TY - JOUR
T1 - Methylene Group Transfer in Carbonyl Compounds Discovered in silico and Detected Experimentally
AU - Gridnev, Ilya D.
AU - Zherebker, Alexander
AU - Kostyukevich, Yury
AU - Nikolaev, Eugene
PY - 2018/1/1
Y1 - 2018/1/1
N2 - 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).
AB - 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).
KW - ab initio calculations
KW - carbonyl compounds
KW - density functional calculations
KW - heated capillary
KW - mass spectrometry
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U2 - 10.1002/cphc.201800945
DO - 10.1002/cphc.201800945
M3 - Article
C2 - 30523648
AN - SCOPUS:85058935151
JO - ChemPhysChem
JF - ChemPhysChem
SN - 1439-4235
ER -