Helical chiral N‐heterocyclic carbene ligands in enantioselective gold catalysis
International audience The first chiral helicene-NHC gold(I) complexes efficient in enantioselective catalysis were prepared. The L-shaped chiral ligand is composed of an imidazo[1,5-a]pyridin-3-ylidene (IPy) scaffold laterally-substituted by a configurationally stable [5]-helicenoid unit. The chira...
Published in: | Chemistry – A European Journal |
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Main Authors: | , , , , , , , , , |
Other Authors: | , , , , , , , , , , , , , , , , , , |
Format: | Article in Journal/Newspaper |
Language: | English |
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HAL CCSD
2022
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Online Access: | https://hal.science/hal-03575284 https://hal.science/hal-03575284/document https://hal.science/hal-03575284/file/Pallova,%20Helical%20chiral%20N-heterocyclic%20carbene,%202022.pdf https://doi.org/10.1002/chem.202200166 |
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Portail HAL-ANR (Agence Nationale de la Recherche) |
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ftanrparis |
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English |
topic |
Helicenes N-heterocyclic Carbenes Gold Asymmetric catalysis Chirality [CHIM.COOR]Chemical Sciences/Coordination chemistry |
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Helicenes N-heterocyclic Carbenes Gold Asymmetric catalysis Chirality [CHIM.COOR]Chemical Sciences/Coordination chemistry Pallova, Lenka Abella, Laura Jean, Marion Vanthuyne, Nicolas Barthes, Cécile Vendier, Laure Autschbach, Jochen Crassous, Jeanne Bastin, Stéphanie César, Vincent Helical chiral N‐heterocyclic carbene ligands in enantioselective gold catalysis |
topic_facet |
Helicenes N-heterocyclic Carbenes Gold Asymmetric catalysis Chirality [CHIM.COOR]Chemical Sciences/Coordination chemistry |
description |
International audience The first chiral helicene-NHC gold(I) complexes efficient in enantioselective catalysis were prepared. The L-shaped chiral ligand is composed of an imidazo[1,5-a]pyridin-3-ylidene (IPy) scaffold laterally-substituted by a configurationally stable [5]-helicenoid unit. The chiral information was introduced in a key post-functionalization step of a NHC-gold(I) complex bearing a symmetrical anionic fluoreno[5]helicene substituent, leading to a racemic mixture of complexes featuring three correlated elements of chirality, namely central, axial and helical chirality. After HPLC enantiomeric resolution, X-ray crystallography and theoretical calculations enabled structural and stereochemical characterization of these configurationally stable NHC-gold(I) complexes. The high potential in asymmetric catalysis is demonstrated in the benchmark cycloisomerization of N-tethered 1,6-enynes with up to 95:5 er. |
author2 |
Laboratoire de chimie de coordination (LCC) Institut de Chimie de Toulouse (ICT) Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3) Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP) Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3) Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS) Department of Chemistry Buffalo University at Buffalo SUNY (SUNY Buffalo) State University of New York (SUNY)-State University of New York (SUNY) Institut des Sciences Moléculaires de Marseille (ISM2) Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS) Institut des Sciences Chimiques de Rennes (ISCR) Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes) Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS) Institut de Physique de Rennes (IPR) Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS) Centre National de la Recherche Scientifique (CNRS) National Science Foundation (Grant CHE-1855470) ANR-16-CE07-0019,HEL-NHC,Carbènes N-hétérocycliques (NHC) hélicéniques: synthèse, structure, propriétés photophysiques et activité catalytique(2016) |
format |
Article in Journal/Newspaper |
author |
Pallova, Lenka Abella, Laura Jean, Marion Vanthuyne, Nicolas Barthes, Cécile Vendier, Laure Autschbach, Jochen Crassous, Jeanne Bastin, Stéphanie César, Vincent |
author_facet |
Pallova, Lenka Abella, Laura Jean, Marion Vanthuyne, Nicolas Barthes, Cécile Vendier, Laure Autschbach, Jochen Crassous, Jeanne Bastin, Stéphanie César, Vincent |
author_sort |
Pallova, Lenka |
title |
Helical chiral N‐heterocyclic carbene ligands in enantioselective gold catalysis |
title_short |
Helical chiral N‐heterocyclic carbene ligands in enantioselective gold catalysis |
title_full |
Helical chiral N‐heterocyclic carbene ligands in enantioselective gold catalysis |
title_fullStr |
Helical chiral N‐heterocyclic carbene ligands in enantioselective gold catalysis |
title_full_unstemmed |
Helical chiral N‐heterocyclic carbene ligands in enantioselective gold catalysis |
