Reagent‐Controlled Stereoselectivity in Titanocene‐Catalyzed Epoxide Openings: Reductions and Intermolecular Additions to α,β‐Unsaturated Carbonyl Compounds

The generation and addition reactions of metal bound radicals derived from normal and meso epoxides by electron transfer from titanocene(III) reagents is described. The control of enantioselectivity and diastereoselectivity of these transformations is investigated by variation of the ligands of the metal complex. The reaction can lead to unprecedented and highly selective reactions, in which synthetically useful alcohols may be prepared. The synthesis presented also circumvents the use of toxic metals. Another advantage is that there is no loss of two functional groups as usually observed in reductive radical chain reactions.