Stereoselectivity in Atmospheric Autoxidation.

J Phys Chem Lett

Department of Chemistry , University of Copenhagen, DK-2100 Copenhagen Ø , Denmark.

Published: October 2019

We show that the diastereomers of hydroxy peroxy radicals formed from OH and O addition to C2 and C3, respectively, of crotonaldehyde (CHCHCHCHO) 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.

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http://dx.doi.org/10.1021/acs.jpclett.9b01972DOI Listing

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