Theoretical Study on Electronic Properties of Deoxyfluorinating Sulfur-Based Reagents

Organofluorine compounds have become increasingly important as pharmaceuticals, radiopharmaceuticals, agrochemicals, and material science. Recent advances on the efficient introduction of fluorine to organic molecules are mainly results of development of transition metal catalysts and fluorination reagents. Among the various fluorination reagents, we have been interested in developing more efficient sulfur-based deoxyfluorinating reagents. Here we report various electronic properties of five popular sulfur-based deoxyfluorinating reagents using density functional theory calculation. We believe that the theoretical study on the reagents will assist the rational design of new deoxyfluorinating reagents.22

Cobalt-Catalyzed Defluorosilylation of Aryl Fluorides via Grignard Reagent Formation

Transition-metal-catalyzed transformations of the carbon-fluorine bond not only tackle an interesting problem of challenging bond activation but also offer new synthetic strategies where the relatively inert C-F bond is converted to versatile functional groups. Herein we report a practical cobalt-catalyzed silylation of aryl fluorides that uses a cheap electrophilic silicon source with magnesium. This method is compatible with various silicon sources and can be operated under aerobic conditions. Mechanistic studies support the in situ formation of a Grignard reagent, which is captured by the electrophilic silicon source.11Nsciescopu

Reversible ammonia uptake at room temperature in a robust and tunable metal-organic framework

Ammonia is useful for the production of fertilizers and chemicals for modern technology, but its high toxicity and corrosiveness are harmful to the environment and human health. Here, we report the recyclable and tunable ammonia adsorption using a robust imidazolium-based MOF (JCM-1) that uptakes 5.7 mmol g(-1) of NH3 at 298 K reversibly without structural deformation. Furthermore, a simple substitution of NO3- with Cl- in a post-synthetic manner leads to an increase in the NH3 uptake capacity of JCM-1(Cl-) up to 7.2 mmol g(-1).11Nsciescopu

Cobalt-Catalyzed C-F Bond Borylation of Aryl Fluorides

A mild and practical cobalt-catalyzed defluoroborylation of fluoroarenes is presented for the first time. The method permits straightforward functionalization of fluoroarenes, with high selectivity for borylation of C-F over C-H bonds, and a tolerance for aerobic conditions. Furthermore, two-step 18F-fluorination was achieved for expanding the scope of 18F-positron emission tomography probes. c. 2018 American Chemical Societ