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Citation
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HERO ID
3120148
Reference Type
Journal Article
Title
Molecular Dynamics of Dimethyldioxirane C-H Oxidation
Author(s)
Yang, Z; Yu, P; Houk, KN
Year
2016
Is Peer Reviewed?
Yes
Journal
Journal of the American Chemical Society
ISSN:
0002-7863
EISSN:
1520-5126
Volume
138
Issue
12
Page Numbers
4237-4242
Language
English
PMID
26964643
DOI
10.1021/jacs.6b01028
Abstract
We report molecular dynamics simulations of the reaction of dimethyldioxirane (DMDO) with isobutane. The reaction involves hydrogen atom abstraction in the transition state, and trajectories branch to the oxygen rebound pathway, which gives tert-butanol and acetone, or a separated radical pair. In the gas phase, only 10% of the reactive trajectories undergo the oxygen rebound pathway, but this increases to 90% in simulations in an implicit acetone solvent (SMD) because the oxygen rebound becomes barrierless in solution. Short-lived diradical species were observed in the oxygen rebound trajectories. The time gap between C-H bond-breaking and C-O bond formation ranges from 30 to 150 fs, close to the <200 fs lifetime of radical pairs from DMDO hydroxylation of trans-1-phenyl-2-ethylcyclopropane measured by Newcomb.
Tags
IRIS
•
tert-Butanol
Excluded/ Not on Topic
Other Chemical/Non-tert-butanol
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