Evolution of a Synthetic Strategy:  Total Synthesis of (±)-Welwitindolinone A Isonitrile

An efficient and highly stereoselective total synthesis of the natural product (±)-welwitindolinone A isonitrile (1) is described. The bicyclo[4.2.0]octane core of 1 was established by a regio- and diastereoselective [2+2] ketene cycloaddition. The C12 quaternary center and vicinal stereogenic chlor...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2008-02, Vol.130 (6), p.2087-2100
Main Authors: Reisman, Sarah E, Ready, Joseph M, Weiss, Matthew M, Hasuoka, Atsushi, Hirata, Makoto, Tamaki, Kazuhiko, Ovaska, Timo V, Smith, Catherine J, Wood, John L
Format: Article
Language:English
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Summary:An efficient and highly stereoselective total synthesis of the natural product (±)-welwitindolinone A isonitrile (1) is described. The bicyclo[4.2.0]octane core of 1 was established by a regio- and diastereoselective [2+2] ketene cycloaddition. The C12 quaternary center and vicinal stereogenic chlorine were installed in a single operation with excellent stereocontrol via a chloronium ion mediated semipinacol rearrangement. Described strategies for construction of the spiro-oxinole include a SmI2−LiCl mediated reductive cyclization and a novel anionic cyclization that simultaneously constructs the spiro-oxindole and vinyl isonitrile moieties.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja076663z