Direct Experimental Characterization of a Bridged Bicyclic Glycosyl Dioxacarbenium Ion by 1H and 13C NMR Spectroscopy: Importance of Conformation on Participation by Distal Esters
- 21 October 2021
- journal article
- research article
- Published by Wiley in Angewandte Chemie
- Vol. 60 (48), 25397-25403
- https://doi.org/10.1002/anie.202110212
Abstract
Low-temperature NMR studies with a 4- C -methyl-4- O -benzoyl galactopyranosyl donor enable for the first time the observation and characterization of a bridged bicyclic dioxacarbenium ion arising from participation by a distal ester. Variable temperature NMR studies reveal this bridged ion to decompose at temperatures above ~-30 °C. In the absence of the methyl group, the formation of a bicyclic ion is not observed. It is concluded that participation by typical secondary distal esters in glycosylation reactions is disfavored in the ground state conformation of the ester from which it is stereoelectronically impossible. Methylation converts the secondary ester to a conformationally more labile tertiary, removes this barrier, and renders participation more favorable. Nevertheless, the minor changes in selectivity in model glycosylation reactions on going from the secondary to the tertiary esters at both low and room temperature argue against distal group participation being a major stereodirecting factor even for the tertiary system.Funding Information
- National Institute of General Medical Sciences (GM62160)
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