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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...

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Autores principales: Sailer, Joshua K., Sharland, Jack C., Bacsa, John, Harris, Caleb F., Berry, John F., Musaev, Djamaladdin G., Davies, Huw M. L.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
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.
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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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