Catalytic Direct‐type 1,4‐Addition Reactions of Alkylazaarenes

1,4‐addition reactions of alkylazaarenes catalyzed by strong Brønsted bases have been developed for the first time. The desired reactions with α,β‐unsaturated amides proceeded under mild reaction conditions to give the 1,4‐adducts in high yields. Both ortho‐ and para‐substituted azaarenes afforded the desired adducts in high yields. Regioselective reactions of di‐ or trimethylpyridine were found to be possible depending on the acidity of the α‐hydrogen atoms. Furthermore, a candidate of allosteric protein kinase modulators was synthesized in two steps. An asymmetric variant of this reaction was also found to be feasible.