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

Boris Maryasin; Dainis Kaldre; Renan Galaverna; Immo Klose; Stefan Ruider; Martina Drescher; Hanspeter Kählig; Leticia González; Marcos N. Eberlin; Igor D. Jurberg; Nuno Maulide

doi:10.1039/C7SC04736C

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

Boris Maryasin,

*^ab Dainis Kaldre,‡^a Renan Galaverna,‡^c Immo Klose,^a Stefan Ruider,^ab Martina Drescher,^a Hanspeter Kählig,^a Leticia González,

^b Marcos N. Eberlin,^c Igor D. Jurberg

*^d and Nuno Maulide

*^a

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* Corresponding authors

^a University of Vienna, Faculty of Chemistry, Institute of Organic Chemistry, Währinger Strasse 38, 1090 Vienna, Austria
E-mail: nuno.maulide@univie.ac.at, boris.maryasin@univie.ac.at

^b University of Vienna, Faculty of Chemistry, Institute of Theoretical Chemistry, Währinger Strasse 17, 1090 Vienna, Austria

^c State University of Campinas, ThoMSon Mass Spectrometry Laboratory, Institute of Chemistry, Rua Monteiro Lobato 270, Campinas, Brazil

^d State University of Campinas, Institute of Chemistry, Rua Monteiro Lobato 270, Campinas, Brazil
E-mail: idjurberg@iqm.unicamp.br

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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Chemical Science

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

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

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