Kremsmair Alexander, Harenberg Johannes H, Schwärzer Kuno, Hess Andreas, Knochel Paul
Department of Chemistry, Ludwig-Maximilans-Universität München Butenandtstraße 5-13 81377 München Germany
Chem Sci. 2021 Mar 16;12(17):6011-6019. doi: 10.1039/d1sc00685a.
Polyfunctional organometallics of magnesium and zinc are readily prepared from organic halides a direct metal insertion in the presence of LiCl or a Br/Mg-exchange using iPrMgCl·LiCl (turbo-Grignard) or related reagents. Alternatively, such functionalized organometallics are prepared by metalations with TMP-bases (TMP = 2,2,6,6-tetramethylpiperidyl). The scope of these methods is described as well as applications in new Co- or Fe-catalyzed cross-couplings or aminations. It is shown that the use of a continous flow set-up considerably expands the field of applications of these methods and further allows the preparation of highly reactive organosodium reagents.
镁和锌的多官能有机金属化合物可通过有机卤化物轻松制备，即在LiCl存在下直接进行金属插入反应，或使用异丙基氯化镁·氯化锂（快速格氏试剂）或相关试剂进行溴/镁交换反应。另外，此类官能化有机金属化合物可通过用TMP碱（TMP = 2,2,6,6-四甲基哌啶基）进行金属化反应来制备。本文描述了这些方法的适用范围以及在新型钴或铁催化的交叉偶联反应或胺化反应中的应用。结果表明，采用连续流动装置可显著拓展这些方法的应用领域，并进一步实现高活性有机钠试剂的制备。
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