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Shi S, Wang T, Weingand V, et al. Gold(I)-catalyzed diastereoselective hydroacylation of terminal alkynes with glyoxals. Angew Chem Int Ed Engl. 2013;53(4):1148-51doi: 10.1002/anie.201307685.
Shi, S., Wang, T., Weingand, V., Rudolph, M., & Hashmi, A. S. (2014). Gold(I)-catalyzed diastereoselective hydroacylation of terminal alkynes with glyoxals. Angewandte Chemie (International ed. in English), 53(4), 1148-51. https://doi.org/10.1002/anie.201307685
Shi, Shuai, et al. "Gold(I)-catalyzed diastereoselective hydroacylation of terminal alkynes with glyoxals." Angewandte Chemie (International ed. in English) vol. 53,4 (2014): 1148-51. doi: https://doi.org/10.1002/anie.201307685
Shi S, Wang T, Weingand V, Rudolph M, Hashmi AS. Gold(I)-catalyzed diastereoselective hydroacylation of terminal alkynes with glyoxals. Angew Chem Int Ed Engl. 2014 Jan 20;53(4):1148-51. doi: 10.1002/anie.201307685. Epub 2013 Dec 11. PMID: 24339019.
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Angew Chem Int Ed Engl. 2014 Jan 20;53(4):1148-51. doi: 10.1002/anie.201307685. Epub 2013 Dec 11.

Gold(I)-catalyzed diastereoselective hydroacylation of terminal alkynes with glyoxals.

Angewandte Chemie (International ed. in English)

Shuai Shi, Tao Wang, Vanessa Weingand, Matthias Rudolph, A Stephen K Hashmi

Affiliations

  1. Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany) http://www.hashmi.de.

PMID: 24339019 DOI: 10.1002/anie.201307685

Abstract

The reaction of an α-ketoaldehyde and a terminal alkyne in the presence of piperidine and a catalytic amount of AuCl delivers 1,2-dicarbonyl-3-enes, products of the formal hydroacylation of the triple bond. The scope of the method is broad; different aryl substituents on the dicarbonyl unit and on the alkyne are well tolerated. The products can be transformed selectively into vinylquinoxalines. Mechanistic studies, including isotope-labeling experiments, indicate that after an initial A(3) -type conversion to propargylic amines, a subsequent base-mediated alkyne-to-allene isomerization and a hydrolysis of the enamine substructure during the workup deliver the formal hydroacylation products.

Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: 1,2-dicarbonyl compounds; Michael acceptors; alkynes; gold; quinoxaline

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