Gold(I)-catalyzed diastereoselective hydroacylation of terminal alkynes with glyoxals
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 t...
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| Main Authors: | , , , , |
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| Format: | Article (Journal) Editorial |
| Language: | English |
| Published: |
2014
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| In: |
Angewandte Chemie. International edition
Year: 2014, Volume: 53, Issue: 4, Pages: 1148-1151 |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.201307685 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/anie.201307685 Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201307685 
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| Author Notes: | Shuai Shi, Tao Wang, Vanessa Weingand, Matthias Rudolph, and A. Stephen K. Hashmi |
| Summary: | 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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| Item Description: | Published online: December 11, 2013 Gesehen am 06.11.2020 |
| Physical Description: | Online Resource |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.201307685 |