Iron/B₂ pin₂ catalytic system enables the generation of alkyl radicals from inert alkyl C-O bonds for amine synthesis

A method for the generation of alkyl radicals from inert alkyl C-O bonds has been developed via an iron/borane reagent/alkoxide catalytic system, which can be employed for the synthesis of amines from nitroarenes with excellent efficiency. This reductive amination features good functional group compatibility and enables the late-stage amination of bio-relevant compounds, thus providing good opportunities for applications in medicinal chemistry. Preliminary mechanistic studies reveal that the amine synthesis may be involving a Fe/Li cation-assisted single electron transfer pathway to form alkyl radicals, and the low-valent iron species may be the active intermediates.(c) 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.