title: Studies Toward the Syntheses of Pluramycin Natural Products. The First Total Synthesis of Isokidamycin.
abstract: We report the first total synthesis of the complex C-aryl glycoside isokidamycin, the epimer of the naturally-occurring pluramycin antibiotic kidamycin. The synthesis features a highly efficientDiels-Alder reaction between a substituted naphthyne and a glycosylatedfuran to form the anthracene core bearing a pendant angolosamine C-glycoside. The regiochemical outcome of the Diels-Alder reaction was controlled by employing a disposable silicon-tether to link the reactive napthyne and the glycosyl furan, rendering the cycloaddition intramolecular. The benzopyranone moietyof the aromatic nucleus was appended by cyclization of a functionalized vinylogous amide onto an advanced anthrol intermediate. The vancosamine amino glycoside was introduced by an O→C-glycoside rearrangement that produced the β-anomer. Subsequent refunctionalizations then led to isokidamycin.
authors.affiliation: Department of Chemistry and Biochemistry The University of Texas at Austin, 1 University Station A5300 Austin, TX 78712-0165.
authors.forename: B Michael
authors.initials: BM
authors.lastname: O'Keefe
authors.forename: Douglas M
authors.initials: DM
authors.lastname: Mans
authors.forename: David E
authors.initials: DE
authors.lastname: Kaelin
authors.forename: Stephen F
authors.initials: SF
authors.lastname: Martin