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

Chemical Science
Boris MaryasinNuno Maulide

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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Citations

Aug 29, 2018·Chemical Communications : Chem Comm·Anat Milo, Mónica H Pérez Temprano
Sep 29, 2019·Chemical Communications : Chem Comm·Gui-Juan ChengXinhao Zhang
Sep 7, 2019·Chemistry : a European Journal·Tomoyuki YanagiHideki Yorimitsu
Jan 22, 2019·Monatshefte für chemie·Bogdan R BrutiuNuno Maulide
Oct 20, 2020·Chemical Society Reviews·Ciarán C LynchChristian Wolf
Sep 6, 2018·Organic Letters·Lucas L BaldassariDiogo S Lüdtke
Jul 30, 2021·Chemistry : a European Journal·Tomoyuki Yanagi, Hideki Yorimitsu

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Methods Mentioned

BETA
NMR
X-ray

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