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Theoretical Investigations on the Rh(III)-Catalyzed Oxidative C–H Activation/Annulation of Salicylaldehydes with Masked Enynes: Mechanism Insights and Regioselectivity Origins
[Image: see text] The mechanism underlying the rhodium(III)-catalyzed reaction of the C–H alkenylation/annulation reaction of salicylaldehydes with enynes has been thoroughly investigated using DFT calculations. Based on mechanistic studies, our focus primarily lies on the regioselectivity of asymme...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10688203/ https://www.ncbi.nlm.nih.gov/pubmed/38046303 http://dx.doi.org/10.1021/acsomega.3c07381 |
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author | Xiang, Xin Wei, Wei Zhao, Zeng-Xia Zhang, Hong-Xing |
author_facet | Xiang, Xin Wei, Wei Zhao, Zeng-Xia Zhang, Hong-Xing |
author_sort | Xiang, Xin |
collection | PubMed |
description | [Image: see text] The mechanism underlying the rhodium(III)-catalyzed reaction of the C–H alkenylation/annulation reaction of salicylaldehydes with enynes has been thoroughly investigated using DFT calculations. Based on mechanistic studies, our focus primarily lies on the regioselectivity of asymmetric alkynes inserting into the Rh–C bond and the involvement of the auxiliary group OAc(–) in these reactions. Our theoretical study uncovers that, with acetate assistance, a stepwise S(N)2′ cyclization, 1,3-Rh migration, β-H elimination, and reductive elimination process occur. Furthermore, we also explore the role of substitution at C(α) (CH(3) vs H) in the reaction. As demonstrated in this work, these findings are applicable to other related reactions. |
format | Online Article Text |
id | pubmed-10688203 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-106882032023-12-01 Theoretical Investigations on the Rh(III)-Catalyzed Oxidative C–H Activation/Annulation of Salicylaldehydes with Masked Enynes: Mechanism Insights and Regioselectivity Origins Xiang, Xin Wei, Wei Zhao, Zeng-Xia Zhang, Hong-Xing ACS Omega [Image: see text] The mechanism underlying the rhodium(III)-catalyzed reaction of the C–H alkenylation/annulation reaction of salicylaldehydes with enynes has been thoroughly investigated using DFT calculations. Based on mechanistic studies, our focus primarily lies on the regioselectivity of asymmetric alkynes inserting into the Rh–C bond and the involvement of the auxiliary group OAc(–) in these reactions. Our theoretical study uncovers that, with acetate assistance, a stepwise S(N)2′ cyclization, 1,3-Rh migration, β-H elimination, and reductive elimination process occur. Furthermore, we also explore the role of substitution at C(α) (CH(3) vs H) in the reaction. As demonstrated in this work, these findings are applicable to other related reactions. American Chemical Society 2023-11-17 /pmc/articles/PMC10688203/ /pubmed/38046303 http://dx.doi.org/10.1021/acsomega.3c07381 Text en © 2023 The Authors. Published by 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 | Xiang, Xin Wei, Wei Zhao, Zeng-Xia Zhang, Hong-Xing Theoretical Investigations on the Rh(III)-Catalyzed Oxidative C–H Activation/Annulation of Salicylaldehydes with Masked Enynes: Mechanism Insights and Regioselectivity Origins |
title | Theoretical Investigations
on the Rh(III)-Catalyzed
Oxidative C–H Activation/Annulation of Salicylaldehydes with
Masked Enynes: Mechanism Insights and Regioselectivity Origins |
title_full | Theoretical Investigations
on the Rh(III)-Catalyzed
Oxidative C–H Activation/Annulation of Salicylaldehydes with
Masked Enynes: Mechanism Insights and Regioselectivity Origins |
title_fullStr | Theoretical Investigations
on the Rh(III)-Catalyzed
Oxidative C–H Activation/Annulation of Salicylaldehydes with
Masked Enynes: Mechanism Insights and Regioselectivity Origins |
title_full_unstemmed | Theoretical Investigations
on the Rh(III)-Catalyzed
Oxidative C–H Activation/Annulation of Salicylaldehydes with
Masked Enynes: Mechanism Insights and Regioselectivity Origins |
title_short | Theoretical Investigations
on the Rh(III)-Catalyzed
Oxidative C–H Activation/Annulation of Salicylaldehydes with
Masked Enynes: Mechanism Insights and Regioselectivity Origins |
title_sort | theoretical investigations
on the rh(iii)-catalyzed
oxidative c–h activation/annulation of salicylaldehydes with
masked enynes: mechanism insights and regioselectivity origins |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10688203/ https://www.ncbi.nlm.nih.gov/pubmed/38046303 http://dx.doi.org/10.1021/acsomega.3c07381 |
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