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Regiodivergent synthesis of pyrazino-indolines vs. triazocines via α-imino carbenes addition to imidazolidines
Hexahydropyrazinoindoles were prepared in a single step from N-sulfonyl triazoles and imidazolidines. Under dirhodium catalysis, α-imino carbenes were generated and formed nitrogen ylide intermediates that, after subsequent aminal opening, afforded the pyrazinoindoles predominantly via formal [1,2]-...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179195/ https://www.ncbi.nlm.nih.gov/pubmed/34163911 http://dx.doi.org/10.1039/d0sc05725h |
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author | Guarnieri-Ibáñez, Alejandro de Aguirre, Adiran Besnard, Céline Poblador-Bahamonde, Amalia I. Lacour, Jérôme |
author_facet | Guarnieri-Ibáñez, Alejandro de Aguirre, Adiran Besnard, Céline Poblador-Bahamonde, Amalia I. Lacour, Jérôme |
author_sort | Guarnieri-Ibáñez, Alejandro |
collection | PubMed |
description | Hexahydropyrazinoindoles were prepared in a single step from N-sulfonyl triazoles and imidazolidines. Under dirhodium catalysis, α-imino carbenes were generated and formed nitrogen ylide intermediates that, after subsequent aminal opening, afforded the pyrazinoindoles predominantly via formal [1,2]-Stevens and tandem Friedel–Crafts cyclizations. Of mechanistic importance, a regiodivergent reactivity was engineered through the use of a specific unsymmetrically substituted imidazolidine that promoted the exclusive formation of 8-membered ring 1,3,6-triazocines. Based on DFT calculations, an original Curtin–Hammett-like situation was demonstrated for the mechanism. Further derivatizations led to functionalized tetrahydropyrazinoindoles in high yields. |
format | Online Article Text |
id | pubmed-8179195 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81791952021-06-22 Regiodivergent synthesis of pyrazino-indolines vs. triazocines via α-imino carbenes addition to imidazolidines Guarnieri-Ibáñez, Alejandro de Aguirre, Adiran Besnard, Céline Poblador-Bahamonde, Amalia I. Lacour, Jérôme Chem Sci Chemistry Hexahydropyrazinoindoles were prepared in a single step from N-sulfonyl triazoles and imidazolidines. Under dirhodium catalysis, α-imino carbenes were generated and formed nitrogen ylide intermediates that, after subsequent aminal opening, afforded the pyrazinoindoles predominantly via formal [1,2]-Stevens and tandem Friedel–Crafts cyclizations. Of mechanistic importance, a regiodivergent reactivity was engineered through the use of a specific unsymmetrically substituted imidazolidine that promoted the exclusive formation of 8-membered ring 1,3,6-triazocines. Based on DFT calculations, an original Curtin–Hammett-like situation was demonstrated for the mechanism. Further derivatizations led to functionalized tetrahydropyrazinoindoles in high yields. The Royal Society of Chemistry 2020-11-23 /pmc/articles/PMC8179195/ /pubmed/34163911 http://dx.doi.org/10.1039/d0sc05725h Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Guarnieri-Ibáñez, Alejandro de Aguirre, Adiran Besnard, Céline Poblador-Bahamonde, Amalia I. Lacour, Jérôme Regiodivergent synthesis of pyrazino-indolines vs. triazocines via α-imino carbenes addition to imidazolidines |
title | Regiodivergent synthesis of pyrazino-indolines vs. triazocines via α-imino carbenes addition to imidazolidines |
title_full | Regiodivergent synthesis of pyrazino-indolines vs. triazocines via α-imino carbenes addition to imidazolidines |
title_fullStr | Regiodivergent synthesis of pyrazino-indolines vs. triazocines via α-imino carbenes addition to imidazolidines |
title_full_unstemmed | Regiodivergent synthesis of pyrazino-indolines vs. triazocines via α-imino carbenes addition to imidazolidines |
title_short | Regiodivergent synthesis of pyrazino-indolines vs. triazocines via α-imino carbenes addition to imidazolidines |
title_sort | regiodivergent synthesis of pyrazino-indolines vs. triazocines via α-imino carbenes addition to imidazolidines |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179195/ https://www.ncbi.nlm.nih.gov/pubmed/34163911 http://dx.doi.org/10.1039/d0sc05725h |
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