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Preparation of functionalized organoaluminiums by direct insertion of aluminium to unsaturated halides

Nature Chemistry volume 2, pages 313–318 (2010)Cite this article

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Abstract

The preparation of polyfunctional organometallics is important in organic synthesis as these reagents are very popular nucleophiles. The preparation of functionalized aluminium reagents by direct insertion of aluminium powder is in general not possible. Such a reaction would be of special importance owing to the low price of aluminium compared with magnesium (it is half the price), the low toxicity of this metal and the chemoselectivity of the resultant organoaluminium reagents. We have now found that by adding catalytic amounts of selected metallic chlorides (TiCl4, BiCl3, InCl3 or PbCl2) in the presence of LiCl, aluminium powder inserts into various unsaturated iodides and bromides under mild conditions. These resulting new organoaluminium reagents undergo smooth Pd-catalysed cross-coupling and acylation reactions, as well as copper-catalysed allylic substitutions, affording various interesting products for pharmaceutical and material science applications.

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Acknowledgements

Y.-H.C. thanks the Humboldt Foundation for financial support. We thank the Fonds der Chemischen Industrie, the DFG and the European Research Council for financial support. We thank Chemetall and BASF for the generous gift of chemicals.

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Authors and Affiliations

  1. Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13, Haus F. 81377, München, Germany

    Tobias Blümke, Yi-Hung Chen, Zhihua Peng & Paul Knochel

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  1. Tobias Blümke
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  2. Yi-Hung Chen
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  3. Zhihua Peng
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  4. Paul Knochel
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Contributions

T.B. and Y.-H.C. contributed equally to this work. Z.P. assisted in conducting and analysing the chemical experiments. P.K. designed and directed the project and wrote the manuscript with contributions from Y.-H.C. and T.B. All authors contributed to discussions.

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Correspondence to Paul Knochel.

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Blümke, T., Chen, YH., Peng, Z. et al. Preparation of functionalized organoaluminiums by direct insertion of aluminium to unsaturated halides. Nature Chem 2, 313–318 (2010). https://doi.org/10.1038/nchem.590

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