Transition-metal catalyzed C-H bond functionalization became an important tool to construct C-C bonds . In this context, non-directed nickel(0)-catalyzed (hetero)arene C(sp 2 )-H activations and downstream reaction with olefins opened a successful strategy towards olefin hydro-arylations under relatively mild conditions and full atom-efficiency (Fig. ) . Mechanistically, the underlying nickel-catalyzed C(sp )-H bond activation process operates via a ligand-to-ligand hydrogen transfer (LLHT) instead of the typical oxidative addition process . The C(sp 2 )-C(sp 3 )-reductive elimination is considered as the rate determining step (Figure ). Based on these findings, we hypothesized that an extension of this concept could help to address the α-C(sp )-H bond of ketones under comparable conditions and open new catalysis manifold for ketone α-functionalizations (Fig. ). This pivotal step could be either envisaged by coordination of the ketone and acceptor olefin to the nickel(0) triggering a LLHT of the carbonyl α-C(sp )-H. The LLHT would involve a 7-membered transition state and lead to a favorable oxa-π-allyl nickel(II) species. Alternatively, one could formulate a C(sp )-H oxidative addition forming oxa-π-allyl nickel(II) hydride. Subsequent insertion of the olefin would lead to the same alkyl nickel intermediate. The energy barrier of a straight C(sp )-C(sp ) reductive elimination leading to direct 1,2-hydroalkylation product is higher than a corresponding C(sp 2 )-C(sp ) reductive elimination . We thus hypothesized that the enhanced lifetime of the alkyl nickel intermediate would allow to trigger complexity-generating downstream reactions. For instance, alkyl Ni(II) species can engage in chain-walking processes . In the present context such increased molecular complexity comes together with challenges of controlling regio-, diastereo-, and ultimately enantioselectivity. Capitalizing on our long-standing experience in the design and application of chiral NHC ligands for Ni(0)catalyzed C-H functionalizations, we initiated the development of a competent catalyst system to address these challenges and channel.