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

1,4-addition reactions of alkylazaarenes catalyzed by strong Bronsted bases have been developed for the first time. The desired reactions with alpha,beta-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 a-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.