Stereoselectivity in Atmospheric Autoxidation
Abstract
We show that the diastereomers of hydroxy peroxy radicals formed from OH and O_2 addition to C2 and C3, respectively, of crotonaldehyde (CH_3CHCHCHO) 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.
Additional Information
© 2019 American Chemical Society. Received: July 8, 2019; Accepted: September 23, 2019; Published: September 23, 2019. All ωB97X-D/aug-cc-pVTZ and F12 output files, which include the ωB97X-D/aug-cc-pVTZ optimized geometries are available at https://sid.erda.dk/public/archives/bfad8e9ca7cf171e6d225371b36c3372/published-archive.html. The authors thank Hannah M. Allen for helpful discussions. K.H.M. acknowledges the financial support of the Danish Ministry for Higher Education and Science's Elite Research travel grant and the Niels Bohr Foundation. We are grateful for the funding from the National Science Foundation (Grant CHE-1508526), the Alfred P. Sloan Foundation's program Chemistry of Indoor Environments, the Independent Research Fund Denmark, and the University of Copenhagen. The authors declare no competing financial interest.Attached Files
Supplemental Material - jz9b01972_si_001.pdf
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Additional details
- Eprint ID
- 98824
- Resolver ID
- CaltechAUTHORS:20190924-092009258
- Ministry of Higher Education and Science (Denmark)
- Niels Bohr Foundation
- CHE-1508526
- NSF
- Alfred P. Sloan Foundation
- Independent Research Fund Denmark
- University of Copenhagen
- Created
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2019-09-24Created from EPrint's datestamp field
- Updated
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2021-11-16Created from EPrint's last_modified field
- Caltech groups
- Division of Geological and Planetary Sciences