Unsaturated chiral-only-at-metal rhodium(iii) complexes bearing SiN-type ligands

Enantiopure chiral-at-metal rhodium(III) unsaturated 16e complexes have been obtained from racemic [Rh(SiN)2Cl] (SiN= 8-(dimethylsilyl)quinoline) using a readily accessible chiral spiroborate as chiral resolution agent. This strategy allows an easy access to enantiopure neutral Δ/Λ-Rh(SiN)2Cl and ca...

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Autores: Prieto Pascual, Unai, Bustos Rosas, Itxaso, Salcedo Abraira, Pablo, Vitorica Yrezabal, Iñigo J., Landa Álvarez, Aitor, Freixa Fernández, Zoraida, Huertos Mansilla, Miguel Angel
Formato: artículo
Fecha de publicación:2024
País:España
Recursos:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/70057
Acesso em linha:http://hdl.handle.net/10810/70057
Access Level:acceso abierto
Palavra-chave:rhodium(iii) complexes
chiral-at-metal
Diels Alder
Danishefsky's diene
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spelling Unsaturated chiral-only-at-metal rhodium(iii) complexes bearing SiN-type ligandsPrieto Pascual, UnaiBustos Rosas, ItxasoSalcedo Abraira, PabloVitorica Yrezabal, Iñigo J.Landa Álvarez, AitorFreixa Fernández, ZoraidaHuertos Mansilla, Miguel Angelrhodium(iii) complexeschiral-at-metalDiels AlderDanishefsky's dieneEnantiopure chiral-at-metal rhodium(III) unsaturated 16e complexes have been obtained from racemic [Rh(SiN)2Cl] (SiN= 8-(dimethylsilyl)quinoline) using a readily accessible chiral spiroborate as chiral resolution agent. This strategy allows an easy access to enantiopure neutral Δ/Λ-Rh(SiN)2Cl and cationic Δ/Λ-Rh(SiN)2[BAr4F] unsaturated complexes, wherein rhodium(III) is coordinated to two inert silylquinoline ligands in a propeller-like arrangement. Graphical abstract: Unsaturated chiral-only-at-metal rhodium(iii) complexes bearing SiN-type ligands In the field of asymmetric catalysis, transition metal catalysts are commonly used due to their remarkable efficiency.1 The predominant methodology in transition metal asymmetric catalysis involves the use of chiral ligands. However, there is a growing interest in a less studied method involving chiral-at-metal complexes formed by non-chiral ligands, mainly due to the seminal work of E. Meggers.2 This approach consists of a metal centre coordinated by two bidentate ligands in a propeller-type fashion. High configurational stability at the stereogenic metal centre is the main requirement for chiral metal catalysts. In addition, for the substrate to interact with the metal centre of the catalyst, the presence of labile auxiliary ligands, such as acetonitrile, is required. Two advantages of using chiral-at-metal complexes as asymmetric catalysts should be noted. First, the non-chiral ligands are easier to prepare than their chiral counterparts, thus offering a wider variety. Secondly, in chiral-at-metal catalysts, the metal centre, which is the reaction centre for catalysis, is also the stereogenic centre responsible for the overall enantioselectivity. Most of the chiral-at-metal complexes used as asymmetric catalysts reported to date are octahedral complexes with d6 transition metals.3–6 Cationic complexes of iridium(iii)3 and rhodium(iii)4 with two bidentate anionic ligands (CN ligands; Fig. 1a left) and two labile acetonitrile ligands have been widely used chiral-at-metal catalysts. More recently, ruthenium(ii)5 and iron(ii)6 di-cationic complexes bearing bidentate neutral ligands (CN ligands; Fig. 1a right) and also two labile acetonitrile ligands have also been studied.Financial support for this work was provided by UPV/EHU (EHU-G23/03), Gobierno Vasco (IT1741-22) and MCIN/AEI/10.13039/501100011033 and FEDER A way of making Europe to projects PID2019-111281GB-I00 and PID2022-139760NB-I00.RSC202420242024info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/70057reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/MCIN/PID2019-111281GB-I00/info:eu-repo/grantAgreement/MCIN/PID2022-139760NB-I00/https://doi.org/10.1039/D4CC03665Dinfo:eu-repo/semantics/openAccess© 2024 The Royal Society of Chemistryoai:addi.ehu.eus:10810/700572026-06-18T09:23:17Z
dc.title.none.fl_str_mv Unsaturated chiral-only-at-metal rhodium(iii) complexes bearing SiN-type ligands
title Unsaturated chiral-only-at-metal rhodium(iii) complexes bearing SiN-type ligands
spellingShingle Unsaturated chiral-only-at-metal rhodium(iii) complexes bearing SiN-type ligands
Prieto Pascual, Unai
rhodium(iii) complexes
chiral-at-metal
Diels Alder
Danishefsky's diene
title_short Unsaturated chiral-only-at-metal rhodium(iii) complexes bearing SiN-type ligands
title_full Unsaturated chiral-only-at-metal rhodium(iii) complexes bearing SiN-type ligands
title_fullStr Unsaturated chiral-only-at-metal rhodium(iii) complexes bearing SiN-type ligands
title_full_unstemmed Unsaturated chiral-only-at-metal rhodium(iii) complexes bearing SiN-type ligands
title_sort Unsaturated chiral-only-at-metal rhodium(iii) complexes bearing SiN-type ligands
dc.creator.none.fl_str_mv Prieto Pascual, Unai
Bustos Rosas, Itxaso
Salcedo Abraira, Pablo
Vitorica Yrezabal, Iñigo J.
