Total Synthesis of (±)-Alopecuridine and Its Biomimetic Transformation into (±)-Sieboldine A

Authors

  • Xiao-Ming Zhang,

    1. Department of Chemistry, State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5557
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  • Prof. Dr. Yong-Qiang Tu,

    Corresponding author
    1. Department of Chemistry, State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5557
    • Department of Chemistry, State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5557===

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  • Prof. Dr. Fu-Min Zhang,

    1. Department of Chemistry, State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5557
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  • Hui Shao,

    1. Department of Chemistry, State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5557
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  • Xing Meng

    1. Department of Chemistry, State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000 (China), Fax: (+86) 931-891-5557
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  • This work was supported by the NSFC (Nos. 20921120404, 20672085, 20732002, and 20972059), the National Basic Research Program of China “973” program (2010CB833200), the “111” program of MOE, and the fundamental research funds for the central universities (lzujbky-2010-k09, lzujbky-2009-76, lzujbky-2009-158). We thank Prof. Yuan-Jiang Pan of Zhejiang University for high-resolution mass spectrometry analysis of compounds 9, 10, and 6.

Abstract

original image

Gerüst-Gymnastik: Die erste Totalsynthese des Lycopodium-Alkaloids Alopecuridin gelang mit 13 Schritten in der längsten linearen Sequenz; zudem konnte Alopecuridin biomimetisch über eine zweistufige Oxidation in Sieboldin A umgewandelt werden. Bei der Synthese kamen eine Semipinacol-Umlagerung eines funktionalisierten Rings mittlerer Größe und eine SmI2-vermittelte intramolekulare Pinacol-Kupplung zur Anwendung (siehe Schema; Boc=tert-Butoxycarbonyl).

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