Non-Cp titanium alkoxide-based homolytic ring-opening of epoxides by an intramolecular hydrogen abstraction in β-titanoxy radical intermediates.

A low-valent titanium species derived in situ from Ti(O-i-Pr)(4), Me(3)SiCl and Mg powder in tetrahydrofuran reacted with epoxides to selectively provide less hindered alcohols via a homolytic ring-opening of epoxides, in which the intermediate β-titanoxy radical intramolecularly abstracted a hydrogen atom from an alkoxy moiety in the titanium complexes.