Preparation of Pyranose-Based Thioimidate N-Oxides (TINOs)

Author： Marquès Stéphanie Schuler Marie Tatibouët Arnaud

E-ISSN： 1099-0690|2015|11|2411-2427

ISSN： 1434-193X

Source： European Journal of Organic Chemistry, Vol.2015, Iss.11, 2015-04, pp. : 2411-2427

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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. Previously unknown pyranose-based thioimidate N-oxides (TINOs) were prepared by two strategies based on the cyclisation of suitably functionalised thiohydroximate functions anchored on various carbohydrate backbones, either through a Mitsunobu-type reaction or through desilylative cyclisation.