Chiral manganese complexes with pinene appended tetradentate ligands as stereoselective epoxidation catalysts

A novel family of chiral manganese complexes Λ-1(CF 3SO3) and Δ-2(CF3SO3), have been stereoselectively prepared, characterized and studied as epoxidation catalysts. The complexes are structurally related to [MnII(CF 3SO3)2(α-MCP)] (MCP = N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)cyclohexane-trans-1, 2-...

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Autores: Gómez Martín, Laura, Garcia Bosch, Isaac, Company Casadevall, Anna, Sala Román, Xavier, Fontrodona, Xavier, Ribas Salamaña, Xavi, Costas Salgueiro, Miquel
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2007
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/12718
Acesso em linha:http://hdl.handle.net/10256/12718
Access Level:acceso embargado
Palavra-chave:Epòxids
Epoxy compounds
Catalitzadors
Catalysts
Manganès -- Compostos -- Oxidació
Manganese compounds -- Oxidation
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spelling Chiral manganese complexes with pinene appended tetradentate ligands as stereoselective epoxidation catalystsGómez Martín, LauraGarcia Bosch, IsaacCompany Casadevall, AnnaSala Román, XavierFontrodona, XavierRibas Salamaña, XaviCostas Salgueiro, MiquelEpòxidsEpoxy compoundsCatalitzadorsCatalystsManganès -- Compostos -- OxidacióManganese compounds -- OxidationA novel family of chiral manganese complexes Λ-1(CF 3SO3) and Δ-2(CF3SO3), have been stereoselectively prepared, characterized and studied as epoxidation catalysts. The complexes are structurally related to [MnII(CF 3SO3)2(α-MCP)] (MCP = N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)cyclohexane-trans-1, 2-diamine), recently reported as a very efficient epoxidation catalyst in combination with peracetic acid. Pinene rings have been fused to the 4 and 5 positions of the two pyridine groups of the ligand, giving rise to complexes where the two labile binding sites of the manganese ion are confined in a better-defined chiral pocket than in the parent [MnII(CF 3SO3)2(α-MCP)]. Chirality in these complexes arises from the stereochemistry of the trans-diaminocyclohexane ring, from the pinene ring and also from the topological chirality adopted by the ligand upon binding to the manganese ion. While previous studies have demonstrated that small modifications in the structure of the MCP ligand result in a dramatic loss of efficiency, Λ-1(CF3SO3) and Δ-2(CF3SO3) exhibit comparable catalytic activity to [MnII(CF3SO3)2(α-MCP)]. In addition, the complexes exhibit a remarkable stereoselectivity (up to 46% ee) in the epoxidation of selected substrates. The results reported in this work point towards modification of the 4 and 5 positions of the pyridine groups as a new strategy towards the design of stereoselective versions of this family of highly active and environmentally benign epoxidation catalystsWe acknowledge financial support by MCYT of Spain through projects CTQ2006–05367/BQU to MC. LG, IG-B and AC thank MEC for PhD grantsRoyal Society of Chemistry (RSC)Ministerio de Educación y Ciencia (Espanya)infoinfo2007info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10256/12718http://hdl.handle.net/10256/12718© Dalton Transactions, 2007, vol. 47, 5539-5545Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1039/b712754einfo:eu-repo/semantics/altIdentifier/issn/1477-9226info:eu-repo/semantics/altIdentifier/eissn/1477-9234MEC/PN 2006-2009/CTQ2006-05367Tots els drets reservatsinfo:eu-repo/semantics/embargoedAccessoai:recercat.cat:10256/127182026-05-29T05:05:01Z
dc.title.none.fl_str_mv Chiral manganese complexes with pinene appended tetradentate ligands as stereoselective epoxidation catalysts
title Chiral manganese complexes with pinene appended tetradentate ligands as stereoselective epoxidation catalysts
spellingShingle Chiral manganese complexes with pinene appended tetradentate ligands as stereoselective epoxidation catalysts
Gómez Martín, Laura
Epòxids
Epoxy compounds
