Pseudopericyclic Dearomative 1,6‐Cyclization of 1‐(2‐Pyridyl)‐2‐azabuta‐1,3‐dienes: Synthesis and Ring–Chain Valence Equilibria of 4<i>H</i>‐Pyrido[1,2‐<i>a</i>]pyrazines

Abstract

The 1,6‐electrocyclization of 1‐(2‐pyridyl)‐2‐azabuta‐1,3‐dienes obtained by Rh II ‐catalyzed reaction of pyridotriazoles with 2 H ‐azirines affords stable non‐aromatic 4 H ‐pyrido[1,2‐ a ]pyrazines despite the fact that the reaction proceeds with irreversible dearomatization of the pyridine aromatic system. This pseudopericyclic cyclization occurs when the 2‐azabutadiene contains H, alkyl, or Ph at the C4 atom and an electron‐withdrawing substituent at the C1 atom. A number of stable 4 H ‐pyrido[1,2‐ a ]pyrazines as well as 1 H ‐pyrazino[1,2‐ a ]quinoline and 4 H ‐benzo[4,5]oxazolo[3,2‐ a ]pyrazine derivatives were synthesized. Whereas 4‐alkyl‐substituted pyridopyrazines are stable at room temperature, 4‐phenyl‐substituted pyridopyrazines exist in ring–chain valence equilibrium with 1‐(2‐pyridyl)‐2‐azabutadienes. Thermodynamic stability of the 4 H ‐pyrido[1,2‐ a ]pyrazine decreases with increasing size of the substituent at the C6 atom.