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

• Verfasst von: Shi, Shuai [VerfasserIn]
• Verfasst von: Wang, Tao [VerfasserIn]
• Verfasst von: Claus, Vanessa [VerfasserIn]
• Verfasst von: Rudolph, Matthias [VerfasserIn]
• Verfasst von: Hashmi, A. Stephen K. [VerfasserIn]
• Titel: Gold(I)-catalyzed diastereoselective hydroacylation of terminal alkynes with glyoxals
• Verf.angabe: Shuai Shi, Tao Wang, Vanessa Weingand, Matthias Rudolph, and A. Stephen K. Hashmi
• Jahr: 2014
• Umfang: 4 S.
• Fussnoten: Published online: December 11, 2013 ; Gesehen am 06.11.2020
• Titel Quelle: Enthalten in: Angewandte Chemie / International edition
• Ort Quelle: Weinheim : Wiley-VCH, 1962
• Jahr Quelle: 2014
• Band/Heft Quelle: 53(2014), 4, Seite 1148-1151
• ISSN Quelle: 1521-3773
• DOI: doi:10.1002/anie.201307685
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: 1
• Sach-SW: 2-dicarbonyl compounds
• Sach-SW: alkynes
• Sach-SW: gold
• Sach-SW: Michael acceptors
• Sach-SW: quinoxaline
• K10plus-PPN: 1738031004

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 A3-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.