ja7b09420_si_001.pdf (8.76 MB)
Site-Selective, Copper-Mediated O‑Arylation of Carbohydrate Derivatives
journal contribution
posted on 2017-10-23, 13:03 authored by Victoria Dimakos, Graham E. Garrett, Mark S. TaylorSite-selective functionalization
of hydroxy groups in sugar derivatives
is a major challenge in carbohydrate synthesis. Methods for achieving
this goal will provide efficient access to new sugar-derived chemical
building blocks and will facilitate the preparation or late-stage
modification of complex oligosaccharides for applications in glycobiology
research and drug discovery. Here, we describe site-selective, copper-promoted
couplings of boronic acids with carbohydrate derivatives. These reactions
generate sugar-derived aryl ethers, a structural class that is challenging
to generate by other means and has not previously been accessed in
a site-selective fashion. Experimental evidence and computational
modeling suggest that the formation of a sugar-derived boronic ester
intermediate is crucial to the selectivity of these processes, accelerating
the arylation of an adjacent hydroxy group. The results demonstrate
how the interactions of sugars with boron compounds can be combined
with transition metal catalysis to achieve new chemical reactivity.
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sugar-derived boronic esterlate-stage modificationtransition metal catalysischemical reactivityboronic acidssugar-derived chemical building blocksdrug discoveryExperimental evidenceCarbohydrate Derivatives Site-selective functionalizationhydroxy groupsite-selective fashioncarbohydrate derivativeshydroxy groupscarbohydrate synthesisboron compoundssugar-derived aryl etherscopper-promoted couplingsglycobiology researchsugar derivatives
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