Issue 17, 2018

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

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

Supplementary files

Article information

Article type
Edge Article
Submitted
02 Nov 2017
Accepted
24 Mar 2018
First published
10 Apr 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 4124-4131

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, 9, 4124 DOI: 10.1039/C7SC04736C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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