Catalitzadors
Catalysts
Manganès -- Compostos -- Oxidació
Manganese compounds -- Oxidation
title_short Chiral manganese complexes with pinene appended tetradentate ligands as stereoselective epoxidation catalysts
title_full Chiral manganese complexes with pinene appended tetradentate ligands as stereoselective epoxidation catalysts
title_fullStr Chiral manganese complexes with pinene appended tetradentate ligands as stereoselective epoxidation catalysts
title_full_unstemmed Chiral manganese complexes with pinene appended tetradentate ligands as stereoselective epoxidation catalysts
title_sort Chiral manganese complexes with pinene appended tetradentate ligands as stereoselective epoxidation catalysts
dc.creator.none.fl_str_mv Gómez Martín, Laura
Garcia Bosch, Isaac
Company Casadevall, Anna
Sala Román, Xavier
Fontrodona, Xavier
Ribas Salamaña, Xavi
Costas Salgueiro, Miquel
author Gómez Martín, Laura
author_facet Gómez Martín, Laura
Garcia Bosch, Isaac
Company Casadevall, Anna
Sala Román, Xavier
Fontrodona, Xavier
Ribas Salamaña, Xavi
Costas Salgueiro, Miquel
author_role author
author2 Garcia Bosch, Isaac
Company Casadevall, Anna
Sala Román, Xavier
Fontrodona, Xavier
Ribas Salamaña, Xavi
Costas Salgueiro, Miquel
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Educación y Ciencia (Espanya)
dc.subject.none.fl_str_mv Epòxids
Epoxy compounds
Catalitzadors
Catalysts
Manganès -- Compostos -- Oxidació
Manganese compounds -- Oxidation
topic Epòxids
Epoxy compounds
Catalitzadors
Catalysts
Manganès -- Compostos -- Oxidació
Manganese compounds -- Oxidation
description A novel family of chiral manganese complexes Λ-1(CF 3SO3) and Δ-2(CF3SO3), have been stereoselectively prepared, characterized and studied as epoxidation catalysts. The complexes are structurally related to [MnII(CF 3SO3)2(α-MCP)] (MCP = N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)cyclohexane-trans-1, 2-diamine), recently reported as a very efficient epoxidation catalyst in combination with peracetic acid. Pinene rings have been fused to the 4 and 5 positions of the two pyridine groups of the ligand, giving rise to complexes where the two labile binding sites of the manganese ion are confined in a better-defined chiral pocket than in the parent [MnII(CF 3SO3)2(α-MCP)]. Chirality in these complexes arises from the stereochemistry of the trans-diaminocyclohexane ring, from the pinene ring and also from the topological chirality adopted by the ligand upon binding to the manganese ion. While previous studies have demonstrated that small modifications in the structure of the MCP ligand result in a dramatic loss of efficiency, Λ-1(CF3SO3) and Δ-2(CF3SO3) exhibit comparable catalytic activity to [MnII(CF3SO3)2(α-MCP)]. In addition, the complexes exhibit a remarkable stereoselectivity (up to 46% ee) in the epoxidation of selected substrates. The results reported in this work point towards modification of the 4 and 5 positions of the pyridine groups as a new strategy towards the design of stereoselective versions of this family of highly active and environmentally benign epoxidation catalysts
publishDate 2007
dc.date.none.fl_str_mv 2007
info
info
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/12718
http://hdl.handle.net/10256/12718
url http://hdl.handle.net/10256/12718
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/b712754e
info:eu-repo/semantics/altIdentifier/issn/1477-9226
info:eu-repo/semantics/altIdentifier/eissn/1477-9234
MEC/PN 2006-2009/CTQ2006-05367
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/embargoedAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv embargoedAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry (RSC)
publisher.none.fl_str_mv Royal Society of Chemistry (RSC)
dc.source.none.fl_str_mv © Dalton Transactions, 2007, vol. 47, 5539-5545
Articles publicats (D-Q)
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
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score 15,811543

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