Selektive Metallierung von Halogenarenen mit Cupraten

Authors

  • Prof. Dr. Yoshinori Kondo,

    1. Department of Heterocyclic Chemistry Faculty of Pharmaceutical Sciences, Tohoku University Aobayama, Aoba-ku, Sendai 980–77 (Japan) Telefax: Int. + 22/217–6864
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  • Tetsuji Matsudaira,

    1. Department of Heterocyclic Chemistry Faculty of Pharmaceutical Sciences, Tohoku University Aobayama, Aoba-ku, Sendai 980–77 (Japan) Telefax: Int. + 22/217–6864
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  • Junko Sato,

    1. Department of Heterocyclic Chemistry Faculty of Pharmaceutical Sciences, Tohoku University Aobayama, Aoba-ku, Sendai 980–77 (Japan) Telefax: Int. + 22/217–6864
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  • Naoko Murata,

    1. Department of Heterocyclic Chemistry Faculty of Pharmaceutical Sciences, Tohoku University Aobayama, Aoba-ku, Sendai 980–77 (Japan) Telefax: Int. + 22/217–6864
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  • Prof. Dr. Takao Sakamoto

    Corresponding author
    1. Department of Heterocyclic Chemistry Faculty of Pharmaceutical Sciences, Tohoku University Aobayama, Aoba-ku, Sendai 980–77 (Japan) Telefax: Int. + 22/217–6864
    • Department of Heterocyclic Chemistry Faculty of Pharmaceutical Sciences, Tohoku University Aobayama, Aoba-ku, Sendai 980–77 (Japan) Telefax: Int. + 22/217–6864
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Abstract

Regioselektiv und nahezu ohne Verlust an Enantiomerenreinheit wird mit [Li3ZnMe3(SCN)2] das 5-exo-(2) und mit [Li3Cu(CN)Me3] das 6-endo-Cyclisierungsprodukt (3) aus dem Epoxid 1 gebildet. Ohne weitere Reagentien gelingt so durch Halogen-Metall-Austausch mit dem jeweiligen At-Komplex und anschließende intramolekulare Epoxidöffnung durch die Arylcuprateinheit die asymmetrische Synthese von 2 und 3, die Vorstufen der Antibiotica CC-1065 und Duocarmycin sind.

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