Heck arylations of pent-4-enoates or allylmalonate using a palladium/tetraphosphine catalyst

The Heck reaction of aryl halides with functionalised alk-1-enes should be a powerful method for the synthesis of functionalised (E)-1-arylalk-1-ene derivatives. The major problem of this reaction is the palladium-catalysed migration of the carbon–carbon double bond along the alkyl chain when there are no substituents on the C3 carbon of the alk-1-enes. We observed that for the arylation of ethyl pent-4-enoate, ethyl 2-methylpent-4-enoate or dimethyl allylmalonate this migration could be partially or completely controlled using appropriate reaction conditions. The ramification on the alkyl chain and the substituents on the aryl halide have also an important influence on this migration. Moreover, the cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane/1/2[PdCl(C3H5)]2 system catalyses this reaction with a wide range of aryl bromides using very high ratio substrate/catalyst in good yields.

Graphical abstractcis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/1/2[PdCl(C3H5)]2 system catalyses the Heck reactions of pent-4-enoates or dimethyl allylmalonate with a wide range of aryl bromides with medium to high selectivity and in high ratio substrate/catalyst.Figure optionsDownload full-size imageDownload as PowerPoint slide