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Expanding Zirconocene Hydride Catalysis: In Situ Generation and Turnover of ZrH Catalysts Enabling Catalytic Carbonyl Reductions
[Image: see text] Despite the wide use and popularity of metal hydride catalysis, methods utilizing zirconium hydride catalysts remain underexplored. Here, we report the development of a mild method for the in situ preparation and use of zirconium hydride catalysts. This robust method requires only...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9169672/ https://www.ncbi.nlm.nih.gov/pubmed/35685613 http://dx.doi.org/10.1021/acscatal.2c00079 |
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author | Kehner, Rebecca A. Hewitt, Matthew Christian Bayeh-Romero, Liela |
author_facet | Kehner, Rebecca A. Hewitt, Matthew Christian Bayeh-Romero, Liela |
author_sort | Kehner, Rebecca A. |
collection | PubMed |
description | [Image: see text] Despite the wide use and popularity of metal hydride catalysis, methods utilizing zirconium hydride catalysts remain underexplored. Here, we report the development of a mild method for the in situ preparation and use of zirconium hydride catalysts. This robust method requires only 2.5–5 mol % of zirconocene dichloride in combination with a hydrosilane as the stoichiometric reductant and does not require careful air- or moisture-free techniques. A key finding of this study concerns an amine-mediated ligand exchange en route to the active zirconocene hydride catalyst. A mechanistic investigation supports the intermediacy of an oxo-bridged dimer precatalyst. The application of this method to the reduction of a wide variety of carbonyl-containing substrates, including ketones, aldehydes, enones, ynones, and lactones, is demonstrated with up to 92% yield and exhibits broad functional group tolerability. These findings open up alternative avenues for the catalytic application of chlorozirconocenes, potentially serving as the foundation for broader applications of zirconium hydride catalysis. |
format | Online Article Text |
id | pubmed-9169672 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-91696722023-01-18 Expanding Zirconocene Hydride Catalysis: In Situ Generation and Turnover of ZrH Catalysts Enabling Catalytic Carbonyl Reductions Kehner, Rebecca A. Hewitt, Matthew Christian Bayeh-Romero, Liela ACS Catal [Image: see text] Despite the wide use and popularity of metal hydride catalysis, methods utilizing zirconium hydride catalysts remain underexplored. Here, we report the development of a mild method for the in situ preparation and use of zirconium hydride catalysts. This robust method requires only 2.5–5 mol % of zirconocene dichloride in combination with a hydrosilane as the stoichiometric reductant and does not require careful air- or moisture-free techniques. A key finding of this study concerns an amine-mediated ligand exchange en route to the active zirconocene hydride catalyst. A mechanistic investigation supports the intermediacy of an oxo-bridged dimer precatalyst. The application of this method to the reduction of a wide variety of carbonyl-containing substrates, including ketones, aldehydes, enones, ynones, and lactones, is demonstrated with up to 92% yield and exhibits broad functional group tolerability. These findings open up alternative avenues for the catalytic application of chlorozirconocenes, potentially serving as the foundation for broader applications of zirconium hydride catalysis. American Chemical Society 2022-01-18 2022-02-04 /pmc/articles/PMC9169672/ /pubmed/35685613 http://dx.doi.org/10.1021/acscatal.2c00079 Text en © 2022 American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Kehner, Rebecca A. Hewitt, Matthew Christian Bayeh-Romero, Liela Expanding Zirconocene Hydride Catalysis: In Situ Generation and Turnover of ZrH Catalysts Enabling Catalytic Carbonyl Reductions |
title | Expanding Zirconocene Hydride Catalysis: In
Situ Generation and Turnover of ZrH Catalysts Enabling Catalytic
Carbonyl Reductions |
title_full | Expanding Zirconocene Hydride Catalysis: In
Situ Generation and Turnover of ZrH Catalysts Enabling Catalytic
Carbonyl Reductions |
title_fullStr | Expanding Zirconocene Hydride Catalysis: In
Situ Generation and Turnover of ZrH Catalysts Enabling Catalytic
Carbonyl Reductions |
title_full_unstemmed | Expanding Zirconocene Hydride Catalysis: In
Situ Generation and Turnover of ZrH Catalysts Enabling Catalytic
Carbonyl Reductions |
title_short | Expanding Zirconocene Hydride Catalysis: In
Situ Generation and Turnover of ZrH Catalysts Enabling Catalytic
Carbonyl Reductions |
title_sort | expanding zirconocene hydride catalysis: in
situ generation and turnover of zrh catalysts enabling catalytic
carbonyl reductions |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9169672/ https://www.ncbi.nlm.nih.gov/pubmed/35685613 http://dx.doi.org/10.1021/acscatal.2c00079 |
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