Synthesis of enantiomers of 3-methyl- and 3-phenyl-3,4-dihydro-2H-{[}1,4]benzothiazines and their 1,1-dioxides via an acylative kinetic resolution protocol / Gruzdev Dmitry A.,Chulakov Evgeny N.,Sadretdinova Liliya Sh,Kodess Mikhail I.,Levit Galina L.,Krasnov Victor P. // TETRAHEDRON-ASYMMETRY. - 2015. - V. 26, l. 4. - P. 186-194.

ISSN/EISSN:

0957-4166 / нет данных

Type:

Article

Abstract:

It has been found that acyl chlorides of (S)-naproxen, N-phthaloyl-(S)-leucine, and N-tosyl-(S)-proline are efficient chiral resolving agents for the acylative kinetic resolution of racemic 3-methyl- and 3-phenyl-3,4-dihydro-3-methyl-2H-{[}1,4]benzothiazines. Based on the experimental results, a preparative protocol comprising the acylative kinetic resolution followed by isolation of a single (major) diastereoisomeric amide and subsequent hydrolysis of amide bond was proposed. Using this approach with various chiral resolving agents, (S)- and (R)-enantiomers of 3,4-dihydro-3-methyl-2H-{[}1,4]benzothiazine (ee >99\%) were obtained. The oxidation of the corresponding diastereoisomers of the amides followed by deacylaton led to the (S)- and (R)-enantiomers of 3,4-dihydro-3-methyl-2H-{[}1,4]benzothiazine-1,1-dioxide (ee >97\%). This method proved to be less suitable for the preparation of the (S)-enantiomer of 3,4-dihydro-3-phenyl-2H-{[}1,4]benzothiazine (ee up to 93\%) and its sulfone (ee 82\%) which were both obtained in low yields. The loss of enantioselectivity for (S)-3,4-dihydro-3-phenyl-2H-{[}1,4]benzothiazine and its sulfone occurred during hydrolysis of the corresponding diastereoisomerically pure amides. (C) 2015 Elsevier Ltd. All rights reserved.

Author keywords:

RACEMIC HETEROCYCLIC AMINES; N-PHTHALOYL-(S)-AMINO ACYL CHLORIDES; N-TOSYL-(S)-PROLYL CHLORIDE; (+/-)-2-METHYL-1,2,3,4-TETRAHYDROQUINOLINE; (+/-)-2-METHYLINDOLINE; BENZOTHIAZINES; DERIVATIVES

DOI:

10.1016/j.tetasy.2015.01.010

Web of Science ID:

ISI:000350076000004

Соавторы в МНС:

—

Другие поля

Поле	Значение
Month	FEB 28
Publisher	PERGAMON-ELSEVIER SCIENCE LTD
Address	THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND
Language	English
Keywords-Plus	RACEMIC HETEROCYCLIC AMINES; N-PHTHALOYL-(S)-AMINO ACYL CHLORIDES; N-TOSYL-(S)-PROLYL CHLORIDE; (+/-)-2-METHYL-1,2,3,4-TETRAHYDROQUINOLINE; (+/-)-2-METHYLINDOLINE; BENZOTHIAZINES; DERIVATIVES
Research-Areas	Chemistry
Web-of-Science-Categories	Chemistry, Inorganic \& Nuclear; Chemistry, Organic; Chemistry, Physical
Author-Email	ca512@ios.uran.ru
Funding-Acknowledgement	Russian Scientific Foundation {[}14-13-01077]; Russian Foundation for Basic Research {[}13-03-00674]
Funding-Text	The authors thank Dr. Pavel A. Slepukhin for performing X-ray diffraction. The work was financially supported by the Russian Scientific Foundation (grant 14-13-01077) in the part of studies on 3,4-dihydro-3-phenyl-2H-{[}1,4]benzothiazine and its derivatives, and the Russian Foundation for Basic Research (grant 13-03-00674) in the part of studies on 3,4-dihydro-3-methyl-2H-{[}1,4]benzothiazine and its derivatives.
Number-of-Cited-References	33
Usage-Count-Since-2013	11
Journal-ISO	Tetrahedron-Asymmetry
Doc-Delivery-Number	CC1BK