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Synfacts 2025; 21(07): 718
DOI: 10.1055/a-2601-5373
Polymer-Supported Synthesis

Reductive N-Formylation of Amines Using an Ionic Polymer under Carbon Dioxide

Contributor(s):
Yasuhiro Uozumi 
,
Shusuke Hattori
Yang X, Zhao J, Zeng J, Chen B, Tang L, Zhang J, Zeb A, Li Z, Zhang S, Zhang Y *. Hunan University, Changsha, P. R. China
Design of Halogen-Free Hyper-Crosslinked Porous Ionic Polymers for Efficient CO2 Capture and Conversion.

Green Chem. 2025;
27: 1729-1739
DOI: 10.1039/d4gc05351f
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Keywords

ionic polymers - formylation - carbon dioxide - amines

Significance

A cross-linked ionic polymer based on guanidinium tetraphenylborate (IP[Gua][BPh4]) was prepared by the Friedel–Crafts-type reaction of [Gua][BPh4] and formaldehyde dimethyl acetal (eq 1). IP[Gua][BPh4] promoted reductive N-formylation of various amines, including primary, secondary, aromatic and aliphatic amines, under CO2 (3 bar) in the presence of PhSiH3 at 80 °C to afford the corresponding N-formylated amines in up to 94 % GC yield (eq 2).


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Comment

Overreduction (N-methylation) was observed at 100 °C under otherwise similar conditions. In the reaction of N-methylaniline, IP[Gua][BPh4] was recovered by filtration and reused four times without a significant loss of its catalytic activity (fresh: 94 % yield, 5th run: 92 % yield). The CO2 adsorption capacity of IP[Gua][BPh4] was confirmed to be 3.2 mmol g−1 at 273 K.


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Publication History

Article published online:
23 June 2025

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