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

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(CH₂CH₂CH₃)]. 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)(η²-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.