Catalysis in water: Highly efficient synthesis of heptadienoic acids by rearrangement of allyl but-3-enoate promoted by Rh(I) complexes

A practical and efficient protocol has been developed to realize the catalytic rearrangement of allyl but-3-enoate to heptadienoic acids in NaHCO3 saturated water, in the presence of catalytic amounts of a rhodium(I) complex, containing olefin, diene or phosphine ligands. The reaction mainly affords the sodium salt of E-2,6-heptadienoic acid, with high catalytic efficiency (3600 TON). A reaction scheme of the process is proposed. The reaction course differs from that observed in organic solvents, where E-3,6-heptadienoic acid is formed predominantly.

Graphical abstractA simple and efficient protocol was developed to realize in aqueous media the rearrangement of allyl but-3-enoate to heptadienoic acids in saturated NaHCO3 water, in the presence of catalytic amounts of a rhodium(I) complex, containing olefin or diene ligands. The reaction affords mainly the sodium salt of E-2,6-heptadienoic acid, with high catalytic efficiency (3600 TON).Figure optionsDownload full-size imageDownload as PowerPoint slide