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Preparation of Pyranose‐Based Thioimidate N ‐Oxides (TINOs)
Author(s) -
Marquès Stéphanie,
Schuler Marie,
Tatibouët Arnaud
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201403619
Subject(s) - pyranose , chemistry , nucleophile , arabinose , furanose , carbohydrate , stereochemistry , iminosugar , pentose , xylose , organic chemistry , combinatorial chemistry , enzyme , ring (chemistry) , catalysis , fermentation
Abstract The synthesis of new pyranose‐based thioimidate N ‐oxides (TINOs) is reported. Original strategies were developed, by taking advantage of the nucleophilic capability of the thiohydroximate function, anchored on a carbohydrate backbone. The key cyclisation step was achieved either through a Mitsunobu‐type reaction or through desilylative cyclisation. These studies enable access to a unique family of polyhydroxypiperidine thioimidate N ‐oxides both from aldopentoses ( D ‐xylose and D ‐arabinose) and from aldohexoses ( D ‐glucose, D ‐mannose), thus extending the previously relatively limited class of cyclic six‐membered nitrone analogues. Typical examples of TINOs were prepared with good yields in six to ten steps in both D ‐ and L ‐series. These compounds should be highly valuable synthetic intermediates in the preparation of various complex iminosugars, or azasugars, as potential modulators of carbohydrate‐processing enzymes.