Cargando…
Nickel-Catalyzed Addition of Aryl Bromides to Aldehydes To Form Hindered Secondary Alcohols
[Image: see text] Transition-metal-catalyzed addition of aryl halides across carbonyls remains poorly developed, especially for aliphatic aldehydes and hindered substrate combinations. We report here that simple nickel complexes of bipyridine and PyBox can catalyze the addition of aryl halides to bo...
Autores principales: | , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2019
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6368192/ https://www.ncbi.nlm.nih.gov/pubmed/30693771 http://dx.doi.org/10.1021/jacs.8b13709 |
_version_ | 1783393939742523392 |
---|---|
author | Garcia, Kevin J. Gilbert, Michael M. Weix, Daniel J. |
author_facet | Garcia, Kevin J. Gilbert, Michael M. Weix, Daniel J. |
author_sort | Garcia, Kevin J. |
collection | PubMed |
description | [Image: see text] Transition-metal-catalyzed addition of aryl halides across carbonyls remains poorly developed, especially for aliphatic aldehydes and hindered substrate combinations. We report here that simple nickel complexes of bipyridine and PyBox can catalyze the addition of aryl halides to both aromatic and aliphatic aldehydes using zinc metal as the reducing agent. This convenient approach tolerates acidic functional groups that are not compatible with Grignard reactions, yet sterically hindered substrates still couple in high yield (33 examples, 70% average yield). Mechanistic studies show that an arylnickel, and not an arylzinc, adds efficiently to cyclohexanecarboxaldehyde, but only in the presence of a Lewis acid co-catalyst (ZnBr(2)). |
format | Online Article Text |
id | pubmed-6368192 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-63681922020-01-29 Nickel-Catalyzed Addition of Aryl Bromides to Aldehydes To Form Hindered Secondary Alcohols Garcia, Kevin J. Gilbert, Michael M. Weix, Daniel J. J Am Chem Soc [Image: see text] Transition-metal-catalyzed addition of aryl halides across carbonyls remains poorly developed, especially for aliphatic aldehydes and hindered substrate combinations. We report here that simple nickel complexes of bipyridine and PyBox can catalyze the addition of aryl halides to both aromatic and aliphatic aldehydes using zinc metal as the reducing agent. This convenient approach tolerates acidic functional groups that are not compatible with Grignard reactions, yet sterically hindered substrates still couple in high yield (33 examples, 70% average yield). Mechanistic studies show that an arylnickel, and not an arylzinc, adds efficiently to cyclohexanecarboxaldehyde, but only in the presence of a Lewis acid co-catalyst (ZnBr(2)). American Chemical Society 2019-01-29 2019-02-06 /pmc/articles/PMC6368192/ /pubmed/30693771 http://dx.doi.org/10.1021/jacs.8b13709 Text en Copyright © 2019 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Garcia, Kevin J. Gilbert, Michael M. Weix, Daniel J. Nickel-Catalyzed Addition of Aryl Bromides to Aldehydes To Form Hindered Secondary Alcohols |
title | Nickel-Catalyzed
Addition of Aryl Bromides to Aldehydes
To Form Hindered Secondary Alcohols |
title_full | Nickel-Catalyzed
Addition of Aryl Bromides to Aldehydes
To Form Hindered Secondary Alcohols |
title_fullStr | Nickel-Catalyzed
Addition of Aryl Bromides to Aldehydes
To Form Hindered Secondary Alcohols |
title_full_unstemmed | Nickel-Catalyzed
Addition of Aryl Bromides to Aldehydes
To Form Hindered Secondary Alcohols |
title_short | Nickel-Catalyzed
Addition of Aryl Bromides to Aldehydes
To Form Hindered Secondary Alcohols |
title_sort | nickel-catalyzed
addition of aryl bromides to aldehydes
to form hindered secondary alcohols |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6368192/ https://www.ncbi.nlm.nih.gov/pubmed/30693771 http://dx.doi.org/10.1021/jacs.8b13709 |
work_keys_str_mv | AT garciakevinj nickelcatalyzedadditionofarylbromidestoaldehydestoformhinderedsecondaryalcohols AT gilbertmichaelm nickelcatalyzedadditionofarylbromidestoaldehydestoformhinderedsecondaryalcohols AT weixdanielj nickelcatalyzedadditionofarylbromidestoaldehydestoformhinderedsecondaryalcohols |