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Catalytic Enantioselective 6π Photocyclization of Acrylanilides
[Image: see text] Controlling absolute stereochemistry in catalytic photochemical reactions is generally challenging owing to high rates of background reactivity. Successful strategies broadly rely on selective excitation of the reaction substrate when associated with a chiral catalyst. Recent studi...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9837842/ https://www.ncbi.nlm.nih.gov/pubmed/36571763 http://dx.doi.org/10.1021/jacs.2c09267 |
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author | Jones, Benjamin A. Solon, Pearse Popescu, Mihai V. Du, Ji-Yuan Paton, Robert Smith, Martin D. |
author_facet | Jones, Benjamin A. Solon, Pearse Popescu, Mihai V. Du, Ji-Yuan Paton, Robert Smith, Martin D. |
author_sort | Jones, Benjamin A. |
collection | PubMed |
description | [Image: see text] Controlling absolute stereochemistry in catalytic photochemical reactions is generally challenging owing to high rates of background reactivity. Successful strategies broadly rely on selective excitation of the reaction substrate when associated with a chiral catalyst. Recent studies have demonstrated that chiral Lewis acid complexes can enable selective energy transfer from a photosensitizer to facilitate enantioselective triplet state reactions. Here, we apply this approach to the enantioselective catalysis of a 6π photocyclization through the design of an iridium photosensitizer optimized to undergo energy transfer to a reaction substrate only in the presence of a chiral Lewis acid complex. Among a group of iridium(III) sensitizers, enantioselectivity and yield closely correlate with photocatalyst triplet energy within a narrow window enabled by a modest reduction in substrate triplet energy upon binding a scandium/ligand complex. These results demonstrate that photocatalyst tuning offers a means to suppress background reactivity and improve enantioselectivity in photochemical reactions. |
format | Online Article Text |
id | pubmed-9837842 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-98378422023-01-14 Catalytic Enantioselective 6π Photocyclization of Acrylanilides Jones, Benjamin A. Solon, Pearse Popescu, Mihai V. Du, Ji-Yuan Paton, Robert Smith, Martin D. J Am Chem Soc [Image: see text] Controlling absolute stereochemistry in catalytic photochemical reactions is generally challenging owing to high rates of background reactivity. Successful strategies broadly rely on selective excitation of the reaction substrate when associated with a chiral catalyst. Recent studies have demonstrated that chiral Lewis acid complexes can enable selective energy transfer from a photosensitizer to facilitate enantioselective triplet state reactions. Here, we apply this approach to the enantioselective catalysis of a 6π photocyclization through the design of an iridium photosensitizer optimized to undergo energy transfer to a reaction substrate only in the presence of a chiral Lewis acid complex. Among a group of iridium(III) sensitizers, enantioselectivity and yield closely correlate with photocatalyst triplet energy within a narrow window enabled by a modest reduction in substrate triplet energy upon binding a scandium/ligand complex. These results demonstrate that photocatalyst tuning offers a means to suppress background reactivity and improve enantioselectivity in photochemical reactions. American Chemical Society 2022-12-26 /pmc/articles/PMC9837842/ /pubmed/36571763 http://dx.doi.org/10.1021/jacs.2c09267 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Jones, Benjamin A. Solon, Pearse Popescu, Mihai V. Du, Ji-Yuan Paton, Robert Smith, Martin D. Catalytic Enantioselective 6π Photocyclization of Acrylanilides |
title | Catalytic Enantioselective
6π Photocyclization
of Acrylanilides |
title_full | Catalytic Enantioselective
6π Photocyclization
of Acrylanilides |
title_fullStr | Catalytic Enantioselective
6π Photocyclization
of Acrylanilides |
title_full_unstemmed | Catalytic Enantioselective
6π Photocyclization
of Acrylanilides |
title_short | Catalytic Enantioselective
6π Photocyclization
of Acrylanilides |
title_sort | catalytic enantioselective
6π photocyclization
of acrylanilides |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9837842/ https://www.ncbi.nlm.nih.gov/pubmed/36571763 http://dx.doi.org/10.1021/jacs.2c09267 |
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