%0 Journal Article %A Tay, Jia-Hui %A Argüelles, Alonso J. %A DeMars, Matthew D. %A Zimmerman, Paul M. %A Sherman, David H. %A Nagorny, Pavel %D 2017 %T Regiodivergent Glycosylations of 6‑Deoxy-erythronolide B and Oleandomycin-Derived Macrolactones Enabled by Chiral Acid Catalysis %U https://acs.figshare.com/articles/journal_contribution/Regiodivergent_Glycosylations_of_6_Deoxy-erythronolide_B_and_Oleandomycin-Derived_Macrolactones_Enabled_by_Chiral_Acid_Catalysis/5116366 %R 10.1021/jacs.7b03198.s001 %2 https://ndownloader.figshare.com/files/8687686 %K chiral acids %K C 11 positions %K macrolactone %K Regiodivergent Glycosylations %K Oleandomycin-Derived Macrolactones Enabled %K rr %K SPINOL-based CPAs %K glycosyl %K reaction mechanism %K C 5 positions %K anomeric phosphates %K introduction %K C 3 alcohol %K boronic acids %K chiral catalysts %K traceless protection %K C 11 position %K control site-selectivity %K BINOL-based chiral phosphoric acids %K reactive intermediates %K selectivity switch %X This work describes the first example of using chiral catalysts to control site-selectivity for the glycosyl­ations of complex polyols such as 6-deoxy­erythro­nolide B and oleando­mycin-derived macrolactones. The regio­divergent introduction of sugars at the C3, C5, and C11 positions of macrolactones was achieved by selecting appropriate chiral acids as catalysts or through introduction of stoichio­metric boronic acid-based additives. BINOL-based chiral phosphoric acids (CPAs) were used to catalyze highly selective glycosyl­ations at the C5 positions of macrolactones (up to 99:1 rr), whereas the use of SPINOL-based CPAs resulted in selectivity switch and glycosyl­ation of the C3 alcohol (up to 91:9 rr). Additionally, the C11 position of macrolactones was selectively function­alized through traceless protection of the C3/C5 diol with boronic acids prior to glycosyl­ation. Investigation of the reaction mechanism for the CPA-controlled glycosyl­ations revealed the involvement of covalently linked anomeric phosphates rather than oxo­carbenium ion pairs as the reactive intermediates. %I ACS Publications