the hydrolysis of which results in the hydroacylation products. a The herein presented approach to olefin hydroacylation is a novel concept whereby ketone synthesis can be achieved by the direct, metal-free coupling of secondary amides and alkenes. This obviates the need for transition metal catalysis and proceeds by an entirely new mechanism that neither requires directing groups nor suffers from deleterious decarbonylation. This work also showcases the potential of carefully designed internal hydride transfer events to provide unique solutions for fundamental, contemporary challenges in organic synthesis.