Studies Toward the Syntheses of Pluramycin Natural Products. The First Total Synthesis of Isokidamycin |
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Authors: | O'Keefe B Michael Mans Douglas M Kaelin David E Martin Stephen F |
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Institution: | Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station A5300 Austin, TX 78712-0165, United States |
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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 efficient Diels-Alder reaction between a substituted naphthyne and a glycosylated furan to form the anthracene core bearing a pendent angolosamine C-glycoside. The regiochemical outcome of the Diels-Alder reaction was controlled by employing a disposable silicon tether to link the reactive naphthyne and the glycosyl furan, rendering the cycloaddition intramolecular. The benzopyranone moiety of 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. |
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Keywords: | Aryne Diels-Alder Glycosyl furans C-Aryl glycosides Pluramycins Carbonylative cross-coupling Natural products Total synthesis |
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