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Gold(I)-Catalyzed Diastereoselective Hydroacylation of Terminal Alkynes with Glyoxals

Authors


  • S.S. and T.W. are grateful to the CSC (Chinese Scholarship Council) for fellowships. Gold salts were generously donated by Umicore AG & Co. KG.

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.

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