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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. An H‐atom transfer, to generate a benzylic radical, serves as a radical translocation step, and an organometallic oxygen rebound as a reductive elimination. The reaction mechanism was studied by high‐level dispersion corrected hybrid functional DFT with implicit solvation. The low‐energy conformational space was searched by the efficient CREST program. The stereoselectivity was deduced from the lowest lying benzylic radical structures and their conformations are controlled by hyperconjugative interactions and steric interactions between the titanocene catalyst and the aryl groups of the substrate. An interesting mechanistic aspect is that the oxidation of the benzylic center occurs under reducing conditions., Oxidations with reducing agents? Fact and not fiction in a reaction featuring titanocene(III) catalysis, H‐atom transfer, and an organometallic oxygen rebound. Acetals and hemiaminals can be readily prepared from benzylic ethers and amines, respectively, under mild reaction conditions and in high yields. The structures of the radical intermediates were elucidated by the CREST program.

We describe a combination of catalysts that allows the coupling of titanocene(III) catalysis with photoredox catalysis. Oxidation of radical intermediates by a photoredox catalyst opens novel catal...

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 Cp2 TiX-catalysts that are prepared in situ from readily available Cp2 TiX2 is achieved by varying the anionic ligand X. Of the complexes investigated, Cp2 TiOMs proved to be either equal or substantially superior to the best catalysts developed earlier. The kinetic and thermodynamic properties pertinent to catalysis have been determined. They allow a mechanistic understanding of the subtle interplay of properties required for an efficient oxidative addition and reduction. Therefore, our study highlights that efficient catalysts do not require the elaborate covalent modification of the cyclopentadienyl ligands.