Chemical synthesis of diglucosyl diacylglycerols utilizing glycosyl donors with stereodirecting cyclic silyl protective groups

Koichi Takato; Motoki Kurita; Nahoko Yagami; Hide-Nori Tanaka; Hiromune Ando; Akihiro Imamura; Hideharu Ishida

doi:10.1016/j.carres.2019.107748

Chemical synthesis of diglucosyl diacylglycerols utilizing glycosyl donors with stereodirecting cyclic silyl protective groups

Carbohydr Res. 2019 Sep 1:483:107748. doi: 10.1016/j.carres.2019.107748. Epub 2019 Jul 18.

Authors

Koichi Takato¹, Motoki Kurita¹, Nahoko Yagami¹, Hide-Nori Tanaka², Hiromune Ando², Akihiro Imamura³, Hideharu Ishida⁴

Affiliations

¹ Department of Applied Bioorganic Chemistry, Gifu University, 1-1 Yanagido, Gifu, 501-1193, Japan.
² Center for Highly Advanced Integration of Nano and Life Sciences (G-CHAIN), Gifu University, 1-1 Yanagido, Gifu, 501-1193, Japan.
³ Department of Applied Bioorganic Chemistry, Gifu University, 1-1 Yanagido, Gifu, 501-1193, Japan. Electronic address: aimamura@gifu-u.ac.jp.
⁴ Department of Applied Bioorganic Chemistry, Gifu University, 1-1 Yanagido, Gifu, 501-1193, Japan; Center for Highly Advanced Integration of Nano and Life Sciences (G-CHAIN), Gifu University, 1-1 Yanagido, Gifu, 501-1193, Japan. Electronic address: ishida@gifu-u.ac.jp.

PMID: 31362138
DOI: 10.1016/j.carres.2019.107748

Abstract

Chemical syntheses of the bacterial diglucosyl diacylglycerols 1-heptadecanoyl-2-pentadecanoyl-3-O-[6-O-(β-d-glucopyranosyl)-β-d-glucopyranosyl]-sn-glycerol and 1-(cis-13-octadecenoyl)-2-palmitoyl-3-O-[2-O-(α-d-glucopyranosyl)-α-d-glucopyranosyl]-sn-glycerol are described. The syntheses feature the stereoselective construction of glycosidic linkages in glycosylation reaction by utilizing glycosyl donors with stereodirecting cyclic silyl protective groups. The 1,1,3,3-tetraisopropyldisiloxane-1,3-diyl (TIPDS) group was used for formation of the β-glycosidic linkage, while the di-tert-butylsilylene (DTBS) group was used for α-linkage formation. The silyl protective groups were chemoselectively cleavable without affecting acyl functionalities on the glycerol moiety and proved effective for the synthesis of diacylglycoglycerolipids.

Keywords: Diglycosyl diacylglycerol; Glycosylation; Silyl protective group; Stereodirecting; Stereoselective.

MeSH terms

Chemical Phenomena
Cyclization
Glycolipids / chemical synthesis*
Glycolipids / chemistry
Glycosides / chemistry*
Glycosylation
Molecular Structure
Stereoisomerism

Substances

Glycolipids
Glycosides
diglucosyl diacylglycerol