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Methylene Group Transfer in Carbonyl Compounds Discovered in silico and Detected Experimentally
Ilya D Gridnev1, Alexander Zherebker2, Yury Kostyukevich2
1Graduate School of Science, Tohoku University Aramaki Aza Aoba 6-3, Aoba-ku, Sendai, 9808578, Japan.
Abstract:
A previously unknown transformation of aldehydes, ketones, and carboxylic acid derivatives leads to the formation of substituted oxiranes, aziridines, and azirines as shown by DFT and MP2 computations. Formations of 2,2-dimethyloxirane-d8 from acetone-d6 , phenylazirine-d2 from benzonitrile and 2-methyl-2-(4-hydroxyphenyl)-oxirane from 4-hydroxyacetophenone were detected experimentally by electrospray ionization mass-spectrometry with a heated desolvating capillary. This reaction is a truly concerted process characterized by high activation barriers (activation enthalpies 320-480 kJ mol-1 ).
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