Chemodivergent Conversion of Ketenimines Bearing Cyclic Dithioacetalic Units into Isoquinoline-1-thiones or Quinolin-4-ones as a Function of the Acetalic Ring Size

Abstract

C-Alkoxycarbonyl-C-phenyl-N-aryl ketenimines bearing 1,3-dithiolan-2-yl or 1,3-dithian-2-yl substituents at ortho position of the C-phenyl ring, respectively, transform into isoquino-line-1-thiones and quinolin-4-ones under thermal treatment in toluene solution. The formation of isoquinolinethiones involves a rare degradation of the 1,3-dithiolane ring, whereas, in contrast, the 1,3-dithiane ring remains intact during the reaction course leading to quinolin-4-ones. Computational density functional theory results support that the kinetically favorable mechanism for the formation of isoquinoline-l-thiones proceeds through a [1,5]-hydride shift/6 pi-electrocyclization cascade, followed by a thiirane extrusion process. Alternative mechanistic paths showing interesting electronic reorganization processes have been also scrutinized but resulted not competitive on energetic grounds.