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Unusual mechanisms in Claisen rearrangements: an ionic fragmentation leading to a meta-selective rearrangement†
Chemical Science ( IF 8.4 ) Pub Date : 2018-04-10 00:00:00 , DOI: 10.1039/c7sc04736c
Boris Maryasin 1, 2, 3, 4, 5 , Dainis Kaldre 1, 2, 3, 4, 5 , Renan Galaverna 6, 7, 8, 9, 10 , Immo Klose 1, 2, 3, 4, 5 , Stefan Ruider 1, 2, 3, 4, 5 , Martina Drescher 1, 2, 3, 4, 5 , Hanspeter Kählig 1, 2, 3, 4, 5 , Leticia González 1, 2, 4, 5, 11 , Marcos N. Eberlin 6, 7, 8, 9, 10 , Igor D. Jurberg 6, 8, 9, 10 , Nuno Maulide 1, 2, 3, 4, 5
Affiliation  

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.

中文翻译:

不寻常的机制克莱森重排:离子碎裂导致-选择性重排

提出了使用电喷雾电离质谱(ESI-MS)和量子化学计算(DFT和MP2)进行的酸催化的酰胺类氧化还原-中性羰基化反应的机理研究。这项研究揭示了从看似简单的经典转化中可以得到的途径和产物的多样性:裂解,不寻常的间位芳构化和竞争的α-羰基阳离子途径是ESI-MS和机理实验揭示的一些替代方法。详细的计算可以解释观察到的趋势并使结果合理化。
更新日期:2018-04-10
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