Volume 2021, Issue 44 p. 5922-5933
Full Paper

Stereoselective Synthesis of 1,2-cis-Glycosyl Sulfones and Their Application in One-Pot Julia Olefination for the Synthesis of exo-Glycals

Prof. Dr. Natsuhisa Oka

Corresponding Author

Prof. Dr. Natsuhisa Oka

Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu, 501-1193 Japan

Center for Highly Advanced Integration of Nano and Life Sciences, Gifu University (G-CHAIN), 1-1 Yanagido, Gifu, 501-1193 Japan

Institute for Glyco-core Research (iGCORE), Gifu University, 1-1 Yanagido, Gifu, 501-1193 Japan

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Kanna Suzuki

Kanna Suzuki

Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu, 501-1193 Japan

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Ayumi Mori

Ayumi Mori

Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu, 501-1193 Japan

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Prof. Dr. Kaori Ando

Corresponding Author

Prof. Dr. Kaori Ando

Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu, 501-1193 Japan

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First published: 30 October 2021
Citations: 1

Graphical Abstract

The stereoselective synthesis of 1,2-cis-glycosyl sulfones and their application to one-pot Julia olefination are reported. Glycosylation of heteroarylthiols using glycosyl iodides as glycosyl donors afforded heteroaryl 1-thioglycosides in a highly 1,2-cis-selective manner. 1,2-cis-Glycosyl sulfones were obtained by oxidation of the resulting 1-thioglycosides by magnesium monoperphthalate. One-pot Julia olefination using 1,2-cis-glycosyl sulfones furnished exo-glycals with E/Z selectivity of up to 91 : 9.

Abstract

Glycosyl sulfones are important intermediates in the synthesis of various sugar derivatives. However, their 1,2-cis-isomers have not been extensively studied because of lower availability. Herein, we report the highly stereoselective synthesis of heteroaryl-substituted 1,2-cis-glycosyl sulfones via glycosylation of heteroarylthiols and subsequent oxidation by magnesium monoperphthalate. One-pot Julia olefination using these 1,2-cis-glycosyl sulfones was also studied. It furnished thermodynamically less stable (E)-exo-glycals with E/Z selectivity of up to 91 : 9.

Conflict of interest

The authors declare no conflict of interest.