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Chiral oxazolidines acting as transient hydroxyalkyl-functionalized N-heterocyclic carbenes: an efficient route to air stable copper and gold complexes for asymmetric catalysis
Optically pure oxazolidines were synthesized in nearly quantitative yields from chiral hydroxyalkyl-functionalized imidazolinium salts. Acting as transient chiral diamino N-heterocyclic carbenes (NHCs), these oxazolidines allowed the efficient formation of well-defined copper(i) and gold(i) hydroxya...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9350591/ https://www.ncbi.nlm.nih.gov/pubmed/35975143 http://dx.doi.org/10.1039/d2sc02908a |
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author | Pichon-Barré, Delphine Zhang, Ziyun Cador, Aël Vives, Thomas Roisnel, Thierry Baslé, Olivier Jarrige, Lucie Cavallo, Luigi Falivene, Laura Mauduit, Marc |
author_facet | Pichon-Barré, Delphine Zhang, Ziyun Cador, Aël Vives, Thomas Roisnel, Thierry Baslé, Olivier Jarrige, Lucie Cavallo, Luigi Falivene, Laura Mauduit, Marc |
author_sort | Pichon-Barré, Delphine |
collection | PubMed |
description | Optically pure oxazolidines were synthesized in nearly quantitative yields from chiral hydroxyalkyl-functionalized imidazolinium salts. Acting as transient chiral diamino N-heterocyclic carbenes (NHCs), these oxazolidines allowed the efficient formation of well-defined copper(i) and gold(i) hydroxyalkyl-NHC complexes, which could be isolated, for the first time, as air stable complexes after silica gel chromatography. Interestingly, X-ray analysis of gold complexes revealed that the hydroxyl-function is not chelated to the metal. Computational studies suggested that both cyclisation to produce oxazolidine and O–H bond elimination to form the transient carbene (prior to coordination) occur through a concerted mechanism. The novel chiral copper-catalysts, as well as oxazolidines alone (copper free), demonstrated excellent performances in asymmetric conjugate addition and allylic alkylation with high regio- and enantio-selectivities (up to 99% ee). |
format | Online Article Text |
id | pubmed-9350591 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-93505912022-08-15 Chiral oxazolidines acting as transient hydroxyalkyl-functionalized N-heterocyclic carbenes: an efficient route to air stable copper and gold complexes for asymmetric catalysis Pichon-Barré, Delphine Zhang, Ziyun Cador, Aël Vives, Thomas Roisnel, Thierry Baslé, Olivier Jarrige, Lucie Cavallo, Luigi Falivene, Laura Mauduit, Marc Chem Sci Chemistry Optically pure oxazolidines were synthesized in nearly quantitative yields from chiral hydroxyalkyl-functionalized imidazolinium salts. Acting as transient chiral diamino N-heterocyclic carbenes (NHCs), these oxazolidines allowed the efficient formation of well-defined copper(i) and gold(i) hydroxyalkyl-NHC complexes, which could be isolated, for the first time, as air stable complexes after silica gel chromatography. Interestingly, X-ray analysis of gold complexes revealed that the hydroxyl-function is not chelated to the metal. Computational studies suggested that both cyclisation to produce oxazolidine and O–H bond elimination to form the transient carbene (prior to coordination) occur through a concerted mechanism. The novel chiral copper-catalysts, as well as oxazolidines alone (copper free), demonstrated excellent performances in asymmetric conjugate addition and allylic alkylation with high regio- and enantio-selectivities (up to 99% ee). The Royal Society of Chemistry 2022-07-11 /pmc/articles/PMC9350591/ /pubmed/35975143 http://dx.doi.org/10.1039/d2sc02908a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Pichon-Barré, Delphine Zhang, Ziyun Cador, Aël Vives, Thomas Roisnel, Thierry Baslé, Olivier Jarrige, Lucie Cavallo, Luigi Falivene, Laura Mauduit, Marc Chiral oxazolidines acting as transient hydroxyalkyl-functionalized N-heterocyclic carbenes: an efficient route to air stable copper and gold complexes for asymmetric catalysis |
title | Chiral oxazolidines acting as transient hydroxyalkyl-functionalized N-heterocyclic carbenes: an efficient route to air stable copper and gold complexes for asymmetric catalysis |
title_full | Chiral oxazolidines acting as transient hydroxyalkyl-functionalized N-heterocyclic carbenes: an efficient route to air stable copper and gold complexes for asymmetric catalysis |
title_fullStr | Chiral oxazolidines acting as transient hydroxyalkyl-functionalized N-heterocyclic carbenes: an efficient route to air stable copper and gold complexes for asymmetric catalysis |
title_full_unstemmed | Chiral oxazolidines acting as transient hydroxyalkyl-functionalized N-heterocyclic carbenes: an efficient route to air stable copper and gold complexes for asymmetric catalysis |
title_short | Chiral oxazolidines acting as transient hydroxyalkyl-functionalized N-heterocyclic carbenes: an efficient route to air stable copper and gold complexes for asymmetric catalysis |
title_sort | chiral oxazolidines acting as transient hydroxyalkyl-functionalized n-heterocyclic carbenes: an efficient route to air stable copper and gold complexes for asymmetric catalysis |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9350591/ https://www.ncbi.nlm.nih.gov/pubmed/35975143 http://dx.doi.org/10.1039/d2sc02908a |
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