N‐Heterocyclic Carbene Catalyzed Photoenolization/Diels–Alder Reaction of Acid Fluorides

The combination of light activation and N‐heterocyclic carbene (NHC) organocatalysis has enabled the use of acid fluorides as substrates in a UVA‐light‐mediated photochemical transformation previously observed only with aromatic aldehydes and ketones. Stoichiometric studies and TD‐DFT calculations s...

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Autores principales: Mavroskoufis, Andreas, Rajes, Keerthana, Golz, Paul, Agrawal, Arush, Ruß, Vincent, Götze, Jan P., Hopkinson, Matthew N.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7027522/
https://www.ncbi.nlm.nih.gov/pubmed/31814280
http://dx.doi.org/10.1002/anie.201914456
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author Mavroskoufis, Andreas
Rajes, Keerthana
Golz, Paul
Agrawal, Arush
Ruß, Vincent
Götze, Jan P.
Hopkinson, Matthew N.
author_facet Mavroskoufis, Andreas
Rajes, Keerthana
Golz, Paul
Agrawal, Arush
Ruß, Vincent
Götze, Jan P.
Hopkinson, Matthew N.
author_sort Mavroskoufis, Andreas
collection PubMed
description The combination of light activation and N‐heterocyclic carbene (NHC) organocatalysis has enabled the use of acid fluorides as substrates in a UVA‐light‐mediated photochemical transformation previously observed only with aromatic aldehydes and ketones. Stoichiometric studies and TD‐DFT calculations support a mechanism involving the photoactivation of an ortho‐toluoyl azolium intermediate, which exhibits “ketone‐like” photochemical reactivity under UVA irradiation. Using this photo‐NHC catalysis approach, a novel photoenolization/Diels–Alder (PEDA) process was developed that leads to diverse isochroman‐1‐one derivatives.
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spelling pubmed-70275222020-02-24 N‐Heterocyclic Carbene Catalyzed Photoenolization/Diels–Alder Reaction of Acid Fluorides Mavroskoufis, Andreas Rajes, Keerthana Golz, Paul Agrawal, Arush Ruß, Vincent Götze, Jan P. Hopkinson, Matthew N. Angew Chem Int Ed Engl Communications The combination of light activation and N‐heterocyclic carbene (NHC) organocatalysis has enabled the use of acid fluorides as substrates in a UVA‐light‐mediated photochemical transformation previously observed only with aromatic aldehydes and ketones. Stoichiometric studies and TD‐DFT calculations support a mechanism involving the photoactivation of an ortho‐toluoyl azolium intermediate, which exhibits “ketone‐like” photochemical reactivity under UVA irradiation. Using this photo‐NHC catalysis approach, a novel photoenolization/Diels–Alder (PEDA) process was developed that leads to diverse isochroman‐1‐one derivatives. John Wiley and Sons Inc. 2020-01-09 2020-02-17 /pmc/articles/PMC7027522/ /pubmed/31814280 http://dx.doi.org/10.1002/anie.201914456 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the 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
Mavroskoufis, Andreas
Rajes, Keerthana
Golz, Paul
Agrawal, Arush
Ruß, Vincent
Götze, Jan P.
Hopkinson, Matthew N.
N‐Heterocyclic Carbene Catalyzed Photoenolization/Diels–Alder Reaction of Acid Fluorides
title N‐Heterocyclic Carbene Catalyzed Photoenolization/Diels–Alder Reaction of Acid Fluorides
title_full N‐Heterocyclic Carbene Catalyzed Photoenolization/Diels–Alder Reaction of Acid Fluorides
title_fullStr N‐Heterocyclic Carbene Catalyzed Photoenolization/Diels–Alder Reaction of Acid Fluorides
title_full_unstemmed N‐Heterocyclic Carbene Catalyzed Photoenolization/Diels–Alder Reaction of Acid Fluorides
title_short N‐Heterocyclic Carbene Catalyzed Photoenolization/Diels–Alder Reaction of Acid Fluorides
title_sort n‐heterocyclic carbene catalyzed photoenolization/diels–alder reaction of acid fluorides
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7027522/
https://www.ncbi.nlm.nih.gov/pubmed/31814280
http://dx.doi.org/10.1002/anie.201914456
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