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

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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