Synthesis of 3-(aminomethyl)pyridine by traceless C3-selective umpolung of 1-amidopyridin-1-ium salts

A natural product inspired rapid access of 3-(aminomethyl)pyridine by one-pot reaction of 1-amidopyridin-1-ium salt with aminal followed by reductive cleavage of the N-N bond is developed. This C3-selective formal C-H activation of pyridine features a traceless umpolung of the 1-amidopyridin-1-ium salt toward a Mannich type C-C bond formation of the in situ generated 1-amido-2-dialkylamino-1,2-dihydropyridine intermediate.