Efficient E-Selective Transfer Semihydrogenation of Alkynes by Means of Ligand-Metal Cooperating Ruthenium Catalyst

The manuscript describes an efficient protocol for the E‐selective transfer semihydrogenation of internal alkynes employing a previously described bifunctional ruthenium‐based PC(sp3)P complex, 20 mol% of sodium formate and nearly stoichiometric formic acid. Semihydrogenation of the terminal alkynes results in the formation of the corresponding styrenes. The mechanism of the reaction includes stepwise transfer of both the hydride and the proton of the formic acid to the substrate. This fact allowed for the development of a facile protocol for the synthesis of monodeuterated alkenes by simply applying formic acid/sodium formate/D2O mixture as a hydrogen source. High yields, selectivity and functional group compatibility have been generally achieved.