Evidence for spontaneous release of acrylates from a transition-metal complex upon coupling ethene or propene with a carboxylic moiety or CO(2).

The development of a new synthetic approach to acrylates based on the formation of alkyl esters of acrylic acids has been studied. A preformed Pd-COOMe moiety is used as a model system to investigate the insertion of an olefin into the Pd--C bond. The fast elimination of acrylate is observed. Density functional calculations support the experimental findings and allow the characterization of transition states along the reaction pathway. The first example of olefin/CO(2) coupling with facile release of ethyl acrylate is also presented.