We reported a remote control glycosylation method using the picoloyl protecting group for 2-deoxy-β-glycosidic bond formation. The method is applicable to various 2-deoxythioglycosyl donors and the utility is illustrated by the synthesis of a deoxytrisaccharide component of landomycins.
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http://dx.doi.org/10.1039/c4cc08465a | DOI Listing |
J Org Chem
November 2022
Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry and Sichuan Province, Sichuan Engineering Laboratory for Plant-Sourced Drug and Sichuan Research Center for Drug Precision Industrial Technology, West China School of Pharmacy, Sichuan University, Chengdu 610041, P. R. China.
Inulin-type fructooligosaccharides (FOSs) constitute an abundant subgroup of fructans with important biological activities. However, the availability of individual fructooligosaccharides with an accurate structure in high purity and quality remains challenging. We herein report the first iterative synthesis of five inulin-type FOSs with degrees of polymerization ranging from 3 to 7 via highly stereoselective β-(2 → 1)-d-fructofuranosylation on a gram scale.
View Article and Find Full Text PDFFront Chem
September 2022
Department of Chemistry, Saint Louis University, St. Louis, MO, United States.
Presented herein is a streamlined synthesis of building blocks of a rare sugar D-altrosamine. Also investigated was the glycosylation of different glycosyl acceptors with differentially protected altrosamine donors. High facial stereoselectivity was achieved with 3--picoloyl donors and reactive glycosyl acceptors the H-bond-mediated aglycone delivery (HAD) pathway.
View Article and Find Full Text PDFChemistry
March 2021
Institut de Chimie des Substances Naturelles, UPR 2301, CNRS Université Paris-Saclay, 91198, Gif-sur-Yvette, France.
We give a full account of the total synthesis of tiacumicin B (Tcn-B), a natural glycosylated macrolide with remarkable antibiotic properties. Our strategy is based on our experience with the synthesis of the tiacumicin B aglycone and on unique 1,2-cis-glycosylation steps. We used sulfoxide anomeric leaving-groups in combination with a remote 3-O-picoloyl group on the donors that allowed highly β-selective rhamnosylation and noviosylation that rely on H-bond-mediated aglycone delivery.
View Article and Find Full Text PDFOrg Biomol Chem
September 2020
Department of Chemistry and Biochemistry, University of Missouri - St. Louis, One University Boulevard, St. Louis, MO 63121, USA.
O-Picoloyl protecting groups at remote positions can affect the stereoselectivity of glycosylation by means of the H-bond-mediated aglycone delivery (HAD) pathway. A new practical method for the stereoselective synthesis of β-glycosides of mannosamine is reported. The presence of the O-picoloyl group at the C-3 position of a mannosamine donor can provide high or complete stereocontrol.
View Article and Find Full Text PDFOrg Biomol Chem
July 2020
Department of Chemistry and Biochemistry, University of Missouri - St Louis, One University Boulevard, St Louis, MO 63121, USA.
The picoloyl ester (Pico) has proven to be a versatile protecting group in carbohydrate chemistry. It can be used for the purpose of stereocontrolling glycosylations via an H-bond-mediated Aglycone Delivery (HAD) method. It can also be used as a temporary protecting group that can be efficiently introduced and chemoselectively cleaved in the presence of practically all other common protecting groups used in synthesis.
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