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.
Carbohydr Res. 2019 Sep 1;483:107748. doi: 10.1016/j.carres.2019.107748. Epub 2019 Jul 18.
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.
细菌二葡糖基二酰基甘油 1-十七烷酰基-2-十五烷酰基-3-O-[6-O-(β-D-吡喃葡萄糖基)-β-D-吡喃葡萄糖基]-sn-甘油和 1-(顺-13-十八烯酰基)-2-棕榈酰基-3-O-[2-O-(α-D-吡喃葡萄糖基)-α-D-吡喃葡萄糖基]-sn-甘油的化学合成描述如下。这些合成方法的特点是通过利用具有立体定向环状硅基保护基的糖基供体，在糖基化反应中立体选择性地构建糖苷键。1,1,3,3-四异丙基二硅氧烷-1,3-二基（TIPDS）基团用于形成β-糖苷键，而二叔丁基硅烯（DTBS）基团用于α-键形成。硅基保护基可通过化学选择性裂解，而不影响甘油部分上的酰基官能团，并且对二酰基甘油糖脂的合成有效。
