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.