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

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Abstract

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.

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

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Publication details

The article was received on 02 Nov 2017, accepted on 24 Mar 2018 and first published on 10 Apr 2018


Article type: Edge Article
DOI: 10.1039/C7SC04736C
Citation: Chem. Sci., 2018, Advance Article
  • Open access: Creative Commons BY license
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    Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement

    B. Maryasin, D. Kaldre, R. Galaverna, I. Klose, S. Ruider, M. Drescher, H. Kählig, L. González, M. N. Eberlin, I. D. Jurberg and N. Maulide, Chem. Sci., 2018, Advance Article , DOI: 10.1039/C7SC04736C

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