Transition Metal-catalysed intramolecular carbenoid C-H insertion for pyrrolidine formation by decomposition of α-diazoesters

The use of Pd‐, Rh(II)‐ and Ru(II)‐based catalysts has been explored in the transition metal‐catalysed intramolecular carbenoid C−H insertion of α‐diazoesters leading to pyrrolidines. Although the outcome of the reaction was highly substrate‐dependent, in general, it was possible to control the chem...

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Authors: Solé Arjó, Daniel, Amenta, Arianna, Mariani, Francesco, Bennasar Fèlix, M. Lluïsa, Fernández Cadenas, Israel
Format: article
Status:Versión aceptada para publicación
Publication Date:2017
Country:España
Institution:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repository:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/127844
Online Access:https://hdl.handle.net/2445/127844
Access Level:Open access
Keyword:Carbens
Diazocomposts
Pirroles
Pal·ladi (Element químic)
Catàlisi
Teoria del funcional de densitat
Complexitat computacional
Carbenes
Diazo compounds
Pyrroles
Palladium
Catalysis
Density functionals
Computational complexity
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oai_identifier_str oai:recercat.cat:2445/127844
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repository_id_str
spelling Transition Metal-catalysed intramolecular carbenoid C-H insertion for pyrrolidine formation by decomposition of α-diazoestersSolé Arjó, DanielAmenta, AriannaMariani, FrancescoBennasar Fèlix, M. LluïsaFernández Cadenas, IsraelCarbensDiazocompostsPirrolesPal·ladi (Element químic)CatàlisiTeoria del funcional de densitatComplexitat computacionalCarbenesDiazo compoundsPyrrolesPalladiumCatalysisDensity functionalsComputational complexityThe use of Pd‐, Rh(II)‐ and Ru(II)‐based catalysts has been explored in the transition metal‐catalysed intramolecular carbenoid C−H insertion of α‐diazoesters leading to pyrrolidines. Although the outcome of the reaction was highly substrate‐dependent, in general, it was possible to control the chemoselectivity of the process towards pyrrolidines by adequate catalyst selection. The Pd(0)‐catalysts were as efficient as [Rh(Ph3CCO2)2]2 in promoting the C(sp3)−H insertion of ortho‐substituted anilines. In contrast, for anilines bearing meta‐ and para‐substituents, the Rh(II)‐catalyst provided the best chemoselectivities and reaction yields. On the other hand, [Ru(p‐cymene)Cl2]2 was the most efficient catalyst for the insertion reaction of the N‐benzyl‐N‐phenyl and N,N‐dibenzyl α‐diazoesters, while the C(sp3)−H insertion of the N‐benzylsulfonamide substrate was only promoted by [Rh(Ph3CCO2)2]2. According to density functional theory (DFT) calculations, the mechanism involved in the Pd(0)‐ and Ru(II)‐catalysed C(sp3)−H insertions differs considerably from that typically proposed for the Rh(II)‐catalysed transformation. Whereas the Pd(0)‐catalysed reaction involves a Pd‐mediated 1,5‐H migration from the C(sp3)−H bond to the carbenoid carbon atom leading to the formal oxidation of the transition metal, a Ru(II)‐promoted Mannich type reaction involving a zwitterionic intermediate seems to be operative in the Ru(II)‐catalysed transformation. Keywords: carbenoid insertion; diazo compounds; pyrrolidines; palladium-catalysis; density functional theory calculationsWiley-VCH2019201920172019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion11 p.application/pdfhttps://hdl.handle.net/2445/127844Articles publicats en revistes (Farmacologia, Toxicologia i Química Terapèutica)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió postprint del document publicat a: https://doi.org/10.1002/adsc.201700840Advanced Synthesis & Catalysis, 2017, vol. 359, num. 20, p. 3654-3664https://doi.org/10.1002/adsc.201700840(c) Wiley-VCH, 2017info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1278442026-05-29T05:05:01Z
dc.title.none.fl_str_mv Transition Metal-catalysed intramolecular carbenoid C-H insertion for pyrrolidine formation by decomposition of α-diazoesters
title Transition Metal-catalysed intramolecular carbenoid C-H insertion for pyrrolidine formation by decomposition of α-diazoesters
spellingShingle Transition Metal-catalysed intramolecular carbenoid C-H insertion for pyrrolidine formation by decomposition of α-diazoesters
