Ruthenium-Catalyzed Alkoxycarbonylation of Alkenes with Paraformaldehyde as a Carbon Monoxide Substitute

The first efficient use of paraformaldehyde in the alkoxycarbonylation of alkenes is reported. Using a combination of readily available [Ru-3(CO)(12)] and PCy3 (Cy=cyclohexyl) as catalyst, industrially important esters are produced in good to high yield (up to 90%) at relatively low temperature. This new method is applicable to a series of alkenes and alcohols. Moreover, the use of formaldehyde as the carbonyl source provides the potential to avoid both reliance on CO in carbonylation reactions, and the requirement for special high-pressure reactors.