Cobalt−chiral diphoshine catalytic systems promote intramolecular hydroacylation reactions of 2- acylbenzaldehydes and 2-alkenylbenzaldehydes to afford phthalide and indanone derivatives, respectively, in moderate to good yields with high enantioselectivities. The ketone hydroacylation did not exhibit a significant H/ D kinetic isotope effect (KIE) with respect to the aldehyde C−H bond, indicating that C−H activation would not be involved in the rate-limiting step.