Novel stereospecific dehydration of β-hydroxy-α-amino acids using Martin's sulfurane

doi:10.1016/S0040-4039(02)02179-2

Tetrahedron Letters

Volume 43, Issue 48, 25 November 2002, Pages 8679-8682

https://doi.org/10.1016/S0040-4039(02)02179-2 Get rights and content

Abstract

The stereospecific dehydration of threo-N-acyl-β-hydroxy-α-amino acid derivatives was performed using Martin's sulfurane to give (Z)-α,β-dehydroamino acids, while erythro-N-acyl-β-hydroxy-α-amino acid amides were converted to 4,5-trans-oxazolines using analogous reaction conditions.

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Acknowledgements

This work was financially supported in part by Grant-in-Aids from the Uehara Memorial Foundation (to F.Y.), the Fujisawa Foundation (to F.Y.), and the Ministry of Education, Science, Sports and Culture, Japan.

References (9)

F. Yokokawa et al.
Tetrahedron Lett.
(2002)
A. Srinivasan et al.
J. Org. Chem.
(1977)
T.J. Nitz et al.
J. Org. Chem.
(1981)
R.J. Arhart et al.
J. Am. Chem. Soc.
(1972)
L. Somekh et al.
J. Org. Chem.
(1983)

There are more references available in the full text version of this article.

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Citation Excerpt :
Oxazoles and thiazoles are synthesized by the oxidation of oxazolines and thiazolines, respectively. Although several methods have been reported for the synthesis of oxazolines and thiazolines using stoichiometric dehydrating reagents,2 few dehydrating catalysts are known to be effective for the dehydrative cyclization of N-(β-hydroxyethyl)amides or N-(β-mercaptoethyl)amides to oxazolines or thiazolines: 3-nitrophenylboric acid,3 a tetranuclear zinc cluster,4 a lanthanide chloride,5 a zeolite,6 TiCl4,7 TsOH,8 etc. However, these catalytic methods are limited to simple substrates derived from an amino alcohol or a monopeptide (amino acid).
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^†: Present address: Tsukuba Research Institute, Novartis Pharma K.K., Ohkubo 8, Tsukuba, Ibaraki 300-2611, Japan.

^‡: Present address: Graduate School of Environmental and Human Sciences, Meijo University, Shiogamaguchi, Tempaku, Nagoya 468-8502, Japan.

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Novel stereospecific dehydration of β-hydroxy-α-amino acids using Martin's sulfurane

Abstract

Section snippets

Acknowledgements

Tetrahedron Lett.

J. Org. Chem.

J. Org. Chem.

J. Am. Chem. Soc.

J. Org. Chem.