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. 2024 Jun 17;27(23):e202400067.
doi: 10.1002/ejoc.202400067. Epub 2024 Apr 10.

n-Bu4NI/K2S2O8-MEDIATED C-N COUPLING BETWEEN ALDEHYDES AND AMIDES

Xiaochen Liu  1   2 , Samual Hee  1   2 , Netanel G Sapir  1 , Alvin Li  1 , Syed Farkruzzaman  1 , Jianbo Liu  1   2 , Yu Chen  1   2
Affiliations

n-Bu4NI/K2S2O8-MEDIATED C-N COUPLING BETWEEN ALDEHYDES AND AMIDES

Xiaochen Liu et al. European J Org Chem. .

Abstract

n-Bu4NI/K2S2O8 mediated C-N coupling between aldehydes and amides is reported. A strong electronic effect is observed on the aromatic aldehyde substrates. The transformylation from aldehyde to amide takes place exclusively when an aromatic aldehyde bears electron-donating groups at either the ortho or para position of the formyl group, while the cross-dehydrogenative coupling dominates in the absence of these groups. Both the density functional theory (DFT) thermochemistry calculations and experimental data support the proposed single electron transfer mechanism with the formation of an acyl radical intermediate in the cross-dehydrogenative coupling. The n-Bu4NI/K2S2O8 mediated oxidative cyclization between 2-aminobenzamide and aldehydes is also reported, with four quinazolin-4(3H)-ones prepared in 65-99% yields.

Keywords: C–N coupling; cross-dehydrogenative coupling; imides; potassium persulfate; quinazolin-4(3H)-ones.

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Figures

Scheme 1.
Scheme 1.
Synthesis of imides by cross-dehydrogenative coupling between aldehydes and amides.
Scheme 2.
Scheme 2.
Synthesis of 2,3-dihydroquinazolin-4(1H)-one (4) and n-Bu4NI/K2S2O8-mediated oxidation of 4 to 3a.
Scheme 3.
Scheme 3.
Proposed mechanism for the n-Bu4NI/K2S2O8-mediated cross dehydrogenative coupling between aldehydes and amides.
Scheme 4.
Scheme 4.
Proposed mechanism for the n-Bu4NI/K2S2O8-mediated transformylation from p-anisaldehyde to primary amides.
See this image and copyright information in PMC

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