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Synthesis 2008(23): 3761-3768  
DOI: 10.1055/s-0028-1083221
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Ether-Linked Sugar by Nucleophilic Opening of Carbohydrate Oxiranes

Kazusa Nishiyama, Takahiro Nakayama, Hideaki Natsugari, Hideyo Takahashi*
School of Pharmaceutical Sciences, Teikyo University, Sagamiko, Sagamihara, Kanagawa 229-0195, Japan
Fax: +81(426)853728; e-Mail: hide-tak@pharm.teikyo-u.ac.jp;
Further Information

Publication History

Received 9 July 2008
Publication Date:
14 November 2008 (online)

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Abstract

A new synthesis of ether-linked sugar utilizing the nucleophilic ring-opening reaction of carbohydrate α- or β-oxirane was developed. The reaction of 2,3-anhydro-α-d-mannopyranosides resulted in the expected high regioselectivity. In contrast, 2,3-anhydro-α-d-allopyranosides showed an unusual regioselectivity shift. The differentiating properties of carbohydrate α- or β-oxirane were investigated by comparing various conditions of the reaction.

Key words

carbohydrates - epoxides - ethers - ring opening - regio­selectivity

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14

In every reaction, the theoretical amount of alcohol was recovered almost completely.

15

The product was derivatized as its acetate to confirm the structure.

20

TMSOTf might be deactivated by partially deprotected oxirane and product, which would lower the yield of 12.