Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement.
Chem Sci
; 9(17): 4124-4131, 2018 May 07.
Article
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| MEDLINE
| ID: mdl-29780542
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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