Transition-Metal-Free Transfer Hydrogenative Cascade Reaction of Nitroarenes with Amines/Alcohols: Redox-Economical Access to Benzimidazoles

Abstract

This report describes an efficient transition-metal-free process toward the transfer hydrogenative cascade reaction between nitroarenes and amines or alcohols. The developed redox-economical approach was realized using a combination of KO^<i>t</i>Bu and Et₃SiH as reagents, which allows the synthesis of benzimidazole derivatives via σ-bond metathesis. The reaction conditions hold well over a wide range of substrates embedded with diverse functional groups to deliver the desired products in good to excellent yields. The mechanistic proposal has been depicted on the basis of a series of control experiments, mass spectroscopic evidence which is well supported by density functional theory (DFT) calculations with a feasible energy profile.