Copper‐Catalyzed Intermolecular Aminocyanation and Diamination of Alkenes

′N′ front and center: The facile construction of CN bonds by the generation of nitrogen-centred radicals from N-fluorobenzenesulfonimide results in the aminative difuctionalization of alkenes. The first copper-catalyzed intermolecular aminocyanation of alkenes and diamination of styrenes were realized. Si–F and B–F interactions play a significant role in the reaction. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.