Stereoselectivity in Atmospheric Autoxidation

Kristian H. Moller; Eric Praske; Lu Xu; John D. Crounse; Paul O. Wennberg; Henrik G. Kjaergaard

doi:10.1021/acs.jpclett.9b01972

Stereoselectivity in Atmospheric Autoxidation

Kristian H. Moller, Eric Praske, Lu Xu, John D. Crounse, Paul O. Wennberg, Henrik G. Kjaergaard

Department of Chemistry

8 Citations (Scopus)

Abstract

We show that the diastereomers of hydroxy peroxy radicals formed from OH and O₂ addition to C2 and C3, respectively, of crotonaldehyde (CH₃CHCHCHO) undergo gas-phase unimolecular aldehydic hydrogen shift (H-shift) chemistry with rate coefficients that differ by an order of magnitude. The stereospecificity observed here for crotonaldehyde is general and will lead to a significant diastereomeric-specific chemistry in the atmosphere. This enhancement of specific stereoisomers by stereoselective gas-phase reactions could have widespread implications given the ubiquity of chirality in nature. The H-shift rate coefficients calculated using multiconformer transition state theory (MC-TST) agree with those determined experimentally using stereoisomer-specific gas-chromatography chemical ionization mass spectroscopy (GC-CIMS) measurements.

Original language	English
Journal	Journal of Physical Chemistry Letters
Volume	10
Issue number	20
Pages (from-to)	6260-6266
ISSN	1948-7185
DOIs	https://doi.org/10.1021/acs.jpclett.9b01972
Publication status	Published - 17 Oct 2019

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title = "Stereoselectivity in Atmospheric Autoxidation",

abstract = "We show that the diastereomers of hydroxy peroxy radicals formed from OH and O2 addition to C2 and C3, respectively, of crotonaldehyde (CH3CHCHCHO) undergo gas-phase unimolecular aldehydic hydrogen shift (H-shift) chemistry with rate coefficients that differ by an order of magnitude. The stereospecificity observed here for crotonaldehyde is general and will lead to a significant diastereomeric-specific chemistry in the atmosphere. This enhancement of specific stereoisomers by stereoselective gas-phase reactions could have widespread implications given the ubiquity of chirality in nature. The H-shift rate coefficients calculated using multiconformer transition state theory (MC-TST) agree with those determined experimentally using stereoisomer-specific gas-chromatography chemical ionization mass spectroscopy (GC-CIMS) measurements.",

author = "Moller, {Kristian H.} and Eric Praske and Lu Xu and Crounse, {John D.} and Wennberg, {Paul O.} and Kjaergaard, {Henrik G.}",

year = "2019",

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day = "17",

doi = "10.1021/acs.jpclett.9b01972",

language = "English",

volume = "10",

pages = "6260--6266",

journal = "Journal of Physical Chemistry Letters",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Stereoselectivity in Atmospheric Autoxidation

AU - Moller, Kristian H.

AU - Praske, Eric

AU - Xu, Lu

AU - Crounse, John D.

AU - Wennberg, Paul O.

AU - Kjaergaard, Henrik G.

PY - 2019/10/17

Y1 - 2019/10/17

N2 - We show that the diastereomers of hydroxy peroxy radicals formed from OH and O2 addition to C2 and C3, respectively, of crotonaldehyde (CH3CHCHCHO) undergo gas-phase unimolecular aldehydic hydrogen shift (H-shift) chemistry with rate coefficients that differ by an order of magnitude. The stereospecificity observed here for crotonaldehyde is general and will lead to a significant diastereomeric-specific chemistry in the atmosphere. This enhancement of specific stereoisomers by stereoselective gas-phase reactions could have widespread implications given the ubiquity of chirality in nature. The H-shift rate coefficients calculated using multiconformer transition state theory (MC-TST) agree with those determined experimentally using stereoisomer-specific gas-chromatography chemical ionization mass spectroscopy (GC-CIMS) measurements.

AB - We show that the diastereomers of hydroxy peroxy radicals formed from OH and O2 addition to C2 and C3, respectively, of crotonaldehyde (CH3CHCHCHO) undergo gas-phase unimolecular aldehydic hydrogen shift (H-shift) chemistry with rate coefficients that differ by an order of magnitude. The stereospecificity observed here for crotonaldehyde is general and will lead to a significant diastereomeric-specific chemistry in the atmosphere. This enhancement of specific stereoisomers by stereoselective gas-phase reactions could have widespread implications given the ubiquity of chirality in nature. The H-shift rate coefficients calculated using multiconformer transition state theory (MC-TST) agree with those determined experimentally using stereoisomer-specific gas-chromatography chemical ionization mass spectroscopy (GC-CIMS) measurements.

U2 - 10.1021/acs.jpclett.9b01972

DO - 10.1021/acs.jpclett.9b01972

M3 - Letter

C2 - 31545897

SN - 1948-7185

VL - 10

SP - 6260

EP - 6266

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

IS - 20

ER -

Stereoselectivity in Atmospheric Autoxidation

Abstract

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