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Additive-Controlled Switchable Divergent Fluorination/Chlorination of Bicyclic Azaamides via Palladium Catalysis
Chandrasekaran Sivaraj1,2, Ajay Thonipalliyalil Udayan1, Thirumanavelan Gandhi1
1Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore 632014, Tamil Nadu, India.
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A silver-controlled switchable halogenation of bicyclic azaamides via palladium catalysis has been developed, exhibiting broad functional group tolerance. The switchable divergent reactivity between fluorination and chlorination is dependent on the additive. The presence of Ag2CO3 promotes fluorination through activation of an electrophilic fluorinating agent, whereas its absence selectively favors chlorination via activation of the DCE solvent as a chlorine source. Comprehensive experimental and mechanistic investigations elucidate the reaction pathway and reveal the key factors governing this switchable divergent outcome.
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