Copper-mediated sequential cyanation of aryl C-B and arene C-H bonds using ammonium iodide and DMF.

Jinho Kim, Jiho Choi, Kwangmin Shin, Sukbok Chang

Index: J. Am. Chem. Soc. 5th ed., 134 , 2528-2531, (2012)

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Abstract

The cyanation of aromatic boronic acids, boronate esters, and borate salts was developed under copper-mediated oxidative conditions using ammonium iodide and DMF as the source of nitrogen and carbon atom of the cyano unit, respectively. The procedure was successfully extended to the cyanation of electron-rich benzenes, and regioselective introduction of a cyano group at the arene C-H bonds was also achieved. The observation that the reaction proceeds via a two-step process, initial iodination and then cyanation, led us to propose that ammonium iodide plays a dual role to provide iodide and nitrogen atom of the cyano moiety.