10.1021/ja211389g
The research explores a novel method for the cyanation of aromatic compounds using copper-mediated oxidative conditions. The study aims to develop an efficient and versatile protocol for converting aryl boronic acids, boronate esters, and borate salts into nitriles, which are important structural motifs in pharmaceuticals, agrochemicals, and dyes. The key chemicals used in this research include ammonium iodide (NH4I) and N,N-dimethylformamide (DMF), which serve as the nitrogen and carbon sources for the cyano unit, respectively. Copper salts, such as Cu(NO3)2·3H2O, are employed to mediate the reaction, and acetic acid is used as an additive. The researchers discovered that the cyanation process involves a two-step mechanism: initial iodination followed by cyanation. This dual role of ammonium iodide—providing both iodide and the nitrogen atom of the cyano group—represents a significant innovation. The method was successfully applied to a wide range of substrates, including electron-rich arenes, demonstrating high functional group tolerance and broad substrate scope. The study concludes that this copper-mediated cyanation protocol offers a practical and efficient route for the synthesis of nitriles from various boronate compounds and electron-rich arenes, with potential applications in the synthesis of complex organic molecules.
10.1021/ol400659p
The study presents a novel copper-mediated oxidative cyanation method for transforming organosilanes into nitriles using ammonium iodide and DMF as the nitrogen and carbon sources, respectively. The researchers optimized the reaction conditions, finding that Cu(NO?)?·3H?O as the copper species and KF as an additive were most effective. The reaction proceeds via a two-step process: initial iodination of the organosilanes to form iodo intermediates, followed by cyanation. A wide range of substrates, including aryl-, diaryldimethyl-, styryl-, and benzylsilanes, were successfully converted to nitriles with high functional group tolerance. The study also explored the cyanation of Hiyama silanes and vinylsilanes, demonstrating the versatility of the method. The authors propose that iodoarenes are key intermediates in the cyanation process and suggest a sequential mechanism involving initial iodination and subsequent cyanation.
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