Hydroboration of Terminal Alkynes Catalyzed by a Mn(I) Alkyl PCP Pincer Complex Following Two Diverging Pathways

A stereo- and regioselective Mn(I)-catalyzed hydroboration of terminal alkynes with pinacolborane (HBPin) is described. The hydroboration reaction is highly <i>Z</i>-selective in the case of aryl alkynes and <i>E</i>-selective in the case of aliphatic alkynes. The reaction requires no additives or solvents and proceeds with a catalyst loading of 1 mol % at 50-70 °C. The most active precatalyst is the bench-stable alkyl Mn(I) complex <i>cis</i>-[Mn(PCP-<i>i</i>Pr)(CO)₂(CH₂CH₂CH₃)]. The catalytic process is initiated by the migratory insertion of a CO ligand into the M<i>n</i>-alkyl bond to yield an acyl intermediate. This species undergoes C-H and B-H bond cleavage of the alkyne (aromatic alkynes) and HBPin (in the case of aliphatic alkynes) forming the active Mn(I) alkynyl and boryl catalysts [Mn(PCP-<i>i</i>Pr)(CO)(C≡CR)] and [Mn(PCP-<i>i</i>Pr)(CO)(BPin)], respectively. A broad variety of aromatic and aliphatic alkynes was efficiently and selectively borylated. Mechanistic insights are provided based on experimental data and DFT calculations. The functionalized alkenes can be used for further applications in cross-coupling reactions.