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Post-functionalization of dibenzothiophene to functionalized biphenyls via a photoinduced thia-Baeyer-Villiger oxidation

The Baeyer-Villiger reaction is used extensively in organic chemistry. Sila- and bora-variants have also been documented widely, with these processes underpinning, for example, the Fleming-Tamao oxidation and hydroborative alkene hydration, respectively. By contrast, the development of thia-Baeyer-V...

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Autores principales: Ma, Xiaofeng, Liu, Yazhou, Du, Le, Zhou, Jingwei, Markó, István E.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7021910/
https://www.ncbi.nlm.nih.gov/pubmed/32060269
http://dx.doi.org/10.1038/s41467-020-14522-7
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author Ma, Xiaofeng
Liu, Yazhou
Du, Le
Zhou, Jingwei
Markó, István E.
author_facet Ma, Xiaofeng
Liu, Yazhou
Du, Le
Zhou, Jingwei
Markó, István E.
author_sort Ma, Xiaofeng
collection PubMed
description The Baeyer-Villiger reaction is used extensively in organic chemistry. Sila- and bora-variants have also been documented widely, with these processes underpinning, for example, the Fleming-Tamao oxidation and hydroborative alkene hydration, respectively. By contrast, the development of thia-Baeyer-Villiger reactions involving sulfoxides has long been considered unlikely because competitive oxidation to the sulfone occurs exclusively. Here, we disclose a photoinduced thia-Baeyer-Villiger-type oxidations; specifically, we find that exposure of dibenzothiophene (DBT) derivatives to an iron porphyrin catalyst under Ultraviolet irradiation in the presence of t-BuOOH generates sulfinic esters in up to 87% yield. The produced sulfinic esters are transformed to a variety of biphenyl substrates including biphenyl sulfoxides, sulfones and sulfonamides in 1-2 steps. These results provide a mild process for the selective functionalization of sulfur compounds, and offer a biomimetic approach to convert DBT into 2-hydroxybiphenyl under controllable stepwise pathway. Based upon experimental evidences and DFT calculation, a mechanism is proposed.
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spelling pubmed-70219102020-02-21 Post-functionalization of dibenzothiophene to functionalized biphenyls via a photoinduced thia-Baeyer-Villiger oxidation Ma, Xiaofeng Liu, Yazhou Du, Le Zhou, Jingwei Markó, István E. Nat Commun Article The Baeyer-Villiger reaction is used extensively in organic chemistry. Sila- and bora-variants have also been documented widely, with these processes underpinning, for example, the Fleming-Tamao oxidation and hydroborative alkene hydration, respectively. By contrast, the development of thia-Baeyer-Villiger reactions involving sulfoxides has long been considered unlikely because competitive oxidation to the sulfone occurs exclusively. Here, we disclose a photoinduced thia-Baeyer-Villiger-type oxidations; specifically, we find that exposure of dibenzothiophene (DBT) derivatives to an iron porphyrin catalyst under Ultraviolet irradiation in the presence of t-BuOOH generates sulfinic esters in up to 87% yield. The produced sulfinic esters are transformed to a variety of biphenyl substrates including biphenyl sulfoxides, sulfones and sulfonamides in 1-2 steps. These results provide a mild process for the selective functionalization of sulfur compounds, and offer a biomimetic approach to convert DBT into 2-hydroxybiphenyl under controllable stepwise pathway. Based upon experimental evidences and DFT calculation, a mechanism is proposed. Nature Publishing Group UK 2020-02-14 /pmc/articles/PMC7021910/ /pubmed/32060269 http://dx.doi.org/10.1038/s41467-020-14522-7 Text en © The Author(s) 2020 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/.
spellingShingle Article
Ma, Xiaofeng
Liu, Yazhou
Du, Le
Zhou, Jingwei
Markó, István E.
Post-functionalization of dibenzothiophene to functionalized biphenyls via a photoinduced thia-Baeyer-Villiger oxidation
title Post-functionalization of dibenzothiophene to functionalized biphenyls via a photoinduced thia-Baeyer-Villiger oxidation
title_full Post-functionalization of dibenzothiophene to functionalized biphenyls via a photoinduced thia-Baeyer-Villiger oxidation
title_fullStr Post-functionalization of dibenzothiophene to functionalized biphenyls via a photoinduced thia-Baeyer-Villiger oxidation
title_full_unstemmed Post-functionalization of dibenzothiophene to functionalized biphenyls via a photoinduced thia-Baeyer-Villiger oxidation
title_short Post-functionalization of dibenzothiophene to functionalized biphenyls via a photoinduced thia-Baeyer-Villiger oxidation
title_sort post-functionalization of dibenzothiophene to functionalized biphenyls via a photoinduced thia-baeyer-villiger oxidation
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7021910/
https://www.ncbi.nlm.nih.gov/pubmed/32060269
http://dx.doi.org/10.1038/s41467-020-14522-7
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