Complementary Site-Selective Halogenation of Nitrogen-Containing (Hetero)Aromatics with Superacids.
Alexander MamontovAgnès Martin-MingotBenoit MétayerOmar KaramFabien ZuninoFodil BouazzaSébastien ThibaudeauPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2020)
Site-selective functionalization of arenes that is complementary to classical aromatic substitution reactions remains a long-standing quest in organic synthesis. Exploiting the generation of halenium ion through oxidative process and the protonation of the nitrogen containing function in HF/SbF5 , the chlorination and iodination of classically inert Csp2 -H bonds of aromatic amines occurs. Furthermore, the superacid-promoted (poly)protonation of the molecules acts as a protection, favoring the late-stage selective halogenation of natural alkaloids and active pharmaceutical ingredients.
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