Issue 12, 2017

Tunable regiodivergent phosphine-catalyzed [3 + 2] cycloaddition of alkynones and trifluoroacetyl phenylamides

Abstract

Alkynones can be activated by phosphine as a nucleophilic catalyst, and then trapped by a series of trifluoroacetyl phenylamides to afford cycloaddition products. Through subtly adjusting the substituent of trifluoroacetyl phenylamides, the addition of water and changing the reaction temperature, two kinds of highly regioselective cycloaddition products were obtained in moderate to excellent yields. Plausible mechanisms were proposed and supported by the deuterium-labeling experiments and DFT calculations. DFT calculations demonstrate that the currently accepted intramolecular proton transfer processes involved in these reactions are impossible, and these proton transfer processes can proceed with the assistance of substrates containing an acidic moiety or by the addition of water. Our mechanistic studies provide reasonable explanations for the regioselectivity affected by the protic additive H2O, and the reaction temperature.

Graphical abstract: Tunable regiodivergent phosphine-catalyzed [3 + 2] cycloaddition of alkynones and trifluoroacetyl phenylamides

Supplementary files

Article information

Article type
Research Article
Submitted
26 jun 2017
Accepted
28 ago 2017
First published
29 ago 2017

Org. Chem. Front., 2017,4, 2392-2402

Tunable regiodivergent phosphine-catalyzed [3 + 2] cycloaddition of alkynones and trifluoroacetyl phenylamides

Y. Sun, Y. Wei and M. Shi, Org. Chem. Front., 2017, 4, 2392 DOI: 10.1039/C7QO00512A

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