Ruthenium Complex Catalyzed Intermolecular Hydroacylation and Transhydroformylation of Olefins with Aldehydes

Article abstract of DOI:10.1021/jo00291a035

Low-valent ruthenium complexes such as dodecacarbonyltriruthenium (Ru3(CO)12), (η⁴-1,5-cyclooctadiene)(η⁶-1,3,5-cyclooctatriene)ruthenium (Ru(COD)(COT)) and bis(η⁵-cyclooctadienyl)ruthenium showed high catalytic activity for the intermolecular hydroacylation of olefins with various aromatic and heteroaromatic aldehydes at 180-200 deg C for 24-48 h under an initial carbon monoxide pressure of 20 kg cm^-2 to give unsymmetric ketones in moderate to good yields.In the reaction of 2-thiophenecarbaldehyde with cyclohexene, cyclohexyl 2-thienyl ketone was obtained in 62 percent yield.On the other hand, when the aliphatic aldehyde, heptanal, was treated with cyclohexene, the corresponding ketone was not obtained at all, and a transhydroformylation reaction proceeded; i.e., the formyl group of heptanal was apparently transformed to cyclohexene to give cyclohexanecarbaldehyde in 29 percent yield, together with their Tishchenko-type reaction products.