Cargando…

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...

Descripción completa

Detalles Bibliográficos
Autores principales: Kehner, Rebecca A., Hewitt, Matthew Christian, Bayeh-Romero, Liela
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
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
_version_ 1784721251537780736
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
work_keys_str_mv AT kehnerrebeccaa expandingzirconocenehydridecatalysisinsitugenerationandturnoverofzrhcatalystsenablingcatalyticcarbonylreductions
AT hewittmatthewchristian expandingzirconocenehydridecatalysisinsitugenerationandturnoverofzrhcatalystsenablingcatalyticcarbonylreductions
AT bayehromeroliela expandingzirconocenehydridecatalysisinsitugenerationandturnoverofzrhcatalystsenablingcatalyticcarbonylreductions