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

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 kJmol_-1).

Original language	English
Pages (from-to)	361-365
Number of pages	5
Journal	ChemPhysChem
Volume	20
Issue number	3
DOIs	https://doi.org/10.1002/cphc.201800945
State	Published - 1 Jan 2019
Externally published	Yes

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 kJmol-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} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2019",

month = jan,

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doi = "10.1002/cphc.201800945",

language = "English",

volume = "20",

pages = "361--365",

journal = "ChemPhysChem",

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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: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

PY - 2019/1/1

Y1 - 2019/1/1

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 kJmol-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 kJmol-1).

KW - Ab initio calculations

KW - Carbonyl compounds

KW - Density functional calculations

KW - Heated capillary

KW - Mass spectrometry

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DO - 10.1002/cphc.201800945

M3 - Article

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AN - SCOPUS:85058935151

SN - 1439-4235

VL - 20

SP - 361

EP - 365

JO - ChemPhysChem

JF - ChemPhysChem

IS - 3

ER -

Methylene group transfer in carbonyl compounds discovered in silico and detected experimentally

Abstract

Keywords

ASJC Scopus subject areas

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