Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 14, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202200204
Keywords
Aminoacrylonitriles; Palladium; Silylcyanation; Vinylsilanes; Ynamides
Categories
Funding
- French Ministry of Higher Education, Research and Innovation
- CNRS
- University of Strasbourg
- French National Agency of Research (ANR) [ANR-CE07-19-0016]
- UPSaclay
- Ecole polytechnique
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The palladium-catalyzed silylcyanation of ynamides is highly selective, producing exclusively tetrasubstituted 2-aminoacrylonitriles derivatives. The stereoselectivity is directly controlled by the nature of the substituent at the beta-position of the ynamide. The reaction is tolerant of various functional groups and provides a general method to access fully substituted 2-aminoacrylonitriles. The mechanism of this intriguing transformation is elucidated by computational study, and the range of 2-aminoacrylonitriles is expanded through postfunctionalization using the newly installed vinylsilane functionality.
The palladium-catalyzed silylcyanation of ynamides is described. This reaction is fully regioselective, delivering tetrasubstituted 2-aminoacrylonitriles derivatives exclusively. Unexpectedly, the nature (aryl or alkyl) of the substituent located at the beta-position of the ynamide directly controls the stereoselectivity. The reaction tolerates a number of functional groups and can be considered as the first general access to fully substituted 2-aminoacrylonitriles. Given the singular reactivity observed, a computational study was performed to shed light on the mechanism of this intriguing transformation. Relying on the specific reactivity of the newly installed vinylsilane functionality, the scope of 2-aminoacrylonitriles has been enlarged by postfunctionalization.
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