Divergent Synthesis of Functionalized Indenopyridin-2-ones and 2-Pyridones via Benzyl Group Transfer: Two Cases of Aza-semipinacol-Type Rearrangement

The synthesis of bromo-substituted indeno[1,2-b]-pyridin-2-ones and 3-iodo-5-benzyl-substituted 2-pyridones, starting from easily available 6-benzyl-3,6-dihydropyridin-2(1H)-ones, trig-gered by NBS and NIS, respectively, is described. In both syntheses, a transfer of a benzyl group from the C6 to C5 lactam position occurred, indicating a novel aza-semipinacol-type rearrangement. Identification of intermediate compounds in both transformations supported the proposed reaction mechanisms. In the process of checking the scope of the method's application, functionalized indeno[1,2-b]pyridin-2-ones and 5-benzyl-2-pyridones were obtained.

Automated summary

The synthesis of bromo-substituted indeno[1,2-b]-pyridin-2-ones and 3-iodo-5-benzyl-substituted 2-pyridones, starting from easily available 6-benzyl-3,6-dihydropyridin-2(1H)-ones, triggered by NBS and NIS, respectively, was reported. A novel aza-semipinacol-type rearrangement was observed with a transfer of a benzyl group from the C6 to C5 lactam position in both syntheses. The identification of intermediate compounds supported the proposed reaction mechanisms, and functionalized indeno[1,2-b]pyridin-2-ones and 5-benzyl-2-pyridones were obtained during the scope check of the method's application.