Abstract
The decatungstate W10O32 4- catalyzed photooxygenation of cumenes in the presence of molecular oxygen and triethylsilane has been thoroughly studied. In all cases the corresponding tertiary hydroperoxides were formed as the major products. Based on stereoisotopic studies as well as on primary and β-secondary isotope effects, we provide strong evidence for a stepwise mechanism, in which a hydrogen atom abstraction occurs in the rate-determining step of the reaction. In addition, the oxidation of (S)-2-phenylbutane by decatungstate/Et3SiH catalytic system, shows the formation of the two enantiomeric alcohols, (R)-2-phenylbutan-2-ol and (S)-2-phenylbutan-2-ol, in equimolar amounts. This product racemization confirms further the presence of a stepwise mechanism and support the formation of a free carbon-centered radical intermediate.
Call for Papers in Thematic Issues
Catalytic C-H bond activation as a tool for functionalization of heterocycles
The major topic is the functionalization of heterocycles through catalyzed C-H bond activation. The strategies based on C-H activation not only provide straightforward formation of C-C or C-X bonds but, more importantly, allow for the avoidance of pre-functionalization of one or two of the cross-coupling partners. The beneficial impact of ...read more
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