Computational techniques applied to the study of the oxidation kinetics of iron and molybdenum cyanocomplexes by peroxynitrous acid

The oxidation kinetics of iron and molybdenum cyanocomplexes by peroxynitrous acid were studied by computational techniques. The rate constants of ONOOH decomposition and substrate oxidation were calculated by fitting the experimental data to the solution of the ordinary differential equations mechanism. There is a linear relationship between the rate constants which is solved by varying the initial concentration of one of the reactive species. The rate constants of the steps involved in ONOOH decomposition were also determined following the same procedure and considering a linear relationship between the rate constants. The results are consistent with the values previously found using the conventional method of integration, and they validate the prior steady state assumption. Copyright © 2008 John Wiley & Sons, Ltd.     

Pentafluorocyclopropanation of (Hetero)arenes Using Sulfonium Salts: Applications in Late-Stage Functionalization

The evaluation of the pentafluorocyclopropyl group as a chemotype in crop protection and medicinal chemistry has been hampered in the past by the lack of suitable methodologies that enable the practical incorporation of this moiety into advanced synthetic intermediates. Herein, we report the gram-scale synthesis of an unprecedented sulfonium salt, 5-(pentafluorocyclopropyl)dibenzothiophenium triflate, and its use as a versatile reagent for the photoinduced C−H pentafluorocyclopropylation of a broad series of non-previously functionalized (hetero)arenes through a radical mediated mechanism. The scope and potential benefits of the protocol developed are further demonstrated by the late-stage introduction of the pentafluorocyclopropyl unit into biologically relevant molecules and widely used pharmaceuticals.