Ruthenium-catalysed alkoxycarbonylation of alkenes with carbon dioxide

Alkene carbonylations represent a major technology for the production of value-added bulk and fine chemicals. Nowadays, all industrial carbonylation processes make use of highly toxic and flammable carbon monoxide. Here we show the application of abundantly available carbon dioxide as C1 building block for the alkoxycarbonylations of industrially important olefins in the presence of a convenient and inexpensive ruthenium catalyst system. In our system, carbon dioxide works much better than the traditional combination of carbon monoxide and alcohols. The unprecedented in situ formation of carbon monoxide from carbon dioxide and alcohols permits an efficient synthesis of carboxylic acid esters, which can be used as detergents and polymer-building blocks. Notably, this transformation allows the catalytic formation of C–C bonds with carbon dioxide as C1 source and avoids the use of sensitive and/or expensive reducing agents (for example, Grignard reagents, diethylzinc or triethylaluminum). The conversion of alkenes to esters is performed on a large scale worldwide, but relies on the use of toxic and flammable carbon monoxide. Here, the authors show a catalytic system where carbon dioxide—normally unreactive, but cheap and abundant—can be employed instead.