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Published on: January 22, 2019
Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement
Boris Maryasin1,2, Dainis Kaldre1, Renan Galaverna3
1University of Vienna , Faculty of Chemistry , Institute of Organic Chemistry , Währinger Strasse 38 , 1090 Vienna , Austria . Email: nuno.maulide@univie.ac.at ;
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.
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