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 β‐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.
Tetrasubstituted 2‐aminoacrylonitriles (α‐enaminonitriles) are underinvestigated building blocks due to the lack of methodologies to synthesize them in a controlled manner. A general access to these valuable scaffolds accompanied by mechanistic investigations and DFT calculations is described. This highly regio‐ and stereoselective strategy relies on the use of the first intermolecular silylcyanation of ynamides.
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 β‐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.
Tetrasubstituted 2‐aminoacrylonitriles (α‐enaminonitriles) are underinvestigated building blocks due to the lack of methodologies to synthesize them in a controlled manner. A general access to these valuable scaffolds accompanied by mechanistic investigations and DFT calculations is described. This highly regio‐ and stereoselective strategy relies on the use of the first intermolecular silylcyanation of ynamides.
The fully regio‐ and stereoselective Zn‐catalyzed hydrocyanation of ynamides is reported and represents a general access to various trisubstituted E‐α‐enamidonitriles. The catalyst‐free ...photoisomerization selectively yields the energetically comparable Z‐stereoisomer. Finally, the synthetic potential of these new α‐enamidonitriles was evaluated through the synthesis of original heterocycles.
Trisubstituted E‐2‐amidoacrylonitriles are produced by direct hydrocyanation of ynamides. Z isomers can be obtained selectively using a thermo‐neutral catalyst‐free photoisomerization.
Herein we report the efficient and selective two-step synthesis of various 3-silyl-2-amidoindenones from easily accessible ynamides. This sequence involves a regio- and stereo-selective ...silylcyanation followed by a Houben-Hoesch type cyclization. Thanks to post-transformations, various 3-substituted 2-amidoindenones could be obtained.
A simple and selective two-step sequence is reported for the synthesis of polyfunctionalized 2-amidoindenones. Remarkably, this method achieves true structural diversity at position 3.
An efficient copper-catalyzed synthesis of (annelated) benzimidazoles is reported. This transformation is based on a simple and straightforward one-pot sequence involving a copper-catalyzed cross ...coupling between o-haloanilines and lactams/amides followed by a subsequent cyclization under acidic conditions. A variety of (annelated) benzimidazoles could be easily obtained in high yields from readily available starting materials, and this procedure could be further applied to the synthesis of the antihypertensive blockbuster drug telmisartan.
In this paper we report the annulation reaction between 2-iodobenzaldehyde derivatives and various ynamides. This palladium-catalyzed reaction leads to rare polysubstituted amino-indenones in good ...yields with a regioselectivity up to complete. Remarkably, a regiodivergent selectivity has been identified between aryl and alkyl or silyl ynamides, with the first leading mainly to 2-amido-indenones and the second to 3-amido-indenones.
