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

ABSTRACT: 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 a

SUBMITTER: Funk P 

PROVIDER: S-EPMC7986230 | biostudies-literature | 2021 Mar

REPOSITORIES: biostudies-literature