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A Heteroleptic Dirhodium Catalyst for Asymmetric Cyclopropanation with α‐Stannyl α‐Diazoacetate. “Stereoretentive” Stille Coupling with Formation of Chiral Quarternary Carbon Centers
The heteroleptic dirhodium paddlewheel catalyst 7 with a chiral carboxylate/acetamidate ligand sphere is uniquely effective in asymmetric [2+1] cycloadditions with α‐diazo‐α‐trimethylstannyl (silyl, germyl) acetate. Originally discovered as a trace impurity in a sample of the homoleptic parent compl...
Autores principales: | , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7496581/ https://www.ncbi.nlm.nih.gov/pubmed/32426901 http://dx.doi.org/10.1002/anie.202004377 |
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author | Caló, Fabio P. Fürstner, Alois |
author_facet | Caló, Fabio P. Fürstner, Alois |
author_sort | Caló, Fabio P. |
collection | PubMed |
description | The heteroleptic dirhodium paddlewheel catalyst 7 with a chiral carboxylate/acetamidate ligand sphere is uniquely effective in asymmetric [2+1] cycloadditions with α‐diazo‐α‐trimethylstannyl (silyl, germyl) acetate. Originally discovered as a trace impurity in a sample of the homoleptic parent complex [Rh(2)((R)‐TPCP)(4)] (5), it is shown that the protic acetamidate ligand is quintessential for rendering 7 highly enantioselective. The ‐NH group is thought to lock the ensuing metal carbene in place via interligand hydrogen bonding. The resulting stannylated cyclopropanes undergo “stereoretentive” cross coupling, which shows for the first time that even chiral quarternary carbon centers can be made by the Stille–Migita reaction. |
format | Online Article Text |
id | pubmed-7496581 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-74965812020-09-25 A Heteroleptic Dirhodium Catalyst for Asymmetric Cyclopropanation with α‐Stannyl α‐Diazoacetate. “Stereoretentive” Stille Coupling with Formation of Chiral Quarternary Carbon Centers Caló, Fabio P. Fürstner, Alois Angew Chem Int Ed Engl Research Articles The heteroleptic dirhodium paddlewheel catalyst 7 with a chiral carboxylate/acetamidate ligand sphere is uniquely effective in asymmetric [2+1] cycloadditions with α‐diazo‐α‐trimethylstannyl (silyl, germyl) acetate. Originally discovered as a trace impurity in a sample of the homoleptic parent complex [Rh(2)((R)‐TPCP)(4)] (5), it is shown that the protic acetamidate ligand is quintessential for rendering 7 highly enantioselective. The ‐NH group is thought to lock the ensuing metal carbene in place via interligand hydrogen bonding. The resulting stannylated cyclopropanes undergo “stereoretentive” cross coupling, which shows for the first time that even chiral quarternary carbon centers can be made by the Stille–Migita reaction. John Wiley and Sons Inc. 2020-06-04 2020-08-10 /pmc/articles/PMC7496581/ /pubmed/32426901 http://dx.doi.org/10.1002/anie.202004377 Text en © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Research Articles Caló, Fabio P. Fürstner, Alois A Heteroleptic Dirhodium Catalyst for Asymmetric Cyclopropanation with α‐Stannyl α‐Diazoacetate. “Stereoretentive” Stille Coupling with Formation of Chiral Quarternary Carbon Centers |
title | A Heteroleptic Dirhodium Catalyst for Asymmetric Cyclopropanation with α‐Stannyl α‐Diazoacetate. “Stereoretentive” Stille Coupling with Formation of Chiral Quarternary Carbon Centers |
title_full | A Heteroleptic Dirhodium Catalyst for Asymmetric Cyclopropanation with α‐Stannyl α‐Diazoacetate. “Stereoretentive” Stille Coupling with Formation of Chiral Quarternary Carbon Centers |
title_fullStr | A Heteroleptic Dirhodium Catalyst for Asymmetric Cyclopropanation with α‐Stannyl α‐Diazoacetate. “Stereoretentive” Stille Coupling with Formation of Chiral Quarternary Carbon Centers |
title_full_unstemmed | A Heteroleptic Dirhodium Catalyst for Asymmetric Cyclopropanation with α‐Stannyl α‐Diazoacetate. “Stereoretentive” Stille Coupling with Formation of Chiral Quarternary Carbon Centers |
title_short | A Heteroleptic Dirhodium Catalyst for Asymmetric Cyclopropanation with α‐Stannyl α‐Diazoacetate. “Stereoretentive” Stille Coupling with Formation of Chiral Quarternary Carbon Centers |
title_sort | heteroleptic dirhodium catalyst for asymmetric cyclopropanation with α‐stannyl α‐diazoacetate. “stereoretentive” stille coupling with formation of chiral quarternary carbon centers |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7496581/ https://www.ncbi.nlm.nih.gov/pubmed/32426901 http://dx.doi.org/10.1002/anie.202004377 |
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