Iridium-Catalyzed and pH-Dependent Reductions of Nitroalkenes to Ketones

A highly chemoselective conversion of α,β-disubstituted nitroalkenes to ketones is developed. An acid-compatible iridium catalyst serves as the key to the conversion. At a 2500 S/C ratio, nitroalkenes were readily converted to ketones in up to 72% isolated yields. A new mechanistic mode involving th...

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Autores principales: Wang, Tingting, Liu, Changmeng, Xu, Dong, Xu, Jiaxi, Yang, Zhanhui
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9696932/
https://www.ncbi.nlm.nih.gov/pubmed/36431923
http://dx.doi.org/10.3390/molecules27227822
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author Wang, Tingting
Liu, Changmeng
Xu, Dong
Xu, Jiaxi
Yang, Zhanhui
author_facet Wang, Tingting
Liu, Changmeng
Xu, Dong
Xu, Jiaxi
Yang, Zhanhui
author_sort Wang, Tingting
collection PubMed
description A highly chemoselective conversion of α,β-disubstituted nitroalkenes to ketones is developed. An acid-compatible iridium catalyst serves as the key to the conversion. At a 2500 S/C ratio, nitroalkenes were readily converted to ketones in up to 72% isolated yields. A new mechanistic mode involving the reduction of nitroalkene to nitrosoalkene and N-alkenyl hydroxylamine is proposed. This conversion is ready to amplify to a gram-scale synthesis. The pH value plays an indispensable role in controlling the chemoselectivity.
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spelling pubmed-96969322022-11-26 Iridium-Catalyzed and pH-Dependent Reductions of Nitroalkenes to Ketones Wang, Tingting Liu, Changmeng Xu, Dong Xu, Jiaxi Yang, Zhanhui Molecules Article A highly chemoselective conversion of α,β-disubstituted nitroalkenes to ketones is developed. An acid-compatible iridium catalyst serves as the key to the conversion. At a 2500 S/C ratio, nitroalkenes were readily converted to ketones in up to 72% isolated yields. A new mechanistic mode involving the reduction of nitroalkene to nitrosoalkene and N-alkenyl hydroxylamine is proposed. This conversion is ready to amplify to a gram-scale synthesis. The pH value plays an indispensable role in controlling the chemoselectivity. MDPI 2022-11-13 /pmc/articles/PMC9696932/ /pubmed/36431923 http://dx.doi.org/10.3390/molecules27227822 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Wang, Tingting
Liu, Changmeng
Xu, Dong
Xu, Jiaxi
Yang, Zhanhui
Iridium-Catalyzed and pH-Dependent Reductions of Nitroalkenes to Ketones
title Iridium-Catalyzed and pH-Dependent Reductions of Nitroalkenes to Ketones
title_full Iridium-Catalyzed and pH-Dependent Reductions of Nitroalkenes to Ketones
title_fullStr Iridium-Catalyzed and pH-Dependent Reductions of Nitroalkenes to Ketones
title_full_unstemmed Iridium-Catalyzed and pH-Dependent Reductions of Nitroalkenes to Ketones
title_short Iridium-Catalyzed and pH-Dependent Reductions of Nitroalkenes to Ketones
title_sort iridium-catalyzed and ph-dependent reductions of nitroalkenes to ketones
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9696932/
https://www.ncbi.nlm.nih.gov/pubmed/36431923
http://dx.doi.org/10.3390/molecules27227822
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AT xujiaxi iridiumcatalyzedandphdependentreductionsofnitroalkenestoketones
AT yangzhanhui iridiumcatalyzedandphdependentreductionsofnitroalkenestoketones

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