Studies toward the syntheses of pluramycin natural products. The first total synthesis of isokidamycin

TETRAHEDRON

卷:67

Article

O'Keefe, B. Michael¹  Mans, Douglas M.¹  Kaelin, David E., Jr.¹  Martin, Stephen F.¹ 

[1] Univ Texas Austin, Dept Chem & Biochem, Austin, TX 78712 USA

关键词: Aryne;    Diels-Alder;    Glycosyl furans;    C-Aryl glycosides;    Pluramycins;    Carbonylative cross-coupling;    Natural products;    Total synthesis;   

DOI  :  10.1016/j.tet.2011.05.117

来源: Elsevier

【 摘 要 】

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 beta-anorner. Subsequent refunctionalizations then led to isokidamycin. (C) 2011 Elsevier Ltd. All rights reserved.

【 授权许可】

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