Pd-Catalyzed decarboxylative cross-coupling reactions of epoxides with α,ß-unsaturated carboxylic acids.

A Pd-catalyzed decarboxylative cross-coupling of α,ß-unsaturated carboxylic acids with cyclic and acyclic epoxides has been developed. Both ß-monosubstituted and ß-disubstituted unsaturated carboxylic acids, as well as conjugated diene unsaturated carboxylic acids are suitable reaction substrates. Substituted homoallylic alcohols were obtained in moderate to good yields. The product was obtained as a mixture of diastereomers favoring the anti diastereomer of the cyclic epoxides. This work provides a method for the modification of complex organic molecules containing α,ß-unsaturated carboxylic acids.

Trisubstituted olefin synthesis via Ni-catalyzed hydroalkylation of internal alkynes with non-activated alkyl halides.

The stereoselective synthesis of tri-substituted alkenes is challenging. Herein, we report a Ni-catalyzed regio- and stereo-selective hydroalkylation of internal alkynes with non-activated alkyl halides. This method does not use any sensitive organometallic reagents and shows good functional group compatibility, which enables the efficient synthesis of many tri-substituted olefins from readily available coupling partners. It also provides a straightforward method for the modification of bioactive organic molecules.