Highly chemoselective esterification from O-aminoallylation of carboxylic acids: metal- and reagent-free hydrocarboxylation of allenamides

Pradhan, Tapas R. ORCID: https://orcid.org/0000-0003-1480-7799, Lee, Hae Eun, Gonzalez-Montiel, Gisela A., Cheong, Paul Ha-Yeon and Park, Jin Kyoon 2020. Highly chemoselective esterification from O-aminoallylation of carboxylic acids: metal- and reagent-free hydrocarboxylation of allenamides. Chemistry - A European Journal 26 (61) , pp. 13826-13831. 10.1002/chem.202000778

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Abstract

Metal-free hydrocarboxylation of allenamides with various functionalized carboxylic acids were achieved with complete regio- and stereocontrol (>49:1). This environmentally compatible transformation affords γ-acyloxyenamides with exclusive E-selectivity. Electron rich, electron poor, aliphatic, aryl, and heterocyclic carboxylic acids all gave excellent yields (avg. 89 %, 47 examples). We demonstrate the synthetic potential of this transformation in the late-stage modification of complex natural carboxylic acids and simple modification of the products to three-carbon synthons with ample opportunity for further diversification. DFT studies revealed that the reaction occurs in a stepwise manner through the intermediacy of a conjugated iminum species, which is rapidly captured by the carboxylate ion, resulting in the observed linear selectivity.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Schools > Chemistry
Publisher:	Wiley
ISSN:	0947-6539
Last Modified:	16 May 2024 01:39
URI:	https://orca.cardiff.ac.uk/id/eprint/165577

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