Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 26, Issue 61, Pages 13826-13831Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202000778
Keywords
Bronsted acid; carboxylic acids; (E)-enamides; linear selective; metal-free
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Funding
- Project of Long-term Overseas Dispatch of PNUs Tenure-track Faculty, 2019
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Metal-free hydrocarboxylation of allenamides with various functionalized carboxylic acids were achieved with complete regio- and stereocontrol (>49:1). This environmentally compatible transformation affords gamma-acyloxyenamides with exclusiveE-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.
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