Chuanzhi Sun, Mingshu Liu, Haitao Sun, Fang Hang, Nan Sun and Dezhan Chen (DOI: 10.1002/qua.24791) study the detailed mechanism of rutheniumcatalyzed terminal alkyne hydroboration using density functional theory. The results suggest that the reaction proceeds by alkyne rearrangement and catalyst regeneration with formation of E- and Z-vinylboronates. Noncovalent interaction between the BH bond and the Ru center determines the preferred reaction pathway. A hypothetical control model using 1,2-dimethyl acetylene (internal alkyne) and styrene (terminal alkene) as substrates indicates that the activation barrier of the rate-determining process is too high, which makes the hydroboration of styrene and 1,2-dimethyl acetylene difficult.