Mechanistic and Computational Insights into Asymmetric Intramolecular Iron-Catalyzed Nitrene Transfer into Benzylic C─H Bonds.

ABSTRACT: Chiral, nonracemic amines are valuable synthetic building blocks for diverse bioactive molecules. Asymmetric C─H amination via transition metal-catalyzed nitrene transfer (NT) is a popular strategy to access enantioenriched benzylamines, but many useful chemocatalysts for this transformation are based on precious metals or require elaborate ligands. Iron catalysts supported by simple ligands capable of asymmetric aminations of diverse sulfamates would be valuable but are surprisingly rare. Herein, we study features of the asymmetric iron-catalyzed NT of homo- and bis-homobenzylic sulfamates to better understand why the development of such reactions has proven challenging. Diverse parameters were examined, including ligand, iron source, oxidant, additive, and solvent. Reactions of the preox

SUBMITTER: Seo K 

PROVIDER: S-EPMC12442830 | biostudies-literature | 2025 Mar

REPOSITORIES: biostudies-literature