Selective Manganese-Catalyzed Dimerization and Cross-Coupling of Terminal Alkynes

[Image: see text] Herein, efficient manganese-catalyzed dimerization of terminal alkynes to afford 1,3-enynes is described. This reaction is atom economic, implementing an inexpensive, earth-abundant nonprecious metal catalyst. The precatalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe)(CO)(3)(CH(2)CH(2)CH(3))]. The catalytic process is initiated by migratory insertion of a CO ligand into the Mn–alkyl bond to yield an acyl intermediate that undergoes rapid C–H bond cleavage of alkyne, forming an active Mn(I) acetylide catalyst [Mn(dippe)(CO)(2)(C≡CPh)(η(2)-HC≡CPh)] together with liberated butanal. A range of aromatic and aliphatic terminal alkynes were efficiently and selectively converted into head-to-head Z-1,3-enynes and head-to-tail gem-1,3-enynes, respectively, in good to excellent yields. Moreover, cross-coupling of aromatic and aliphatic alkynes selectively yields head-to-tail gem-1,3-enynes. In all cases, the reactions were performed at 70 °C with a catalyst loading of 1–2 mol %. A mechanism based on density functional theory (DFT) calculations is presented.