Iron N‐Doped Carbon Nanoarchitectonics for C─H Bond Activation of Methylarenes and Esterification Reactions

Abstract Nowadays, selective oxidation of sp³ C−H bond in methylarene to benzaldehyde under eco‐friendly conditions is a promising way to produce aldehyde derivatives. In this work, scalable iron nanoparticles adorned on surface engineered nitrogen‐doped carbon (Fe_NP@NC‐BA) fabricated via wet chemistry followed by high‐temperature pyrolysis. It is observed that nitrogen‐coordinated Fe nanoparticles play a crucial role as active sites in facilitating both the toluene oxidation and esterification reaction due to its nitrogen‐rich Fe NPs contain and low C/N ratio in Fe_NP@NC‐BA catalyst. The Fe_NP@NC−BA catalyst and N‐hydroxyphthalimide cooperatively converted methylarenes to corresponding aryl aldehydes with 99% conversion and selectivity, without over‐oxidation of benzaldehyde to benzoic acid at room temperature. Further, EPR analysis is used to probe the free radical pathway followed in C−H activation. Additionally, Fe_NP@NC‐BA catalyst employed for microwave‐assisted esterification of acids with alcohols leads to 99% conversion and selectivity. The compatibility of Fe_NP@NC‐BA nanoarchitectonics employed for the highly efficient synthesis of selective 24 benzaldehyde derivatives and 42 ester products. Furthermore, a gram‐scale catalyst reusability study proved the wide applicability of Fe_NP@NC‐BA catalyst. Thus, Fe nanoparticles decorated with N‐doped carbon catalysts provide a durable, easily recoverable, and environmentally friendly metal‐based catalyst for oxidation and esterification reactions.