Organic and Inorganic Chemistry

Substituted styrenes are key building blocks in organic synthesis, and are widely used in the manufacturing of fine chemicals and polymers. Moreover, the vinyl group can be used as a hub for further functionalization, for example, by olefin metathesis, carboxylation, (asymmetric) hydrofunctionalization, or heterocycle synthesis. Acrylic acid is presented as an inexpensive, nonvolatile vinylating agent in a palladium-catalyzed decarboxylative vinylation of aryl halides. The reaction proceeds through a Heck reaction of acrylic acid, immediately followed by protodecarboxylation of the cinnamic acid intermediate. The use of the carboxylate group as a deciduous directing group ensures high selectivity for monoarylated products. The vinylation process is generally applicable to diversely substituted substrates. Its utility is shown by the synthesis of drug-like molecules and the gram-scale preparation of key intermediates in drug synthesis.