Stereoselectivity in Atmospheric Autoxidation

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 stereospeci...

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Bibliographic Details
Published in:The journal of physical chemistry letters 2019-10, Vol.10 (20), p.6260-6266
Main Authors: Møller, Kristian H, Praske, Eric, Xu, Lu, Crounse, John D, Wennberg, Paul O, Kjaergaard, Henrik G
Format: Article
Language:English
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Summary: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.
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.9b01972