First protection-free protocol for synthesis of 1-deoxy sugars through glycosyl dithiocarbamate intermediates

doi:10.1016/j.tetlet.2018.08.005

Tetrahedron Letters

Volume 59, Issue 37, 12 September 2018, Pages 3428-3431

https://doi.org/10.1016/j.tetlet.2018.08.005 Get rights and content

Highlights

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Unprotected glycosyl dithiocarbamates as a useful intermediate for 1-deoxy sugar synthesis.
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No protecting-groups are needed to prepare 1-deoxy sugars.
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The 1-deoxy sugars help to elucidate the role of carbohydrates in metabolic cycles.

Abstract

A practical two-step synthetic process for 1-deoxy sugars has been established. The process consists of the direct introduction of a dimethyldithiocarbamate group into the anomeric center of unprotected sugars and subsequent hydrogenation in the AIBN-H₃PO₂-NaHCO₃ system. No protecting groups are needed to synthesize 1-deoxy monosaccharides and 1-deoxy disaccharides.

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Acknowledgments

This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, Japan. We thank Mr. Keisuke Hokotate for experimental support.

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Citation Excerpt :
The reaction was expanded to a one-pot three-component process involving the in situ synthesis of the DTC salt by reaction of CS2 with a dialkylamine in the presence of the Et3N, before the addition of an aqueous solution of the sugar, and finally the DMC, avoiding the need for the isolation of the DTC salts. Usefully these glycosyl dithiocarbamates could be directly converted into 1-deoxy sugars by free radical reduction [66], thus providing the first completely protecting group free synthesis of 1-deoxy sugars (Scheme 15c). Shoda recently reported [67] the DMC-mediated synthesis of glycosyl thiosulfates, also called Bunte salts, by DMC activation in the presence of sodium thiosulfate and Et3N in a D2O/MeCN mixed solvent system.
2-Chloro-1,3-dimethylimidazolinium chloride (DMC, herein also referred to as Shoda's reagent) and its derivatives are useful for numerous synthetic transformations in which the anomeric centre of unprotected reducing sugars is selectively activated in aqueous solution. As such unprotected sugars can undergo anomeric substitution with a range of added nucleophiles, providing highly efficient routes to a range of glycosides and glycoconjugates without the need for traditional protecting group manipulations. This mini-review summarizes the development of DMC and some of its derivatives/analogues, and highlights recent applications for protecting group-free synthesis.
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2023, Chinese Journal of Organic Chemistry
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First protection-free protocol for synthesis of 1-deoxy sugars through glycosyl dithiocarbamate intermediates

Highlights

Abstract

Graphical abstract

Section snippets

Acknowledgments

Clin. Biochem.

Carbohydr. Res.

Arch. Biochem. Biophys.

Cryst. Growth Des.

J. Am. Chem. Soc.

J. Org. Chem.

Tetrahedron Lett.

Org. Biomol. Chem.

Acad. Sci. Fr. Ser. C

J. Am. Chem. Soc.

Biochemistry

Pflug. Arch. Eur. J. Physiol.

Chem. Pharm. Bull.

J. Org. Chem.

Carbohydr. Res.

Bull. Korean Chem. Soc.