Methylene Group Transfer in Carbonyl Compounds Discovered in silico and Detected Experimentally

Ilya D. Gridnev; Alexander Zherebker; Yury Kostyukevich; Eugene Nikolaev

doi:10.1002/cphc.201800945

Methylene Group Transfer in Carbonyl Compounds Discovered in silico and Detected Experimentally

Ilya D. Gridnev, Alexander Zherebker, Yury Kostyukevich, Eugene Nikolaev

SCI - Chemistry

Research output: Contribution to journal › Article › peer-review

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).

Original language	English
Journal	ChemPhysChem
DOIs	https://doi.org/10.1002/cphc.201800945
Publication status	Accepted/In press - 2018

Keywords

ab initio calculations
carbonyl compounds
density functional calculations
heated capillary
mass spectrometry

ASJC Scopus subject areas

Atomic and Molecular Physics, and Optics
Physical and Theoretical Chemistry

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10.1002/cphc.201800945

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title = "Methylene Group Transfer in Carbonyl Compounds Discovered in silico and Detected Experimentally",

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).",

keywords = "ab initio calculations, carbonyl compounds, density functional calculations, heated capillary, mass spectrometry",

author = "Gridnev, {Ilya D.} and Alexander Zherebker and Yury Kostyukevich and Eugene Nikolaev",

note = "Funding Information: I.D.G. thanks Prof. Masahiro Terada (Tohoku University) and Prof. Wanbin Zhang (Shanghai Jiao Tong University) for their continuous support and fruitful discussions. A.Z. and Y.K. acknowledge financial support from Russian Science Foundation through Grant No. 18-79-10127. Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2018",

doi = "10.1002/cphc.201800945",

language = "English",

journal = "ChemPhysChem",

issn = "1439-4235",

publisher = "Wiley-VCH Verlag",

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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

N1 - Funding Information: I.D.G. thanks Prof. Masahiro Terada (Tohoku University) and Prof. Wanbin Zhang (Shanghai Jiao Tong University) for their continuous support and fruitful discussions. A.Z. and Y.K. acknowledge financial support from Russian Science Foundation through Grant No. 18-79-10127. Publisher Copyright: © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2018

Y1 - 2018

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 -

Methylene Group Transfer in Carbonyl Compounds Discovered in silico and Detected Experimentally

Abstract

Keywords

ASJC Scopus subject areas

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