title: Diastereoselective additions of allylmetal reagents to free and protected syn-α,β-dihydroxyketones enable efficient synthetic routes to methyl trioxacarcinoside A.
abstract: Two routes to the 2,6-dideoxysugar methyl trioxacarcinoside A are described. Each was enabled by an apparent α-chelation-controlled addition of an allylmetal reagent to a ketone substrate containing a free α-hydroxyl group and a β-hydroxyl substituent, either free or protected as the corresponding di-tert-butylmethyl silyl ether. Both routes provide practical access to gram quantities of trioxacarcinose A in a form suitable for glycosidic coupling reactions.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Smaltz
authors.forename: Jakub
authors.initials: J
authors.lastname: Švenda
authors.forename: Andrew G
authors.initials: AG
authors.lastname: Myers
mesh_terms: D002614:Chelating Agents / Q000737:chemistry; D006027:Glycosides / Q000138:chemical synthesis* / Q000737:chemistry; D007202:Indicators and Reagents; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D002614:Chelating Agents; D006027:Glycosides; D007202:Indicators and Reagents; D007659:Ketones; C572691:methyl trioxacarcinoside A