title_sort |
helical chiral n‐heterocyclic carbene ligands in enantioselective gold catalysis |
publisher |
HAL CCSD |
publishDate |
2022 |
url |
https://hal.science/hal-03575284 https://hal.science/hal-03575284/document https://hal.science/hal-03575284/file/Pallova,%20Helical%20chiral%20N-heterocyclic%20carbene,%202022.pdf https://doi.org/10.1002/chem.202200166 |
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IPY |
genre_facet |
IPY |
op_source |
ISSN: 0947-6539 EISSN: 1521-3765 Chemistry - A European Journal https://hal.science/hal-03575284 Chemistry - A European Journal, 2022, 28 (17), pp.e202200166. ⟨10.1002/chem.202200166⟩ |
op_relation |
info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.202200166 info:eu-repo/semantics/altIdentifier/pmid/35143078 hal-03575284 https://hal.science/hal-03575284 https://hal.science/hal-03575284/document https://hal.science/hal-03575284/file/Pallova,%20Helical%20chiral%20N-heterocyclic%20carbene,%202022.pdf doi:10.1002/chem.202200166 PUBMED: 35143078 |
op_rights |
info:eu-repo/semantics/OpenAccess |
op_doi |
https://doi.org/10.1002/chem.202200166 |
container_title |
Chemistry – A European Journal |
container_volume |
28 |
container_issue |
17 |
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1799482892659720192 |
spelling |
ftanrparis:oai:HAL:hal-03575284v1 2024-05-19T07:43:11+00:00 Helical chiral N‐heterocyclic carbene ligands in enantioselective gold catalysis Pallova, Lenka Abella, Laura Jean, Marion Vanthuyne, Nicolas Barthes, Cécile Vendier, Laure Autschbach, Jochen Crassous, Jeanne Bastin, Stéphanie César, Vincent Laboratoire de chimie de coordination (LCC) Institut de Chimie de Toulouse (ICT) Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3) Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP) Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3) Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS) Department of Chemistry Buffalo University at Buffalo SUNY (SUNY Buffalo) State University of New York (SUNY)-State University of New York (SUNY) Institut des Sciences Moléculaires de Marseille (ISM2) Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS) Institut des Sciences Chimiques de Rennes (ISCR) Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes) Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS) Institut de Physique de Rennes (IPR) Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS) Centre National de la Recherche Scientifique (CNRS) National Science Foundation (Grant CHE-1855470) ANR-16-CE07-0019,HEL-NHC,Carbènes N-hétérocycliques (NHC) hélicéniques: synthèse, structure, propriétés photophysiques et activité catalytique(2016) 2022-02-10 https://hal.science/hal-03575284 https://hal.science/hal-03575284/document https://hal.science/hal-03575284/file/Pallova,%20Helical%20chiral%20N-heterocyclic%20carbene,%202022.pdf https://doi.org/10.1002/chem.202200166 en eng HAL CCSD Wiley-VCH Verlag info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.202200166 info:eu-repo/semantics/altIdentifier/pmid/35143078 hal-03575284 https://hal.science/hal-03575284 https://hal.science/hal-03575284/document https://hal.science/hal-03575284/file/Pallova,%20Helical%20chiral%20N-heterocyclic%20carbene,%202022.pdf doi:10.1002/chem.202200166 PUBMED: 35143078 info:eu-repo/semantics/OpenAccess ISSN: 0947-6539 EISSN: 1521-3765 Chemistry - A European Journal https://hal.science/hal-03575284 Chemistry - A European Journal, 2022, 28 (17), pp.e202200166. ⟨10.1002/chem.202200166⟩ Helicenes N-heterocyclic Carbenes Gold Asymmetric catalysis Chirality [CHIM.COOR]Chemical Sciences/Coordination chemistry info:eu-repo/semantics/article Journal articles 2022 ftanrparis https://doi.org/10.1002/chem.202200166 2024-04-23T03:09:06Z International audience The first chiral helicene-NHC gold(I) complexes efficient in enantioselective catalysis were prepared. The L-shaped chiral ligand is composed of an imidazo[1,5-a]pyridin-3-ylidene (IPy) scaffold laterally-substituted by a configurationally stable [5]-helicenoid unit. The chiral information was introduced in a key post-functionalization step of a NHC-gold(I) complex bearing a symmetrical anionic fluoreno[5]helicene substituent, leading to a racemic mixture of complexes featuring three correlated elements of chirality, namely central, axial and helical chirality. After HPLC enantiomeric resolution, X-ray crystallography and theoretical calculations enabled structural and stereochemical characterization of these configurationally stable NHC-gold(I) complexes. The high potential in asymmetric catalysis is demonstrated in the benchmark cycloisomerization of N-tethered 1,6-enynes with up to 95:5 er. Article in Journal/Newspaper IPY Portail HAL-ANR (Agence Nationale de la Recherche) Chemistry – A European Journal 28 17 |