CC BY-NC-ND 4.0 UnportedDai, XingchaoWang, XinzhiRabeah, JaborKreyenschulte, CarstenBrückner, AngelikaShi, Feng2022-05-052022-05-052021https://oa.tib.eu/renate/handle/123456789/8863https://doi.org/10.34657/7901The shift from fossil carbon sources to renewable ones is vital for developing sustainable chemical processes to produce valuable chemicals. In this work, value-added formamides were synthesized in good yields by the reaction of amines with C2 and C3 biomass-based platform molecules such as glycolic acid, 1,3-dihydroxyacetone and glyceraldehyde. These feedstocks were selectively converted by catalysts based on Cu-containing zeolite 5A through the in situ formation of carbonyl-containing intermediates. To the best of our knowledge, this is the first example in which all the carbon atoms in biomass-based feedstocks could be amidated to produce formamide. Combined catalyst characterization results revealed preferably single CuII sites on the surface of Cu/5A, some of which form small clusters, but without direct linking via oxygen bridges. By combining the results of electron paramagnetic resonance (EPR) spin-trapping, operando attenuated total reflection (ATR) IR spectroscopy and control experiments, it was found that the formation of formamides might involve a HCOOH-like intermediate and .NHPh radicals, in which the selective formation of .OOH radicals might play a key role. © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbHenghttps://creativecommons.org/licenses/by-nc-nd/4.0/540660C−C bond cleavageaminesbiomass-based feedstockselectron paramagnetic resonance spectroscopyformylationselective oxidationArticle