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

Sven Krieck; Philipp Schüler; Jan M. Peschel; Matthias Westerhausen

doi:10.1055/s-0037-1610407

Synthesis, Table of Contents

CC BY ND NC 4.0 · Synthesis 2019; 51(05): 1115-1122
DOI: 10.1055/s-0037-1610407

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

Authors

Sven Krieck
Philipp Schüler
Jan M. Peschel
Matthias Westerhausen *

Friedrich Schiller University Jena, Institute of Inorganic and Analytical Chemistry, Humboldtstraße 8, D-07743 Jena, Germany Email: m.we@uni-jena.de

Abstract

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Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

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

Key words

calcium amides - hexamethyldisilazides - silylamides - alkaline earth metal amides - amidocalcium complexes

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References

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Supplementary Material

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