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
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author Wicker, Garrit
Zhou, Rundong
Schoch, Roland
Paradies, Jan
author_facet Wicker, Garrit
Zhou, Rundong
Schoch, Roland
Paradies, Jan
author_sort Wicker, Garrit
collection PubMed
description 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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spelling pubmed-94010412022-08-26 Sigmatropic [1,5] Carbon Shift of Transient C3 Ammonium Enolates Wicker, Garrit Zhou, Rundong Schoch, Roland Paradies, Jan Angew Chem Int Ed Engl Communications 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. John Wiley and Sons Inc. 2022-06-10 2022-08-01 /pmc/articles/PMC9401041/ /pubmed/35535567 http://dx.doi.org/10.1002/anie.202204378 Text en © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Wicker, Garrit
Zhou, Rundong
Schoch, Roland
Paradies, Jan
Sigmatropic [1,5] Carbon Shift of Transient C3 Ammonium Enolates
title Sigmatropic [1,5] Carbon Shift of Transient C3 Ammonium Enolates
title_full Sigmatropic [1,5] Carbon Shift of Transient C3 Ammonium Enolates
title_fullStr Sigmatropic [1,5] Carbon Shift of Transient C3 Ammonium Enolates
title_full_unstemmed Sigmatropic [1,5] Carbon Shift of Transient C3 Ammonium Enolates
title_short Sigmatropic [1,5] Carbon Shift of Transient C3 Ammonium Enolates
title_sort sigmatropic [1,5] carbon shift of transient c3 ammonium enolates
topic Communications
url 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
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