The metal-catalyzed hydrogenation of epoxides has advanced rapidly in recent years. In particular, several ruthenium and iron complexes capable of Noyori-type bifunctional catalysis have been shown to selelctively produce the branched isomer of the alcohol product, resulting from hydride attack at the less hindered carbon. Previous reports suggested a Noyori-type mechanism where hydride and proton are transferred together to the carbon and oxygen atoms of the epoxide substrate in a concerted manner. We describe here a comprehensive computational and kinetic study on epoxide hydrogenation catalyzed by PNP and PNN-pincer ruthenium complexes featuring an NH group on the ligand. Our work shows that the key epoxide ring-opening step proceeds not through a Noyori-type concerted mechanism, but through an opposite-side attack of the ruthenium hydride on the epoxide carbon.

Mechanism of ruthenium-cataylzed epoxide hydrogenation

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