期刊
TETRAHEDRON
卷 71, 期 7, 页码 1050-1057出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.tet.2014.12.094
关键词
[3+2] Cycloaddition reactions; Azomethine ylides; Carbonyl ylides; Molecular mechanisms; DFT calculations
资金
- Ministerio de Ciencia e Innovacion of the Spanish Government [CTQ2013-45646-P]
- FONDECYT [1140341]
- Millennium Nucleus of Chemical Processes and Catalysis (CPC) [120082]
The participation of azomethine ylides (AYs) and carbonyl ylides (CYs) in [3+2] cycloaddition (32CA) reactions has been analysed at the DFT B3LYP/6-31G(d) level. The asymmetric substitution breaks the pseudodiradical character of the simplest three-atom-components (TACs), modifying their electrophilic and nucleophilic behaviours. These TACs react quickly towards electrophilic nitroethylene. However, while the reaction with AY takes place via a zw-type mechanism, the reaction with CV appears to take place via a pr-type mechanism. A different behaviour is found in the reactivity towards the nucleophilic methyl vinyl ether. While AY presents a high activation energy, CV presents a high reactivity via a pr-type mechanism. These reactions are completely regioselective, displaying exo stereoselectivity. The present study makes it possible to establish that the substitution provokes a different reactivity pattern in these TACs; while in CYs does not substantially modify their pr-type reactivity, AYs only participate in zw-type 32CA reactions towards electrophilic ethylenes. (C) 2015 Elsevier Ltd. All rights reserved.
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