A novel ruthenium catalyst system of [PPN][Ru3H(CO)(11)]/PCy3 [PPN = bis(tr
iphenylphosphine)iminium, Cy = cyclohexyl] for the direct hydroamidation an
d hydroesterification of alkenes with formamides and alkyl formates has bee
n developed. These addition reactions proceeded smoothly under an argon atm
osphere, and carbon monoxide is not needed to suppress decarbonylation of f
ormyl compounds or to maintain the catalytic activity.