Lewis Acid-Promoted Ring-Contraction of 2,4,6,8-Tetrasubstituted 1,5-Diazacyclooctatetraenes to 2,4,6-Trisubstituted Pyridines.

Ring-contraction of 2,4,6,8-tetrasubstituted 1,5-diazacyclooctatetraenes was highly efficiently promoted by Lewis acid such as TiCl4, affording 2,4,6-trisubstituted pyridines in excellent yields, along with release of a nitrile. A reaction mechanism involving a 6π electrocyclic ring-closing followed by a retro [2 + 2] cyclization of an 1-azetine moiety was supported by both experimental observations and density functional theory calculation. [ABSTRACT FROM AUTHOR]