Highly Selective Catalyst‐Free Oxidative Synthesis of N‐Formamides from C2‐ and C3‐Feedstocks

Abstract The application of bio‐derived feedstocks as building blocks in organic syntheses holds great value with goals of high product yield and minimizing carbon loss. As contribution to this effort, present work explores 5 different C 2 ‐ and C 3 ‐feedstocks (derived from biomass and conventional sources) such as glycerol (GLY), 1,3‐dihydroxyacetone (DHA), ethylene glycol (EG), glycolic acid (GLYAC) and glyoxal (GLYOX) as carbon sources for highly selective, catalyst‐free oxidative synthesis of N ‐formamides from primary and secondary amines. Both DHA and GLYOX showed the best carbon efficiency through carbon source: amine ratio of 1 : 2, resulting in 100 % selectivity of N ‐formanilide with tert ‐butyl hydrogen peroxide (TBHP) as the oxidant. GLYOX was applied further for synthesizing a N ‐formamide library of 21 substrates exemplifying substantial yields ranging from 68–98 %. Moreover, pilot scalability of this methodology achieved a yield of 87 % and 72 % for aniline substrate at 5‐gram scale using GLYOX and DHA respectively in 24 hours.