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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...

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Autores principales: Xiang, Xin, Wei, Wei, Zhao, Zeng-Xia, Zhang, Hong-Xing
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
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.
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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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