Polymethylhydrosiloxane (PMHS) as Sustainable Reductant in the Titanocene Catalyzed Epoxide Hydrosilylation

Here, we describe that polymethylhydrosiloxane (PMHS) is a sustainable terminal reductant in the titanocene catalyzed hydrosilylation of epoxides. The products formally constitute the anti‐Markovnikov products of H2O‐addition to alkenes. PMHS is not only a more sustainable and cheaper reductant than other silanes such as PhSiH3 and Ph(Me)SiH2. It also results in a higher diastereoselectivity of epoxide reduction. Here, we demonstrate that polymethylhydrosiloxane (PMHS) is not only a sustainable terminal reductant and hydrogen atom donor in titanocene catalyzed epoxide hydrosilylations. Moreover, PMHS also results in higher diastereoselectivity of radical reduction. Therefore, Cp2TiCl2 can replace sterically demanding titanocene complexes that have to be used with other silanes, such as PhSiH3, without significant loss of selectivity.