agent (3).

• Journal of the Korean Chemical Society
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• v.46 no.4
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• pp.393-397
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• 2002

• Journal of the Korean Chemical Society
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• v.41 no.3
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• pp.150-156
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• 1997

A precursor of bulgecinine, (4S,5R)-1-acetyl-2-formyl-5-benzyloxymethyl-4-pyrrolidinol (15) has been synthesized from diacetone-D-glucose. Barton deoxygenation, conversion to an L-sugar and displacement with $N_3^-$ at C-5, and one-pot reductive cyclization at C-2 produced (6R)-6-Ο-benzyloxymethyl-(3R)-3-methoxy-2-oxa-5-azabicyclo-[2,2,1]heptane(13), a key intermediate for bulgecinine. N-Acetylation and acid hydrolysis of 13 furnished a precursor of bulgecinine, (2S,4S,5R)-pyrrolidinol derivative 15 and its (2R,4S,5R)-diastereomer.

• Journal of the Korean Chemical Society
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• v.59 no.6
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• pp.488-492
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• 2015

In this study, the effective preparation method of (S)-(+)-pranidipine, the active component of antihypertensive drug as a calcium channel blocker, was developed using optical resolution. The racemic monocarboxylic acid 5 obtained by the hydrolysis of (±)-pranidipine was mixed with optically active quinidine to form salts, and the insoluble diastereomeric salt was collected and successive treatment with base and acid furnished (R)-(-)-carboxylic acid 7. (S)-(+)-Pranidipine was prepared by esterification of this acid with cinnamyl alcohol, and the analysis by chiral HPLC showed 100% enantiomeric excess (ee). This process would be industrially very useful to prepare chiral (S)-(+)-pranidipine, since the use of strong base and anhydrous solvents, and ultra-low temperature condition were excluded in this process.

• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.119-130
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• 1993

The stereochemistry of 1,3-thiazolidine sulfoxides 1 in which 3 chiral centres are present in a molecule was elucidated by deuterium exchange and trapping reactions. 3-Acetoxy-1,3-thiazolidines 5 was oxidized to 6 and 8, corresponding $\alpha$-cis 10, $\alpha$-trans 11, $\beta$ -cis 12, and $\beta$ -trans 13 isomers were separated from their diasteromeric mixtures. Sulfoxide 10 was isomerized to more thermodynamically stable isomer 13 under neutral conditions in refluxing benzene or toluene. The methyl hydrogens of 2-methyl group in the sulfoxide 13 and those of the sulfoxide 11 were deuterated by the deuterium incorporation reactions. The intermediate sulfenic acids 25 and 26 derived from the sulfoxides 10 and 12 via sigmatropic rearrangement were trapped by 2-mercaptobenzothiazole (2-MBT) to give disufides 27 and 28 respectively. However, the sulfoxides 11 and 13 were transformed to ring expansion product dihydro-1,4-thiazine 29 under the same reaction conditions. In the presence of acid catalyst, the sulfoxides 10, 11, and 12 were converted to dihydro-1,4-thiazine 29 through the sulfoxide 13 quantitatively. The mechanisms of isomerization of sulfoxides and the formation of 29 were also discussed.