Formal Anti‐Markovnikov Addition of Water to Olefins by Titanocene‐Catalyzed Epoxide Hydrosilylation: From Stoichiometric to Sustainable Catalytic Reactions

Here, the evolution of the titanocene‐catalyzed hydrosilylation of epoxides that yields the corresponding anti‐Markovnikov alcohols is summarized. The study focuses on aspects of sustainability, efficient catalyst activation, and stereoselectivity. The latest variant of the reaction employs polymethylhydrosiloxane (PMHS), a waste product of the Müller–Rochow process as terminal reductant, features an efficient catalyst activation with benzylMgBr and the use of the bench stable Cp(2)TiCl(2) as precatalyst. The combination of olefin epoxidation and epoxide hydrosilylation provides a uniquely efficient approach to the formal anti‐Markovnikov addition of H(2)O to olefins.