Fe‐catalyzed Selective N‐Formylation Protocol for Amines Using Glycolic Acid as C1 Bio‐Building Block

Abstract Due to current global issues involving climate change and energy crises, it requires several complete overhauls in process developments sectors of energy and chemical manufacturing industries towards more sustainable and readily applicable protocols. As a contribution to this goal with an example of iron‐based catalysis, this work presents a synthetic protocol for synthesis of N ‐formamides with glycolic acid as a C1 bio‐building block, which is catalyzed through earth abundant and magnetically active Fe powder as catalyst. The protocol was applied to a wide variety of substrates affording yields in the range of 68–94 % and also performed well at 1 gram and 5 gram scale with yields of up to 86 % and 83 %, respectively. The catalyst was shown to be reusable up to 4 runs and the spent catalyst has been studied using PXRD and XPS analyses to determine catalyst deactivation and its remediation. Plausible reaction pathway has been suggested based on control experiments and GC‐MS results for the process.