Synlett
DOI: 10.1055/a-1384-2931
letter

Glycosylation by Alkyne Activation of the 2-O-Substituted Propargyl Group in a β-Phenylthioglucoside with a 5 S 1 Conformation

a  Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10, Nishi 8, Kita-ku, Sapporo, 060-0810, Japan
b  School of Science and Technology, Kwansei Gakuin University, 2-1, Gakuen, Sanda, 669-1337, Japan
,
Shintaro Matsumoto
b  School of Science and Technology, Kwansei Gakuin University, 2-1, Gakuen, Sanda, 669-1337, Japan
,
Daiki Ikuta
b  School of Science and Technology, Kwansei Gakuin University, 2-1, Gakuen, Sanda, 669-1337, Japan
,
b  School of Science and Technology, Kwansei Gakuin University, 2-1, Gakuen, Sanda, 669-1337, Japan
› Author Affiliations
JSPS KAKENHI (Grants Nos. JP16H01163 in Middle Molecular Strategy, JP16KT0061, and JP19K15549) partly supported this work.


Abstract

Generally, glycosylation reactions activate an anomeric substituent in a glycosyl donor to generate an oxocarbenium ion intermediate. Here we report a novel glycosylation reaction triggered by the activation of a 2-O-substituted propargyl group in a 3,6-O-1,1′-[(ethane-1,2-diyl)bibenzene-2,2′-bis(methylene)]-β-thioglucoside. This reaction proceeds through a cationic Au(I)-mediated intramolecular migration of the anomeric substituent onto the alkyne moiety of the propargyl group, followed by α-attack by the hydroxy group in the glycosyl acceptor on the oxocarbenium ion. The migration of the anomeric group occurs selectively through a 6-exo-dig pathway. The 2-(phenylsulfanyl)prop-2-en-1-yl group produced during the glycosylation is removable under conditions similar to those used for removing an allyl group. This reaction will be developed for further applications in orthogonal oligosaccharide synthesis.

Supporting Information



Publication History

Received: 18 January 2021

Accepted after revision: 05 February 2021

Publication Date:
05 February 2021 (online)

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
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