Landa Álvarez, Aitor
Freixa Fernández, Zoraida
Huertos Mansilla, Miguel Angel
author Prieto Pascual, Unai
author_facet Prieto Pascual, Unai
Bustos Rosas, Itxaso
Salcedo Abraira, Pablo
Vitorica Yrezabal, Iñigo J.
Landa Álvarez, Aitor
Freixa Fernández, Zoraida
Huertos Mansilla, Miguel Angel
author_role author
author2 Bustos Rosas, Itxaso
Salcedo Abraira, Pablo
Vitorica Yrezabal, Iñigo J.
Landa Álvarez, Aitor
Freixa Fernández, Zoraida
Huertos Mansilla, Miguel Angel
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv rhodium(iii) complexes
chiral-at-metal
Diels Alder
Danishefsky's diene
topic rhodium(iii) complexes
chiral-at-metal
Diels Alder
Danishefsky's diene
description Enantiopure chiral-at-metal rhodium(III) unsaturated 16e complexes have been obtained from racemic [Rh(SiN)2Cl] (SiN= 8-(dimethylsilyl)quinoline) using a readily accessible chiral spiroborate as chiral resolution agent. This strategy allows an easy access to enantiopure neutral Δ/Λ-Rh(SiN)2Cl and cationic Δ/Λ-Rh(SiN)2[BAr4F] unsaturated complexes, wherein rhodium(III) is coordinated to two inert silylquinoline ligands in a propeller-like arrangement. Graphical abstract: Unsaturated chiral-only-at-metal rhodium(iii) complexes bearing SiN-type ligands In the field of asymmetric catalysis, transition metal catalysts are commonly used due to their remarkable efficiency.1 The predominant methodology in transition metal asymmetric catalysis involves the use of chiral ligands. However, there is a growing interest in a less studied method involving chiral-at-metal complexes formed by non-chiral ligands, mainly due to the seminal work of E. Meggers.2 This approach consists of a metal centre coordinated by two bidentate ligands in a propeller-type fashion. High configurational stability at the stereogenic metal centre is the main requirement for chiral metal catalysts. In addition, for the substrate to interact with the metal centre of the catalyst, the presence of labile auxiliary ligands, such as acetonitrile, is required. Two advantages of using chiral-at-metal complexes as asymmetric catalysts should be noted. First, the non-chiral ligands are easier to prepare than their chiral counterparts, thus offering a wider variety. Secondly, in chiral-at-metal catalysts, the metal centre, which is the reaction centre for catalysis, is also the stereogenic centre responsible for the overall enantioselectivity. Most of the chiral-at-metal complexes used as asymmetric catalysts reported to date are octahedral complexes with d6 transition metals.3–6 Cationic complexes of iridium(iii)3 and rhodium(iii)4 with two bidentate anionic ligands (CN ligands; Fig. 1a left) and two labile acetonitrile ligands have been widely used chiral-at-metal catalysts. More recently, ruthenium(ii)5 and iron(ii)6 di-cationic complexes bearing bidentate neutral ligands (CN ligands; Fig. 1a right) and also two labile acetonitrile ligands have also been studied.
publishDate 2024
dc.date.none.fl_str_mv 2024
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/70057
url http://hdl.handle.net/10810/70057
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/MCIN/PID2019-111281GB-I00/
info:eu-repo/grantAgreement/MCIN/PID2022-139760NB-I00/
https://doi.org/10.1039/D4CC03665D
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
© 2024 The Royal Society of Chemistry
eu_rights_str_mv openAccess
rights_invalid_str_mv © 2024 The Royal Society of Chemistry
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv RSC
publisher.none.fl_str_mv RSC
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
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