Aerobic Oxidative Synthesis of Formamides from Amines and Bioderived Formyl Surrogates.
Xingchao DaiYunyan HanHaijun JiaoFeng ShiJabor RabeahAngelika BrücknerPublished in: Angewandte Chemie (International ed. in English) (2024)
Herein we present a new strategy for the oxidative synthesis of formamides from various types of amines and bioderived formyl sources (DHA, GLA and GLCA) and molecular oxygen (O 2 ) as oxidant on g-C 3 N 4 supported Cu catalysts. Combined characterization data from EPR, XAFS, XRD and XPS revealed the formation of single CuN 4 sites on supported Cu phen /C 3 N 4 catalysts. EPR spin trapping experiments disclosed ⋅OOH radicals as reactive oxygen species and ⋅NR 1 R 2 radicals being responsible for the initial C-C bond cleavage. Control experiments and DFT calculations showed that the successive C-C bond cleavage in DHA proceeds via a reaction mechanism co-mediated by ⋅NR 1 R 2 and ⋅OOH radicals based on the well-equilibrated Cu II and Cu I cycle. Our catalyst has much higher activity (TOF) than those based on noble metals.
Keyphrases
- metal organic framework
- transition metal
- density functional theory
- highly efficient
- reactive oxygen species
- aqueous solution
- room temperature
- mass spectrometry
- fatty acid
- molecular dynamics
- dna binding
- molecular dynamics simulations
- ionic liquid
- electronic health record
- single cell
- big data
- reduced graphene oxide
- carbon dioxide
- health risk assessment