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Visible Light Photocatalysis of 6π Heterocyclization

Photo‐mediated 6π cyclization is a valuable method for the formation of fused heterocyclic systems. Here we demonstrate that irradiation of cyclic 2‐aryloxyketones with blue LED light in the presence of an Ir(III) complex leads to efficient and high yielding arylation across a panoply of substrates...

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Detalles Bibliográficos
Autores principales: Münster, Niels, Parker, Nicholas A., van Dijk, Lucy, Paton, Robert S., Smith, Martin D.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5575533/
https://www.ncbi.nlm.nih.gov/pubmed/28640479
http://dx.doi.org/10.1002/anie.201705333
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author Münster, Niels
Parker, Nicholas A.
van Dijk, Lucy
Paton, Robert S.
Smith, Martin D.
author_facet Münster, Niels
Parker, Nicholas A.
van Dijk, Lucy
Paton, Robert S.
Smith, Martin D.
author_sort Münster, Niels
collection PubMed
description Photo‐mediated 6π cyclization is a valuable method for the formation of fused heterocyclic systems. Here we demonstrate that irradiation of cyclic 2‐aryloxyketones with blue LED light in the presence of an Ir(III) complex leads to efficient and high yielding arylation across a panoply of substrates by energy transfer. 2‐Arylthioketones and 2‐arylaminoketones also cyclize effectively under these conditions. Quantum calculation demonstrates that the reaction proceeds via conrotatory ring closure in the triplet excited state. Subsequent suprafacial 1,4‐hydrogen shift and epimerization leads to the observed cis‐fused products.
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spelling pubmed-55755332017-09-18 Visible Light Photocatalysis of 6π Heterocyclization Münster, Niels Parker, Nicholas A. van Dijk, Lucy Paton, Robert S. Smith, Martin D. Angew Chem Int Ed Engl Communications Photo‐mediated 6π cyclization is a valuable method for the formation of fused heterocyclic systems. Here we demonstrate that irradiation of cyclic 2‐aryloxyketones with blue LED light in the presence of an Ir(III) complex leads to efficient and high yielding arylation across a panoply of substrates by energy transfer. 2‐Arylthioketones and 2‐arylaminoketones also cyclize effectively under these conditions. Quantum calculation demonstrates that the reaction proceeds via conrotatory ring closure in the triplet excited state. Subsequent suprafacial 1,4‐hydrogen shift and epimerization leads to the observed cis‐fused products. John Wiley and Sons Inc. 2017-07-04 2017-08-01 /pmc/articles/PMC5575533/ /pubmed/28640479 http://dx.doi.org/10.1002/anie.201705333 Text en © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution (http://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Münster, Niels
Parker, Nicholas A.
van Dijk, Lucy
Paton, Robert S.
Smith, Martin D.
Visible Light Photocatalysis of 6π Heterocyclization
title Visible Light Photocatalysis of 6π Heterocyclization
title_full Visible Light Photocatalysis of 6π Heterocyclization
title_fullStr Visible Light Photocatalysis of 6π Heterocyclization
title_full_unstemmed Visible Light Photocatalysis of 6π Heterocyclization
title_short Visible Light Photocatalysis of 6π Heterocyclization
title_sort visible light photocatalysis of 6π heterocyclization
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5575533/
https://www.ncbi.nlm.nih.gov/pubmed/28640479
http://dx.doi.org/10.1002/anie.201705333
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