TBN‐Catalyzed Dehydrative N‐Alkylation of Anilines with 4‐Hydroxybutan‐2‐one

Until now, the substitution of alcohols by N‐nucleophiles via TBN‐catalyzed dehydrogenation was not known. Herein, we reported a TBN catalyzed dehydrative N ‐alkylation of anilines with 4‐hydroxybutan‐2‐one in the presence of TEMPO, which was different from the TEMPO/TBN catalyzed oxidation reactions. A range of anilines reacted successfully with 4‐hydroxybutan‐2‐one to generate the N ‐monoalkylation products in good yields. Mechanistic studies revealed that this reaction most possibly proceeded through aza‐Michael addition. Water was the only by‐product, making it more environmentally friendly. The gram‐scale reactions verified the synthetic practicality of this protocol.