Oxidation Under Reductive Conditions: From Benzylic Ethers to Acetals with Perfect Atom-Economy by Titanocene(III) Catalysis.

Described here is a titanocene-catalyzed reaction for the synthesis of acetals and hemiaminals from benzylic ethers and benzylic amines, respectively, with pendant epoxides. The reaction proceeds by catalysis in single-electron steps. The oxidative addition comprises an epoxide opening.

Cp TiX Complexes for Sustainable Catalysis in Single-Electron Steps.

We present a combined electrochemical, kinetic, and synthetic study with a novel and easily accessible class of titanocene catalysts for catalysis in single-electron steps. The tailoring of the electronic properties of our Cp TiX-catalysts that are prepared in situ from readily available Cp TiX is achieved by varying the anionic ligand X. Of the complexes investigated, Cp TiOMs proved to be either equal or substantially superior to the best catalysts developed earlier.