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Selective skeletal editing of polycyclic arenes using organophotoredox dearomative functionalization

Reactions that lead to destruction of aromatic ring systems often require harsh conditions and, thus, take place with poor selectivities. Selective partial dearomatization of fused arenes is even more challenging but can be a strategic approach to creating versatile, complex polycyclic frameworks. H...

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Autores principales: Ji, Peng, Davies, Cassondra C., Gao, Feng, Chen, Jing, Meng, Xiang, Houk, Kendall N., Chen, Shuming, Wang, Wei
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9355940/
https://www.ncbi.nlm.nih.gov/pubmed/35931700
http://dx.doi.org/10.1038/s41467-022-32201-7
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author Ji, Peng
Davies, Cassondra C.
Gao, Feng
Chen, Jing
Meng, Xiang
Houk, Kendall N.
Chen, Shuming
Wang, Wei
author_facet Ji, Peng
Davies, Cassondra C.
Gao, Feng
Chen, Jing
Meng, Xiang
Houk, Kendall N.
Chen, Shuming
Wang, Wei
author_sort Ji, Peng
collection PubMed
description Reactions that lead to destruction of aromatic ring systems often require harsh conditions and, thus, take place with poor selectivities. Selective partial dearomatization of fused arenes is even more challenging but can be a strategic approach to creating versatile, complex polycyclic frameworks. Herein we describe a general organophotoredox approach for the chemo- and regioselective dearomatization of structurally diverse polycyclic aromatics, including quinolines, isoquinolines, quinoxalines, naphthalenes, anthracenes and phenanthrenes. The success of the method for chemoselective oxidative rupture of aromatic moieties relies on precise manipulation of the electronic nature of the fused polycyclic arenes. Mechanistic studies show that the addition of a hydrogen atom transfer (HAT) agent helps favor the dearomatization pathway over the more thermodynamically downhill aromatization pathway. We show that this strategy can be applied to rapid synthesis of biologically valued targets and late-stage skeletal remodeling en route to complex structures.
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spelling pubmed-93559402022-08-07 Selective skeletal editing of polycyclic arenes using organophotoredox dearomative functionalization Ji, Peng Davies, Cassondra C. Gao, Feng Chen, Jing Meng, Xiang Houk, Kendall N. Chen, Shuming Wang, Wei Nat Commun Article Reactions that lead to destruction of aromatic ring systems often require harsh conditions and, thus, take place with poor selectivities. Selective partial dearomatization of fused arenes is even more challenging but can be a strategic approach to creating versatile, complex polycyclic frameworks. Herein we describe a general organophotoredox approach for the chemo- and regioselective dearomatization of structurally diverse polycyclic aromatics, including quinolines, isoquinolines, quinoxalines, naphthalenes, anthracenes and phenanthrenes. The success of the method for chemoselective oxidative rupture of aromatic moieties relies on precise manipulation of the electronic nature of the fused polycyclic arenes. Mechanistic studies show that the addition of a hydrogen atom transfer (HAT) agent helps favor the dearomatization pathway over the more thermodynamically downhill aromatization pathway. We show that this strategy can be applied to rapid synthesis of biologically valued targets and late-stage skeletal remodeling en route to complex structures. Nature Publishing Group UK 2022-08-05 /pmc/articles/PMC9355940/ /pubmed/35931700 http://dx.doi.org/10.1038/s41467-022-32201-7 Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Ji, Peng
Davies, Cassondra C.
Gao, Feng
Chen, Jing
Meng, Xiang
Houk, Kendall N.
Chen, Shuming
Wang, Wei
Selective skeletal editing of polycyclic arenes using organophotoredox dearomative functionalization
title Selective skeletal editing of polycyclic arenes using organophotoredox dearomative functionalization
title_full Selective skeletal editing of polycyclic arenes using organophotoredox dearomative functionalization
title_fullStr Selective skeletal editing of polycyclic arenes using organophotoredox dearomative functionalization
title_full_unstemmed Selective skeletal editing of polycyclic arenes using organophotoredox dearomative functionalization
title_short Selective skeletal editing of polycyclic arenes using organophotoredox dearomative functionalization
title_sort selective skeletal editing of polycyclic arenes using organophotoredox dearomative functionalization
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9355940/
https://www.ncbi.nlm.nih.gov/pubmed/35931700
http://dx.doi.org/10.1038/s41467-022-32201-7
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