Dual Nickel/Photoredox‐Catalyzed Synthesis of N‐formyl N,N’‐Diaryl Ethylenediamines via Multiple C−N/C−C Coupling of Nitroarenes with Trimethylamine

Abstract

AbstractN,N’‐Diaryl ethylenediamines are common feedstocks in organic synthesis and important structural motifs in medicinal chemistry. Whereas the C−N formation reactions based on anilines and aryl halides are the most direct methods to access N,N’‐diaryl ethylenediamines, the photocatalytic synthetic version remains undeveloped. Herein we describe the dual nickel/photoredox‐catalyzed amination reaction using nitroarenes and trimethylamine as reaction substrates. This cascade transformation hinges on the multiple C−N and C−C coupling events based on the nitrogen radical and α‐aminomethyl radical derived from nitroarene and trimethylamine, respectively. A variety of N‐formyl N,N’‐diaryl ethylenediamines can be obtained under the reaction protocol. Subsequent hydrolysis offers the N,N’‐diaryl ethylenediamines for further derivatizations.