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Calcium bis[bis(trimethylsilyl)amide] (Ca(HMDS)2) is a widely used reagent in diverse stoichiometric and catalytic applications. These processes necessitate a straightforward and large-scale access of this complex. Calcium does not react with primary and secondary amines, but the addition of excess bromoethane to a mixture of calcium turnings and amines in THF at room temperature yields the corresponding calcium bis(amides), calcium bromide and ethane. This in situ Grignard metalation method (iGMM) allows the preparation of calcium bis(amides) from secondary and primary trialkylsilyl-substituted amines and anilines on a multigram scale. 1 Background 2 The In Situ Grignard Metalation Method (iGMM) 3 Properties of [(thf)2M(HMDS)2] 4 Applications and Perspective

Straightforward One-Pot Syntheses of Silylamides of Magnesium and Calcium via an In Situ Grignard Metalation Method