title: Factors Controlling the Chemoselectivity in the Oxidation of Olefins by Nonheme Manganese(IV)-Oxo Complexes.
abstract: We report the oxidation of cyclic olefins, such as cyclohexene, cyclohexene-d10, and cyclooctene, by mononuclear nonheme manganese(IV)-oxo (Mn(IV)O) and triflic acid (HOTf)-bound Mn(IV)O complexes. In the oxidation of cyclohexene, the Mn(IV)O complexes prefer the C-H bond activation to the C═C double bond epoxidation, whereas the C═C double bond epoxidation becomes a preferred reaction pathway in the cyclohexene oxidation by HOTf-bound Mn(IV)O complexes. In contrast, the oxidation of cyclohexene-d10 and cyclooctene by the Mn(IV)O complexes occurs predominantly via the C═C double bond epoxidation. This conclusion is drawn from the product analysis and kinetic studies of the olefin oxidation reactions, such as the epoxide versus allylic oxidation products, the formation of Mn(II) versus Mn(III) products, and the kinetic analyses. Overall, the experimental results suggest that the energy barrier of the C═C double bond epoxidation is very close to that of the allylic C-H bond activation in the oxidation of cyclic olefins by high-valent metal-oxo complexes. Thus, the preference of the reaction pathways is subject to changes upon small manipulation of the reaction environments, such as the supporting ligands and metal ions in metal-oxo species, the presence of HOTf (i.e., HOTf-bound Mn(IV)O species), and the allylic C-H(D) bond dissociation energies of olefins. This is confirmed by DFT calculations in the oxidation of cyclohexene and cyclooctene, which show multiple pathways with similar rate-limiting energy barriers and depending on the allylic C-H bond dissociation energies. In addition, the possibility of excited state reactivity in the current system is confirmed for epoxidation reactions.
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University , Seoul 03760, Korea.
authors.forename: Surin
authors.initials: S
authors.lastname: Kim
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University , Seoul 03760, Korea.
authors.forename: Kyung-Bin
authors.initials: KB
authors.lastname: Cho
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University , Seoul 03760, Korea.
authors.forename: Yong-Min
authors.initials: YM
authors.lastname: Lee
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University , Seoul 03760, Korea.
authors.forename: Junying
authors.initials: J
authors.lastname: Chen
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University , Seoul 03760, Korea.
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University , Seoul 03760, Korea.
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam