Ni-Catalyzed Alkylative Dimerization of Vinyl Grignard Reagents Using Alkyl Fluorides

Key words

Grignard reagents - alkyl fluorides - alkylation

Significance

For this reaction, alkyl fluorides were found superior as alkylating agents than alkyl chlorides and iodides. Vinylmagnesium chloride serves here as a useful C4-synthon for the construction of a branched carbon skeleton, potentially applicable in various synthetic schemes.

Comment

This approach will be useful for the synthesis of complex molecules and natural products. Alkyl fluorides are usually inert during the most synthetic transformations, thus serving as a ‘protection’ group before being activated by this method. The reaction itself looks very promising as a new tool for selective C-C bond formation. The tentative mechanism includes the formation of cyclic (2-butene-1,4-diyl)magnesium by reductive coupling of two vinyl moieties on the Ni center, which react further with alkyl fluorides.