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. 2024 Nov 1;89(21):15924-15930.
doi: 10.1021/acs.joc.4c02096. Epub 2024 Oct 22.

Ag(I)-Catalyzed Oxidative Cyclization of 1,4-Diynamide-3-ols with N-Oxide for Divergent Synthesis of 2-Substituted Furan-4-carboxamide Derivatives

Akshay Subhash Narode  1 , Debashis Barik  1 , Ping-Hsun Kuo  2 , Mu-Jeng Cheng  2 , Rai-Shung Liu  1
Affiliations

Ag(I)-Catalyzed Oxidative Cyclization of 1,4-Diynamide-3-ols with N-Oxide for Divergent Synthesis of 2-Substituted Furan-4-carboxamide Derivatives

Akshay Subhash Narode et al. J Org Chem. .

Abstract

This work reports Ag(I)-catalyzed oxidative cyclizations of 1,4-diynamide-3-ols with 8-methylquinoline oxide to form 2-substituted furan-4-carboxamides. The reaction chemoselectivity is distinct from that reported in previous work by Hashmi. We performed density functional theory calculations to elucidate our proposed mechanism after evaluation of the energy profiles of two possible pathways. In this Ag(I) catalysis, the calculations suggest that the amide and alkyne groups of the 3,3-dicarbonyl-2-alkyne intermediates tend to chelate with the Ag(I) catalyst, further inducing a formyl attack at the Ag(I)-π-alkyne moiety to deliver the observed products.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Oxidative Cyclizations by N-Oxides
Scheme 2
Scheme 2. Chemical Functionalizations of 3a
Scheme 3
Scheme 3. Gibbs Free Energy Profiles for Two Independent Routes
See this image and copyright information in PMC

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