title: Manganese(IV)-mediated hydroperoxyarylation of alkenes with aryl hydrazines and dioxygen from air.
abstract: We report a new carbooxygenation-type version of the Meerwein arylation in which the introduction of oxygen is achieved by using dioxygen from the air. In this way, hydroperoxides were obtained from activated as well as non-activated alkenes by oxidizing aryl hydrazines with manganese dioxide. The best results were obtained with α-substituted acrylates. Importantly, the aryl hydrazine has to be added slowly to the reaction mixture to allow sufficient uptake of dioxygen from the air. Competition and labeling experiments revealed hydroperoxyl radicals as novel oxygen-centered radical scavengers.
authors.affiliation: Department für Chemie und Pharmazie, Pharmazeutische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Schuhstrasse 19, 91052 Erlangen (Germany).
authors.forename: Stephanie
authors.initials: S
authors.lastname: Kindt
authors.forename: Hannelore
authors.initials: H
authors.lastname: Jasch
authors.forename: Markus R
authors.initials: MR
authors.lastname: Heinrich
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D006834:Hydrazines / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D015394:Molecular Structure
chemical_list: D000475:Alkenes; D006834:Hydrazines; C029424:hydrazine; D008345:Manganese
keywords: aryl hydrazines; carbooxygenation; dioxygen; hydroperoxyl radicals; radical reactions