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In‐situ‐Abfangmethode Zur Metallierung Funktionalisierter Arene Und Heteroarene Mit TMPLi In Gegenwart Von ZnCl2 Und Anderen Metallsalzen

Annette Frischmuth, M. Fernández, Nadja M. Barl, Florian Achrainer, H. Zipse, G. Berionni, H. Mayr, K. Karaghiosoff, P. Knochel
Published 2014 · Chemistry

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Zugabe von TMPLi zu Mischungen einer aromatischen oder heteroaromatischen Verbindung und eines Metallsalzes, beispielsweise MgCl2, ZnCl2 oder CuCN, bei −78 °C fuhrt zunachst zu einer Lithiierung des Arens gefolgt von einer Transmetallierung mit dem Metallsalz zu funktionalisierten Mg-, Zn- bzw. Cu-Organometallverbindungen. Diese In-situ-Abfangmethode ermoglicht die schnelle Metallierung einer Vielzahl an empfindlichen Pyridinen (mit Nitro-, Ester-, oder Cyangruppen) und gestattet die Herstellung kinetischer Regioisomere funktionalisierter Arene und Heterocyclen, die durch ubliche Metallierungsreagentien wie TMPMgCl⋅LiCl oder TMPZnCl⋅LiCl nicht zuganglich sind.
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