Photochemical Rearrangements of Pyridine N-Oxides: Pathways to Oxaziridine Derivatives

The photochemical behavior of substituted pyridine N-Oxides is characterized by complex rearrangements culminating in the formation of valuable photoproducts. The CAS(10,8)/cc-pVDZ approach with NEVPT2 corrections is applied to investigate geometric distortions associated with the $S_1$ excited state, conical intersections, and the ultimate transformation of pyridine N-Oxides into oxaziridine-like derivative formations. Our results reveal that the deactivation of the $S_1$ excited state is driven by an out-of-plane rotation of the N-O oxygen atom, resulting in the formation of a lone pair over the nitrogen atom. Along this excited-state reaction pathway, the N-O bond undergoes significant weakening, while a C=C double bond emerges mainly in the excited state. The deactivation at the minimum-energy conical intersection leading to the ground state reveals the formation of an oxaziridine-like intermediate, which subsequently converts into a 1,2-oxazepine derivative.