The in‐situ Grignard addition method adds intermediately prepared organo alkaline‐earth metal halides onto a suitable substrate. Here, freshly rasped calcium and the carbodiimide R′─N═C═N─R′ (R′ = SiMe 3 , i Pr) are suspended in THF at room temperature and then an organyl halide R─X (X = Br, I) is added.…
Im Vergleich zu Magnesium-basierten Grignard-Reagenzien finden Calcium-Grignard-Verbindungen eine deutlich geringere Aufmerksamkeit in der anorganischen und organischen Synthesechemie. Eine breite Anwendung ist insbesondere auf eine begrenzte Auswahl an Zugangswegen zurückzuführen, welche durch die Reaktionsträgheit…
Organocalcium compounds are highly reactive reagents whereas the alkaline-earth metal itself is a weak reductant. This discrepancy hampered a straightforward development of an organocalcium chemistry. The in situ generation of the highly reactive organocalcium reagent and immediate metalation of a H-acidic…
London: The Royal Society of Chemistry, 2024-08-05
Abstract The alkaline‐earth metals Mg and Ca are too inert for the direct metalation of primary and secondary amines. Consequently, activation prior to use is required. Alternatively, the Grignard reagents RMgX (R=alkyl, aryl, X=halide) can be applied in metalation of amines. However, such a straightforward…
Magnesium and calcium are too inert to deprotonate amines directly. For the synthesis of bulky amides alternative strategies are required and in the past, N ‐bound trialkylsilyl groups have been used to ease metalation reactions. The in situ Grignard reagent formation in stirred suspensions of magnesium…
The in situ Grignard Metalation Method ( i GMM) is a straightforward one‐pot procedure to quickly produce multigram amounts of Hauser bases R 2 N‐MgBr which are valuable and vastly used metalation reagents and novel electrolytes for magnesium batteries. During addition of bromoethane to a suspension…
The in situ Grignard Metalation Method ( i GMM) is a straightforward one‐pot strategy to synthesize alkaline‐earth metal amides in multi‐gram scale with high yields via addition of bromoethane to an ethereal suspension of a primary or secondary amine and magnesium (Part I) or calcium (Part II). This…