Solé Arjó, Daniel
Carbens
Diazocomposts
Pirroles
Pal·ladi (Element químic)
Catàlisi
Teoria del funcional de densitat
Complexitat computacional
Carbenes
Diazo compounds
Pyrroles
Palladium
Catalysis
Density functionals
Computational complexity
title_short Transition Metal-catalysed intramolecular carbenoid C-H insertion for pyrrolidine formation by decomposition of α-diazoesters
title_full Transition Metal-catalysed intramolecular carbenoid C-H insertion for pyrrolidine formation by decomposition of α-diazoesters
title_fullStr Transition Metal-catalysed intramolecular carbenoid C-H insertion for pyrrolidine formation by decomposition of α-diazoesters
title_full_unstemmed Transition Metal-catalysed intramolecular carbenoid C-H insertion for pyrrolidine formation by decomposition of α-diazoesters
title_sort Transition Metal-catalysed intramolecular carbenoid C-H insertion for pyrrolidine formation by decomposition of α-diazoesters
dc.creator.none.fl_str_mv Solé Arjó, Daniel
Amenta, Arianna
Mariani, Francesco
Bennasar Fèlix, M. Lluïsa
Fernández Cadenas, Israel
author Solé Arjó, Daniel
author_facet Solé Arjó, Daniel
Amenta, Arianna
Mariani, Francesco
Bennasar Fèlix, M. Lluïsa
Fernández Cadenas, Israel
author_role author
author2 Amenta, Arianna
Mariani, Francesco
Bennasar Fèlix, M. Lluïsa
Fernández Cadenas, Israel
author2_role author
author
author
author
dc.subject.none.fl_str_mv Carbens
Diazocomposts
Pirroles
Pal·ladi (Element químic)
Catàlisi
Teoria del funcional de densitat
Complexitat computacional
Carbenes
Diazo compounds
Pyrroles
Palladium
Catalysis
Density functionals
Computational complexity
topic Carbens
Diazocomposts
Pirroles
Pal·ladi (Element químic)
Catàlisi
Teoria del funcional de densitat
Complexitat computacional
Carbenes
Diazo compounds
Pyrroles
Palladium
Catalysis
Density functionals
Computational complexity
description The use of Pd‐, Rh(II)‐ and Ru(II)‐based catalysts has been explored in the transition metal‐catalysed intramolecular carbenoid C−H insertion of α‐diazoesters leading to pyrrolidines. Although the outcome of the reaction was highly substrate‐dependent, in general, it was possible to control the chemoselectivity of the process towards pyrrolidines by adequate catalyst selection. The Pd(0)‐catalysts were as efficient as [Rh(Ph3CCO2)2]2 in promoting the C(sp3)−H insertion of ortho‐substituted anilines. In contrast, for anilines bearing meta‐ and para‐substituents, the Rh(II)‐catalyst provided the best chemoselectivities and reaction yields. On the other hand, [Ru(p‐cymene)Cl2]2 was the most efficient catalyst for the insertion reaction of the N‐benzyl‐N‐phenyl and N,N‐dibenzyl α‐diazoesters, while the C(sp3)−H insertion of the N‐benzylsulfonamide substrate was only promoted by [Rh(Ph3CCO2)2]2. According to density functional theory (DFT) calculations, the mechanism involved in the Pd(0)‐ and Ru(II)‐catalysed C(sp3)−H insertions differs considerably from that typically proposed for the Rh(II)‐catalysed transformation. Whereas the Pd(0)‐catalysed reaction involves a Pd‐mediated 1,5‐H migration from the C(sp3)−H bond to the carbenoid carbon atom leading to the formal oxidation of the transition metal, a Ru(II)‐promoted Mannich type reaction involving a zwitterionic intermediate seems to be operative in the Ru(II)‐catalysed transformation. Keywords: carbenoid insertion; diazo compounds; pyrrolidines; palladium-catalysis; density functional theory calculations
publishDate 2017
dc.date.none.fl_str_mv 2017
2019
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/127844
url https://hdl.handle.net/2445/127844
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1002/adsc.201700840
Advanced Synthesis & Catalysis, 2017, vol. 359, num. 20, p. 3654-3664
https://doi.org/10.1002/adsc.201700840
dc.rights.none.fl_str_mv (c) Wiley-VCH, 2017
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Wiley-VCH, 2017
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 11 p.
application/pdf
dc.publisher.none.fl_str_mv Wiley-VCH
publisher.none.fl_str_mv Wiley-VCH
dc.source.none.fl_str_mv Articles publicats en revistes (Farmacologia, Toxicologia i Química Terapèutica)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869408410017988608
score 15,81155

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