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α‐Functionalisation of Ketones Through Metal‐Free Electrophilic Activation

Triflic anhydride mediated activation of acetophenones leads to highly electrophilic intermediates that can undergo a variety of transformations when treated with nucleophiles. This electrophilic ketone activation gives access to α‐arylated and α‐oxyaminated acetophenones under metal‐free conditions...

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Autores principales: Zawodny, Wojciech, Teskey, Christopher J., Mishevska, Magdalena, Völkl, Martin, Maryasin, Boris, González, Leticia, Maulide, Nuno
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7693173/
https://www.ncbi.nlm.nih.gov/pubmed/32914929
http://dx.doi.org/10.1002/anie.202006398
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author Zawodny, Wojciech
Teskey, Christopher J.
Mishevska, Magdalena
Völkl, Martin
Maryasin, Boris
González, Leticia
Maulide, Nuno
author_facet Zawodny, Wojciech
Teskey, Christopher J.
Mishevska, Magdalena
Völkl, Martin
Maryasin, Boris
González, Leticia
Maulide, Nuno
author_sort Zawodny, Wojciech
collection PubMed
description Triflic anhydride mediated activation of acetophenones leads to highly electrophilic intermediates that can undergo a variety of transformations when treated with nucleophiles. This electrophilic ketone activation gives access to α‐arylated and α‐oxyaminated acetophenones under metal‐free conditions in moderate to excellent yields and enables extension to the synthesis of arylated morpholines via generation of vinylsulfonium salts. Computational investigations confirmed the transient existence of intermediates derived from vinyl triflates and the role of the oxygen atoms at the para position of aromatic ring in facilitating their stabilisation.
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spelling pubmed-76931732020-12-11 α‐Functionalisation of Ketones Through Metal‐Free Electrophilic Activation Zawodny, Wojciech Teskey, Christopher J. Mishevska, Magdalena Völkl, Martin Maryasin, Boris González, Leticia Maulide, Nuno Angew Chem Int Ed Engl Communications Triflic anhydride mediated activation of acetophenones leads to highly electrophilic intermediates that can undergo a variety of transformations when treated with nucleophiles. This electrophilic ketone activation gives access to α‐arylated and α‐oxyaminated acetophenones under metal‐free conditions in moderate to excellent yields and enables extension to the synthesis of arylated morpholines via generation of vinylsulfonium salts. Computational investigations confirmed the transient existence of intermediates derived from vinyl triflates and the role of the oxygen atoms at the para position of aromatic ring in facilitating their stabilisation. John Wiley and Sons Inc. 2020-09-11 2020-11-16 /pmc/articles/PMC7693173/ /pubmed/32914929 http://dx.doi.org/10.1002/anie.202006398 Text en © 2020 The Authors. Published by Wiley-VCH GmbH 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
Zawodny, Wojciech
Teskey, Christopher J.
Mishevska, Magdalena
Völkl, Martin
Maryasin, Boris
González, Leticia
Maulide, Nuno
α‐Functionalisation of Ketones Through Metal‐Free Electrophilic Activation
title α‐Functionalisation of Ketones Through Metal‐Free Electrophilic Activation
title_full α‐Functionalisation of Ketones Through Metal‐Free Electrophilic Activation
title_fullStr α‐Functionalisation of Ketones Through Metal‐Free Electrophilic Activation
title_full_unstemmed α‐Functionalisation of Ketones Through Metal‐Free Electrophilic Activation
title_short α‐Functionalisation of Ketones Through Metal‐Free Electrophilic Activation
title_sort α‐functionalisation of ketones through metal‐free electrophilic activation
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7693173/
https://www.ncbi.nlm.nih.gov/pubmed/32914929
http://dx.doi.org/10.1002/anie.202006398
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