Helix-to-Disc Conversion of Thia6helicenes into Coronenes Facilitated by Sulfur Oxidation and Fluorination

Helicenes, with their unique helical structures, have long captured the interest of synthetic chemists, not only as end products, but also as versatile platforms for further chemical transformations. However, transforming [6]helicene into planar coronene typically requires harsh conditions and poses significant challenges. Herein, we demonstrate that replacing the terminal benzene ring of [6]helicene with a thiophene ring enables its photochemical transformation into coronene. Sulfur oxidation of the thiophene ring enables the corresponding thermal transformation, and the terminal tetrafluorination of the opposite benzene ring further accelerates this process, yielding 1,2-difluorocoronene, as confirmed by X-ray crystallography. The transformation begins with an intramolecular Diels-Alder reaction, whose activation energy is significantly lowered by these structural changes. Our findings underscore the utility of strategic modifications such as sulfur oxidation and fluorination in promoting this "helix-to-disc" conversion and opening new avenues for synthesizing functional polycyclic aromatics.Helicenes, with their unique helical structures, have long captured the interest of synthetic chemists, not only as end products, but also as versatile platforms for further chemical transformations. However, transforming [6]helicene into planar coronene typically requires harsh conditions and poses significant challenges. Herein, we demonstrate that replacing the terminal benzene ring of [6]helicene with a thiophene ring enables its photochemical transformation into coronene. Sulfur oxidation of the thiophene ring enables the corresponding thermal transformation, and the terminal tetrafluorination of the opposite benzene ring further accelerates this process, yielding 1,2-difluorocoronene, as confirmed by X-ray crystallography. The transformation begins with an intramolecular Diels-Alder reaction, whose activation energy is significantly lowered by these structural changes. Our findings underscore the utility of strategic modifications such as sulfur oxidation and fluorination in promoting this "helix-to-disc" conversion and opening new avenues for synthesizing functional polycyclic aromatics.