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Diruthenium Tetracarboxylate-Catalyzed Enantioselective Cyclopropanation with Aryldiazoacetates
[Image: see text] A series of chiral bowl-shaped diruthenium(II,III) tetracarboxylate catalysts were prepared and evaluated in asymmetric cyclopropanations with donor/acceptor carbenes derived from aryldiazoacetates. The diruthenium catalysts self-assembled to generate C(4)-symmetric bowl-shaped str...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10428512/ https://www.ncbi.nlm.nih.gov/pubmed/37592951 http://dx.doi.org/10.1021/acs.organomet.3c00268 |
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author | Sailer, Joshua K. Sharland, Jack C. Bacsa, John Harris, Caleb F. Berry, John F. Musaev, Djamaladdin G. Davies, Huw M. L. |
author_facet | Sailer, Joshua K. Sharland, Jack C. Bacsa, John Harris, Caleb F. Berry, John F. Musaev, Djamaladdin G. Davies, Huw M. L. |
author_sort | Sailer, Joshua K. |
collection | PubMed |
description | [Image: see text] A series of chiral bowl-shaped diruthenium(II,III) tetracarboxylate catalysts were prepared and evaluated in asymmetric cyclopropanations with donor/acceptor carbenes derived from aryldiazoacetates. The diruthenium catalysts self-assembled to generate C(4)-symmetric bowl-shaped structures in an analogous manner to their dirhodium counterparts. The optimum catalyst was found to be Ru(2)(S-TPPTTL)(4)·BAr(F) [S-TPPTTL = (S)-2-(1,3-dioxo-4,5,6,7-tetraphenylisoindolin-2-yl)-3,3-dimethylbutanoate, BAr(F) = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate], which resulted in the cyclopropanation of a range of substrates in up to 94% ee. Synthesis and evaluation of first-row transition-metal congeners [Cu(II/II) and Co(II/II)] invariably resulted in catalysts that afforded little to no asymmetric induction. Computational studies indicate that the carbene complexes of these dicopper and dicobalt complexes, unlike the dirhodium and diruthenium systems, are prone to the loss of carboxylate ligands, which would destroy the bowl-shaped structure critical for asymmetric induction. |
format | Online Article Text |
id | pubmed-10428512 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-104285122023-08-17 Diruthenium Tetracarboxylate-Catalyzed Enantioselective Cyclopropanation with Aryldiazoacetates Sailer, Joshua K. Sharland, Jack C. Bacsa, John Harris, Caleb F. Berry, John F. Musaev, Djamaladdin G. Davies, Huw M. L. Organometallics [Image: see text] A series of chiral bowl-shaped diruthenium(II,III) tetracarboxylate catalysts were prepared and evaluated in asymmetric cyclopropanations with donor/acceptor carbenes derived from aryldiazoacetates. The diruthenium catalysts self-assembled to generate C(4)-symmetric bowl-shaped structures in an analogous manner to their dirhodium counterparts. The optimum catalyst was found to be Ru(2)(S-TPPTTL)(4)·BAr(F) [S-TPPTTL = (S)-2-(1,3-dioxo-4,5,6,7-tetraphenylisoindolin-2-yl)-3,3-dimethylbutanoate, BAr(F) = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate], which resulted in the cyclopropanation of a range of substrates in up to 94% ee. Synthesis and evaluation of first-row transition-metal congeners [Cu(II/II) and Co(II/II)] invariably resulted in catalysts that afforded little to no asymmetric induction. Computational studies indicate that the carbene complexes of these dicopper and dicobalt complexes, unlike the dirhodium and diruthenium systems, are prone to the loss of carboxylate ligands, which would destroy the bowl-shaped structure critical for asymmetric induction. American Chemical Society 2023-06-30 /pmc/articles/PMC10428512/ /pubmed/37592951 http://dx.doi.org/10.1021/acs.organomet.3c00268 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Sailer, Joshua K. Sharland, Jack C. Bacsa, John Harris, Caleb F. Berry, John F. Musaev, Djamaladdin G. Davies, Huw M. L. Diruthenium Tetracarboxylate-Catalyzed Enantioselective Cyclopropanation with Aryldiazoacetates |
title | Diruthenium
Tetracarboxylate-Catalyzed Enantioselective
Cyclopropanation with Aryldiazoacetates |
title_full | Diruthenium
Tetracarboxylate-Catalyzed Enantioselective
Cyclopropanation with Aryldiazoacetates |
title_fullStr | Diruthenium
Tetracarboxylate-Catalyzed Enantioselective
Cyclopropanation with Aryldiazoacetates |
title_full_unstemmed | Diruthenium
Tetracarboxylate-Catalyzed Enantioselective
Cyclopropanation with Aryldiazoacetates |
title_short | Diruthenium
Tetracarboxylate-Catalyzed Enantioselective
Cyclopropanation with Aryldiazoacetates |
title_sort | diruthenium
tetracarboxylate-catalyzed enantioselective
cyclopropanation with aryldiazoacetates |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10428512/ https://www.ncbi.nlm.nih.gov/pubmed/37592951 http://dx.doi.org/10.1021/acs.organomet.3c00268 |
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