10.1016/S0022-2860(97)00412-2
The research aimed to determine the molecular structure of perfluoroadamantane using gas-phase electron diffraction. The study sought to examine the structural consequences of hydrogen/fluorine substitution in adamantane, a carbon-cage molecule with high symmetry, by comparing the bond lengths and angles of perfluoroadamantane to those of adamantane. The researchers found that perfluorination expanded the adamantane cage, with a significant lengthening of the C-C bonds by 0.02 ?, attributed to the electron-withdrawing ability of fluorine ligands. The chemicals used in the process included adamantane, sodium fluoride, anhydrous hydrogen fluoride, and Freon-113 for extraction, as well as helium for agitation during the electrochemical fluorination process. The final product, perfluoroadamantane, was obtained with a yield of 31.1% based on the sample fed and a purity of 99.3% as confirmed by gas chromatography.
10.1039/c4ob02208d
The research focuses on the development of a mild and efficient method for the conversion of arylboronic acids into arylthiocyanates using a copper-catalyzed aerobic oxidative process. The study employs trimethylsilylisothiocyanate (TMSNCS) as a thiocyantion reagent and utilizes NaF as a promoter under an oxygen atmosphere, with CuCl serving as the catalyst. The cross-coupling reaction is conducted at ambient temperature and is found to be effective for a broad range of functional groups, including strong electron-withdrawing groups. The experiments involve the optimization of reaction conditions, including the evaluation of various catalysts, ligands, additives, and solvents, ultimately leading to the identification of an optimal condition that involves the use of 20 mol% CuCl, 20 mol% TMEDA as a ligand, 1 equiv. of NaF, and 4 equiv. of K2CO3 in acetonitrile at room temperature for 12 hours, with 3? molecular sieves. The substrate scope was also investigated, demonstrating the versatility of the method with both electron-donating and electron-withdrawing arylboronic acids. The reaction mechanism is proposed based on the formation and reactivity of CuSCN as an intermediate, with both TMEDA and O2 being essential for the transformation. The study concludes that the developed protocol offers a milder and more efficient approach for aromatic oxidative thiocyanation, with potential applications in the synthesis of a variety of aryl thiocyanates.
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