Zinc-Mediated Regiodiverse Synthesis of Vinyl Bromide Derivatives and Their in situ Palladium-Catalysed Cross-Coupling Reactions

Anne Miersch; Corinna Kohlmeyer; Gerhard Hilt

doi:10.1055/s-0033-1339616

Synthesis, Table of Contents

Synthesis 2013; 45(23): 3228-3232
DOI: 10.1055/s-0033-1339616

practical synthetic procedures

Zinc-Mediated Regiodiverse Synthesis of Vinyl Bromide Derivatives and Their in situ Palladium-Catalysed Cross-Coupling Reactions

Anne Miersch

Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35043 Marburg, Germany Fax: +49(6421)2825677 Email: Hilt@chemie.uni-marburg.de

,

Corinna Kohlmeyer

Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35043 Marburg, Germany Fax: +49(6421)2825677 Email: Hilt@chemie.uni-marburg.de

,

Gerhard Hilt*

Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35043 Marburg, Germany Fax: +49(6421)2825677 Email: Hilt@chemie.uni-marburg.de

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Abstract

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Dedicated to Prof. Dr. Reinhard W. Hoffmann on the occasion of his 80^th birthday. Many thanks for the fruitful and entertaining discussions.

Abstract

The synthesis of vinyl bromide derivatives was realised by a zinc-mediated addition of a benzylic bromide to a terminal alkyne. The geometry of the C=C bond is dependent on the amount of zinc powder applied. When 5 mol% of Zn is used, the Z-configured vinyl bromide is generated while with 150 mol% the E-geometry is obtained predominantly. In a three-component one-pot reaction, the in situ generated vinyl bromides were reacted further in a palladium-catalysed Suzuki cross-coupling reaction utilizing aromatic boronic acids to obtain trisubstituted double bonds in good overall yields. The reactions were conducted on a 5–20 mmol scale to visualise that the reactions are also capable of generating larger amounts of products.

Key words

alkynes - cross coupling - palladium - vinyl bromides - zinc

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References

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