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Reactivity of ethyl nitrosoacrylate toward pyrrole, indole and pyrrolo[3,2-c]carbazole: an experimental and theoretical study

Nitrosoalkenes react with 8-methyl-1,6-dihydropyrrolo[3,2-c]carbazole to give both 2- and 3-alkylated products via hetero-Diels-Alder reaction followed by the cycloadduct ring-opening. Quantum chemical calculations, at DFT level of theory, were carried out to investigate the regioselectivity of the...

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Autores principales: Benzi, Alice, Lopes, Susana M. M., Nunes, Sandra C. C., Giorgi, Gianluca, Bianchi, Lara, Tavani, Cinzia, Pais, Alberto A. C. C., Petrillo, Giovanni, Pinho e Melo, Teresa M. V. D.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Frontiers Media S.A. 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10443595/
https://www.ncbi.nlm.nih.gov/pubmed/37614704
http://dx.doi.org/10.3389/fchem.2023.1229669
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author Benzi, Alice
Lopes, Susana M. M.
Nunes, Sandra C. C.
Giorgi, Gianluca
Bianchi, Lara
Tavani, Cinzia
Pais, Alberto A. C. C.
Petrillo, Giovanni
Pinho e Melo, Teresa M. V. D.
author_facet Benzi, Alice
Lopes, Susana M. M.
Nunes, Sandra C. C.
Giorgi, Gianluca
Bianchi, Lara
Tavani, Cinzia
Pais, Alberto A. C. C.
Petrillo, Giovanni
Pinho e Melo, Teresa M. V. D.
author_sort Benzi, Alice
collection PubMed
description Nitrosoalkenes react with 8-methyl-1,6-dihydropyrrolo[3,2-c]carbazole to give both 2- and 3-alkylated products via hetero-Diels-Alder reaction followed by the cycloadduct ring-opening. Quantum chemical calculations, at DFT level of theory, were carried out to investigate the regioselectivity of the cycloaddition of ethyl nitrosoacrylate with 1,6-dihydropyrrolo[3,2-c]carbazoles as well as with pyrrole and indole, allowing a more comprehensive analysis of the reactivity pattern of nitrosoalkenes with five-membered heterocycles. Furthermore, theoretical calculations confirmed that ethyl nitrosoacrylate reacts with these heterocycles via a LUMO(heterodiene)-HOMO(dienophile) controlled cycloaddition. The reactivity of one of the oxime-functionalized 1,6-dihydropyrrolo[3,2-c]carbazole was explored and a new hexahydropyrido[4′,3':4,5]pyrrolo[3,2-c]carbazole system was obtained in high yield via a one-pot, two-step procedure.
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spelling pubmed-104435952023-08-23 Reactivity of ethyl nitrosoacrylate toward pyrrole, indole and pyrrolo[3,2-c]carbazole: an experimental and theoretical study Benzi, Alice Lopes, Susana M. M. Nunes, Sandra C. C. Giorgi, Gianluca Bianchi, Lara Tavani, Cinzia Pais, Alberto A. C. C. Petrillo, Giovanni Pinho e Melo, Teresa M. V. D. Front Chem Chemistry Nitrosoalkenes react with 8-methyl-1,6-dihydropyrrolo[3,2-c]carbazole to give both 2- and 3-alkylated products via hetero-Diels-Alder reaction followed by the cycloadduct ring-opening. Quantum chemical calculations, at DFT level of theory, were carried out to investigate the regioselectivity of the cycloaddition of ethyl nitrosoacrylate with 1,6-dihydropyrrolo[3,2-c]carbazoles as well as with pyrrole and indole, allowing a more comprehensive analysis of the reactivity pattern of nitrosoalkenes with five-membered heterocycles. Furthermore, theoretical calculations confirmed that ethyl nitrosoacrylate reacts with these heterocycles via a LUMO(heterodiene)-HOMO(dienophile) controlled cycloaddition. The reactivity of one of the oxime-functionalized 1,6-dihydropyrrolo[3,2-c]carbazole was explored and a new hexahydropyrido[4′,3':4,5]pyrrolo[3,2-c]carbazole system was obtained in high yield via a one-pot, two-step procedure. Frontiers Media S.A. 2023-08-08 /pmc/articles/PMC10443595/ /pubmed/37614704 http://dx.doi.org/10.3389/fchem.2023.1229669 Text en Copyright © 2023 Benzi, Lopes, Nunes, Giorgi, Bianchi, Tavani, Pais, Petrillo and Pinho e Melo. https://creativecommons.org/licenses/by/4.0/This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
spellingShingle Chemistry
Benzi, Alice
Lopes, Susana M. M.
Nunes, Sandra C. C.
Giorgi, Gianluca
Bianchi, Lara
Tavani, Cinzia
Pais, Alberto A. C. C.
Petrillo, Giovanni
Pinho e Melo, Teresa M. V. D.
Reactivity of ethyl nitrosoacrylate toward pyrrole, indole and pyrrolo[3,2-c]carbazole: an experimental and theoretical study
title Reactivity of ethyl nitrosoacrylate toward pyrrole, indole and pyrrolo[3,2-c]carbazole: an experimental and theoretical study
title_full Reactivity of ethyl nitrosoacrylate toward pyrrole, indole and pyrrolo[3,2-c]carbazole: an experimental and theoretical study
title_fullStr Reactivity of ethyl nitrosoacrylate toward pyrrole, indole and pyrrolo[3,2-c]carbazole: an experimental and theoretical study
title_full_unstemmed Reactivity of ethyl nitrosoacrylate toward pyrrole, indole and pyrrolo[3,2-c]carbazole: an experimental and theoretical study
title_short Reactivity of ethyl nitrosoacrylate toward pyrrole, indole and pyrrolo[3,2-c]carbazole: an experimental and theoretical study
title_sort reactivity of ethyl nitrosoacrylate toward pyrrole, indole and pyrrolo[3,2-c]carbazole: an experimental and theoretical study
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10443595/
https://www.ncbi.nlm.nih.gov/pubmed/37614704
http://dx.doi.org/10.3389/fchem.2023.1229669
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