Sigmatropic [1,5] Carbon Shift of Transient C3 Ammonium Enolates

The stereospecific sigmatropic [1,5] carbon shift of C3 ammonium enolates is discovered. According to mechanistic, kinetic and computational experiments, this new rearrangement proceeds via the catalytic generation of a transient C3 ammonium enolate by intramolecular aza‐Michael addition. This inter...

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Detalles Bibliográficos
Autores principales: Wicker, Garrit, Zhou, Rundong, Schoch, Roland, Paradies, Jan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9401041/
https://www.ncbi.nlm.nih.gov/pubmed/35535567
http://dx.doi.org/10.1002/anie.202204378
Descripción
Sumario:The stereospecific sigmatropic [1,5] carbon shift of C3 ammonium enolates is discovered. According to mechanistic, kinetic and computational experiments, this new rearrangement proceeds via the catalytic generation of a transient C3 ammonium enolate by intramolecular aza‐Michael addition. This intermediate rapidly undergoes [1,5] sigmatropic carbon migration to furnish the respective tetrahydroquinoline‐4‐ones with excellent diastereoselectivities of d.r. >99 : 1 and in 61–98 % yield.

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