Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement

A mechanistic investigation of the acid-catalysed redox-neutral oxoarylation reaction of ynamides using electrospray ionisation mass-spectrometry (ESI-MS) and quantum chemical calculations (DFT and MP2) is presented. This study reveals the diversity of pathways and products available from an otherwi...

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Autores principales: Maryasin, Boris, Kaldre, Dainis, Galaverna, Renan, Klose, Immo, Ruider, Stefan, Drescher, Martina, Kählig, Hanspeter, González, Leticia, Eberlin, Marcos N., Jurberg, Igor D., Maulide, Nuno
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2018
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5941282/
https://www.ncbi.nlm.nih.gov/pubmed/29780542
http://dx.doi.org/10.1039/c7sc04736c
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author Maryasin, Boris
Kaldre, Dainis
Galaverna, Renan
Klose, Immo
Ruider, Stefan
Drescher, Martina
Kählig, Hanspeter
González, Leticia
Eberlin, Marcos N.
Jurberg, Igor D.
Maulide, Nuno
author_facet Maryasin, Boris
Kaldre, Dainis
Galaverna, Renan
Klose, Immo
Ruider, Stefan
Drescher, Martina
Kählig, Hanspeter
González, Leticia
Eberlin, Marcos N.
Jurberg, Igor D.
Maulide, Nuno
author_sort Maryasin, Boris
collection PubMed
description A mechanistic investigation of the acid-catalysed redox-neutral oxoarylation reaction of ynamides using electrospray ionisation mass-spectrometry (ESI-MS) and quantum chemical calculations (DFT and MP2) is presented. This study reveals the diversity of pathways and products available from an otherwise deceptively simple-looking, classical transformation: fragmentation, an unusual meta-arylation and competing α-carbonyl cation pathways are some of the alternatives unveiled by ESI-MS and mechanistic experiments. Detailed calculations explain the observed trends and rationalise the results.
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spelling pubmed-59412822018-05-18 Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement Maryasin, Boris Kaldre, Dainis Galaverna, Renan Klose, Immo Ruider, Stefan Drescher, Martina Kählig, Hanspeter González, Leticia Eberlin, Marcos N. Jurberg, Igor D. Maulide, Nuno Chem Sci Chemistry A mechanistic investigation of the acid-catalysed redox-neutral oxoarylation reaction of ynamides using electrospray ionisation mass-spectrometry (ESI-MS) and quantum chemical calculations (DFT and MP2) is presented. This study reveals the diversity of pathways and products available from an otherwise deceptively simple-looking, classical transformation: fragmentation, an unusual meta-arylation and competing α-carbonyl cation pathways are some of the alternatives unveiled by ESI-MS and mechanistic experiments. Detailed calculations explain the observed trends and rationalise the results. Royal Society of Chemistry 2018-04-10 /pmc/articles/PMC5941282/ /pubmed/29780542 http://dx.doi.org/10.1039/c7sc04736c Text en This journal is © The Royal Society of Chemistry 2018 http://creativecommons.org/licenses/by/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0)
spellingShingle Chemistry
Maryasin, Boris
Kaldre, Dainis
Galaverna, Renan
Klose, Immo
Ruider, Stefan
Drescher, Martina
Kählig, Hanspeter
González, Leticia
Eberlin, Marcos N.
Jurberg, Igor D.
Maulide, Nuno
Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement
title Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement
title_full Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement
title_fullStr Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement
title_full_unstemmed Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement
title_short Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement
title_sort unusual mechanisms in claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5941282/
https://www.ncbi.nlm.nih.gov/pubmed/29780542
http://dx.doi.org/10.1039/c7sc04736c
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