Explorations in Organic Chemistry Leading to the Total Synthesis of (±)-Gelsemine

The total synthesis of (±)-gelsemine (1) is described. A defining phase of the effort involved recourse to a strategic oxetane ring (see compound 25). It was constructed anticipating an intramolecular displacement of the carbon (C17)−oxygen (O4) bond (see product 48). A key intermediate in the stere...

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Veröffentlicht in:Journal of the American Chemical Society 2002-08, Vol.124 (33), p.9812-9824
Hauptverfasser: Ng, Fay W, Lin, Hong, Danishefsky, Samuel J
Format: Artikel
Sprache:eng
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Zusammenfassung:The total synthesis of (±)-gelsemine (1) is described. A defining phase of the effort involved recourse to a strategic oxetane ring (see compound 25). It was constructed anticipating an intramolecular displacement of the carbon (C17)−oxygen (O4) bond (see product 48). A key intermediate in the stereospecific elaboration of the oxetane linkage was enone 22, which was susceptible to two β-face attacks leading to 24 and, thence, 25. Three sigmatropic rearrangements were employed in building the bridgehead (C20) and the spiroanilide (C7) quaternary centers en route to gelsemine.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0204675