Chemo‐ and Regiodivergent Allyl‐Propargyl Cross‐Coupling Reactions for the Construction of 1,4‐Enallenes and 1,5‐Enynes

Catalyst‐controlled divergent transformations represent a vital strategy for the efficient production of structurally diverse molecules from the same readily available precursors. Herein, we report the palladium/phosphine‐catalyst‐driven chemo‐ and regiodivergent allyl‐propargyl cross‐coupling of propargyl carbonates with allyl boronates. Density functional theory (DFT) calculations reveal that the bidentate phosphine ligand plays a crucial role in determining the relative favorability of possible reductive elimination modes from the ƞ 3 ‐allyl‐ƞ 1 ‐allenyl palladium intermediate species. Specifically, MeO‐BIPHEP facilitates the 1,1′‐reductive elimination to form the 1,4‐enallenes; in contrast, XantPhos favors the formation of 1,5‐enynes through a 3,3′‐reductive elimination pathway.