Issue 4, 2023

Cu-Catalysed sustainable synthesis of formamide with glycerol derivatives as a carbonyl source via a radical-relay mechanism

Abstract

Value-added formamides were sustainably synthesized by the N-formylation of amines with glycerol derivatives (1,3-dihydroxyacetone, glyceraldehyde and glycolic acid) as the carbonyl source via in situ C–C bond cleavage catalyzed over zeolite 5A supported Cu-based catalysts. Introducing a second metal ZrIV ions can greatly increase the activity of the Cu/5A catalyst. Catalyst characterization results revealed that the introduction of ZrIV ions decreases the amount of surface acidic sites, in particular, medium–strong acidic sites and promotes the formation of ˙OOH radicals. Isotopic tracing experiments confirmed that all the carbon atoms in the carbonyl group of formamide products are indeed from glycerol derivatives. Combined electron paramagnetic resonance (EPR) spin-trapping, operando attenuated total reflection (ATR)-FTIR spectroscopy and control experiments revealed that the reaction of aniline and DHA with formanilide involves GA and HCOOH intermediates and ˙NHPh radicals via a ˙OH–˙OOH radical-relay mechanism.

Graphical abstract: Cu-Catalysed sustainable synthesis of formamide with glycerol derivatives as a carbonyl source via a radical-relay mechanism

Supplementary files

Article information

Article type
Paper
Submitted
25 10 2022
Accepted
20 1 2023
First published
23 1 2023

Green Chem., 2023,25, 1464-1472

Cu-Catalysed sustainable synthesis of formamide with glycerol derivatives as a carbonyl source via a radical-relay mechanism

X. Dai, X. Wang, C. Kreyenschulte, H. Yuan, A. Brückner, F. Shi and J. Rabeah, Green Chem., 2023, 25, 1464 DOI: 10.1039/D2GC03993A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements