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Exploring the Acid-Catalyzed Reactions of 10,11-Epoxy-Dibenzo[a,d]cycloheptan-5-ol as the Synthetic Modules toward Polycyclic Aromatic Scaffolds

[Image: see text] The structural diversity of polycyclic aromatic hydrocarbons (PAHs) offers exciting opportunities for their applications. Yet, selective synthesis of such conjugated networks poses a formidable challenge. Compared to the prominence of transition-metal-catalyzed cross-coupling and o...

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Autores principales: Hsu, Cheng-Yi, Zheng, Cian-Jhe, Wu, Ying-Yann, Fan, Wen-Hsuan, Lin, Chih-Hsiu
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9244947/
https://www.ncbi.nlm.nih.gov/pubmed/35785270
http://dx.doi.org/10.1021/acsomega.2c01024
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author Hsu, Cheng-Yi
Zheng, Cian-Jhe
Wu, Ying-Yann
Fan, Wen-Hsuan
Lin, Chih-Hsiu
author_facet Hsu, Cheng-Yi
Zheng, Cian-Jhe
Wu, Ying-Yann
Fan, Wen-Hsuan
Lin, Chih-Hsiu
author_sort Hsu, Cheng-Yi
collection PubMed
description [Image: see text] The structural diversity of polycyclic aromatic hydrocarbons (PAHs) offers exciting opportunities for their applications. Yet, selective synthesis of such conjugated networks poses a formidable challenge. Compared to the prominence of transition-metal-catalyzed cross-coupling and oxidative Scholl reactions, cationic rearrangement in the synthesis of polycyclic aromatic hydrocarbon is an underexplored subject. In this study, we reveal that cationic intermediate generated from epoxy dibenzocycloheptanol can be transformed into acenes, azulene-embedded PAHs, and dibenzocycloheptanone derivatives. Reactive patterns, including Meinwald rearrangement, Nazarov cyclization, transannular aryl migration, and transannular Friedel–Crafts cyclization were identified. Both substrate structures and reaction temperature affect the reaction pathways in predictable and manageable manners. A mechanistic scheme was postulated as the working model to guide the reactivity for further application. Substrates containing heterocyclic and ferrocenyl groups exhibit similar reactivity profiles. The inquiry culminates in the selective synthesis of 5, 7, 12, 14-tetrasubstituted C(2h) and C(2v) pentacene derivatives. Our results demonstrate that polycyclic aromatic hydrocarbons can be selectively prepared with this cation-initiated strategy by methodically tuning the reactivity.
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spelling pubmed-92449472022-07-01 Exploring the Acid-Catalyzed Reactions of 10,11-Epoxy-Dibenzo[a,d]cycloheptan-5-ol as the Synthetic Modules toward Polycyclic Aromatic Scaffolds Hsu, Cheng-Yi Zheng, Cian-Jhe Wu, Ying-Yann Fan, Wen-Hsuan Lin, Chih-Hsiu ACS Omega [Image: see text] The structural diversity of polycyclic aromatic hydrocarbons (PAHs) offers exciting opportunities for their applications. Yet, selective synthesis of such conjugated networks poses a formidable challenge. Compared to the prominence of transition-metal-catalyzed cross-coupling and oxidative Scholl reactions, cationic rearrangement in the synthesis of polycyclic aromatic hydrocarbon is an underexplored subject. In this study, we reveal that cationic intermediate generated from epoxy dibenzocycloheptanol can be transformed into acenes, azulene-embedded PAHs, and dibenzocycloheptanone derivatives. Reactive patterns, including Meinwald rearrangement, Nazarov cyclization, transannular aryl migration, and transannular Friedel–Crafts cyclization were identified. Both substrate structures and reaction temperature affect the reaction pathways in predictable and manageable manners. A mechanistic scheme was postulated as the working model to guide the reactivity for further application. Substrates containing heterocyclic and ferrocenyl groups exhibit similar reactivity profiles. The inquiry culminates in the selective synthesis of 5, 7, 12, 14-tetrasubstituted C(2h) and C(2v) pentacene derivatives. Our results demonstrate that polycyclic aromatic hydrocarbons can be selectively prepared with this cation-initiated strategy by methodically tuning the reactivity. American Chemical Society 2022-06-16 /pmc/articles/PMC9244947/ /pubmed/35785270 http://dx.doi.org/10.1021/acsomega.2c01024 Text en © 2022 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 Hsu, Cheng-Yi
Zheng, Cian-Jhe
Wu, Ying-Yann
Fan, Wen-Hsuan
Lin, Chih-Hsiu
Exploring the Acid-Catalyzed Reactions of 10,11-Epoxy-Dibenzo[a,d]cycloheptan-5-ol as the Synthetic Modules toward Polycyclic Aromatic Scaffolds
title Exploring the Acid-Catalyzed Reactions of 10,11-Epoxy-Dibenzo[a,d]cycloheptan-5-ol as the Synthetic Modules toward Polycyclic Aromatic Scaffolds
title_full Exploring the Acid-Catalyzed Reactions of 10,11-Epoxy-Dibenzo[a,d]cycloheptan-5-ol as the Synthetic Modules toward Polycyclic Aromatic Scaffolds
title_fullStr Exploring the Acid-Catalyzed Reactions of 10,11-Epoxy-Dibenzo[a,d]cycloheptan-5-ol as the Synthetic Modules toward Polycyclic Aromatic Scaffolds
title_full_unstemmed Exploring the Acid-Catalyzed Reactions of 10,11-Epoxy-Dibenzo[a,d]cycloheptan-5-ol as the Synthetic Modules toward Polycyclic Aromatic Scaffolds
title_short Exploring the Acid-Catalyzed Reactions of 10,11-Epoxy-Dibenzo[a,d]cycloheptan-5-ol as the Synthetic Modules toward Polycyclic Aromatic Scaffolds
title_sort exploring the acid-catalyzed reactions of 10,11-epoxy-dibenzo[a,d]cycloheptan-5-ol as the synthetic modules toward polycyclic aromatic scaffolds
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9244947/
https://www.ncbi.nlm.nih.gov/pubmed/35785270
http://dx.doi.org/10.1021/acsomega.2c01024
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