Identifying a general method of anomeric selectivity in glycosylation reactions remains a significant challenge in organic chemistry. While the use of participating groups at the neighboring carbon to impart selectivity has been long known, such approaches are not possible with 2-deoxy sugars. In pursuit of donor-independent control for direct glycosylations, our group has developed methods for controlling selectivity in couplings with 2-deoxy donors through promoter control. Using <i>p</i>-toluensulfonyl chloride, β-selective glycosylations could be performed at up to gram scale. During the course of the project, it was unexpectedly found that the use of 2,4,6-triisopropylbenzenesulfonyl chloride could provide strong α-selectivity for couplings with the 2,3,6-trideoxy donors. In order to test the applicability and generality for these methods of selectivity, the pentasaccharide fragment of Saquayamycin Z, consisting of alternating α and β glycoside bonds, was used as model system. Through the use of the two benzenesulfonyl chloride promoters we were able to complete the synthesis of the pentasaccharide chain of Saquayamycin Z with moderate to high yield for each coupling, demonstrating the scope of this method of reagent control. Additionally, the unexpected results of this study have led us to examine the relationship between glycosyl donor reactivity and the reactivity of the sulfonate for controlling selectivity, with the ultimate goal of devising a general method of donor-independent β-selective glycosylation of 2-deoxy and full sugars.<br/>

Promoter controlled glycosylation of 2-deoxy sugars: Synthesis of the saquayamycin Z pentasaccharide

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.