Molecular Dynamics of Dimethyldioxirane C–H Oxidation

Zhongyue Yang, Peiyuan Yu, and K. N. Houk

J. Am. Chem. Soc.,
2016, 138 (12), pp 4237–4242; 10.1021/jacs.6b01028


Dioxiranes have been shown to be efficient and stereospecific reagents for the oxidation of unactivated C–H bonds of alkanes, capable of high conversions under mild conditions without the need for metal catalysis.

There has been significant interest in deducing the origins of this highly desirable reactivity and selectivity profile. Three different mechanisms have been proposed. This research from the Houk group provides and comprehensive examination of the evidence along with detailed molecular dynamics simulations to provide a compelling case for their mechanistic rationale.

Comparing reaction simulations both in the gas phase and using acetone as an implicit solvent they demonstrate a decisive difference between the proposed reactive trajectories that explains the reactivity of this system.

Understanding the factors that underpin the reactivity of this system will inform the design of transformations around this interesting reactive functionality.

Watch an animation that describes the oxygen rebound pathway:

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