Highly Chemoselective Esterification from O ‐Aminoallylation of Carboxylic Acids: Metal‐ and Reagent‐Free Hydrocarboxylation of Allenamides

Autor:	Hae Eun Lee, Tapas R. Pradhan, Paul Ha-Yeon Cheong, Jin Kyoon Park, Gisela A. González-Montiel
Rok vydání:	2020
Předmět:	010405 organic chemistry Chemistry Aryl Organic Chemistry Synthon General Chemistry Conjugated system 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences Metal chemistry.chemical_compound Reagent visual_art visual_art.visual_art_medium Organic chemistry Carboxylate Brønsted–Lowry acid–base theory Selectivity
Zdroj:	Chemistry – A European Journal. 26:13826-13831
ISSN:	1521-3765 0947-6539
Popis:	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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::7a313b5dd4c83648740437d6b92914fe https://doi.org/10.1002/chem.202000778 Zobrazit plný text záznamu Plný text ve formátu PDF Plný text ve formátu HTML
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