6-Aminopyridin-2-ones form Watson–Crick pairs with complementary purine analogues to add a third nucleobase pair to DNA and RNA, if an electron-withdrawing group at position 5 slows oxidation and epimerization. In previous work with a nucleoside analogue trivially named d Z, the electron withdrawing unit was a nitro group. Here, we describe an analogue of d Z (cyano-d Z) having a cyano group instead of a nitro group, including its synthesis, p ...