Ligand-controlled divergent copper-catalyzed enantioselective dihydroallylation and ring-opening hydroallylation of methylenecyclopropanes

We report a tunable, ligand-controlled protocol for the copper-hydride-catalyzed functionalization of methylenecyclopropanes (MCPs) with allyl phosphates. This divergent methodology enables selective access to two distinct classes of unsaturated scaffolds, dictated by the specific phosphine ligand employed. When the chiral bisphosphine ligand ( S,S )-Ph-BPE is utilized, the reaction proceeds via an enantioselective dihydroallylation cascade, affording nonconjugated chiral 1,9-dienes with high yields and excellent enantioselectivities (up to > 99% ee). Alternatively, switching the ligand to Xantphos confines the reaction at the ring-opening stage, selectively delivering nonconjugated 1,6-dienes via mono-allylation. Mechanistic studies support a stepwise pathway initiated by hydrocupration and β -carbon elimination, wherein the mono-allylated intermediate can be isolated and subsequently converted into the di-allylated product. The versatility of this platform is further demonstrated through a modular one-pot cascade employing two distinct allylic phosphates to generate structurally complex chiral dienes. Additionally, the catalytic system has been extended to carbonylative hydroallylation, providing efficient access to α , β -unsaturated ketones and chiral ketones. This strategy represents a robust approach for the stereoselective construction of diverse dienes and carbonyl-containing frameworks from strained ring systems.