Rapid access to polycyclic thiopyrylium compounds from unfunctionalized aromatics by thia-APEX reaction.

We developed a sulfur-embedding annulative π-extension (thia-APEX) reaction that could construct a sulfur-embedding cationic hexagonal aromatic ring, thiopyrylium, onto unfunctionalized aromatics in one step. The key of thia-APEX is the use of -imidated -arenoyl arenethiols, and a variety of π-extended thiopyryliums can easily be synthesized. The synthesized thiopyryliums showed diverse absorption and emission properties over the visible light to NIR region, depending on minor structural differences.

π-Extended Rubrenes via Dearomative Annulative π-Extension Reaction.

Among a large variety of organic semiconducting materials, rubrene (5,6,11,12-tetraphenyltetracene) represents one of the most prominent molecular entities mainly because of its unusually high carrier mobility. Toward finding superior rubrene-based organic semiconductors, several synthetic strategies for related molecules have been established. However, despite its outstanding properties and significant attention in the field of materials science, late-stage functionalizations of rubrene remains undeveloped, thereby limiting the accessible chemical space of rubrene-based materials.

Synthesis of Nitrogen-Containing Polyaromatics by Aza-Annulative π-Extension of Unfunctionalized Aromatics.

Nitrogen-containing polycyclic aromatic compounds (N-PACs) are an important class of compounds in materials science. Reported here is a new aza-annulative π-extension (aza-APEX) reaction that allows rapid access to a range of N-PACs in 11-84 % yields from readily available unfunctionalized aromatics and imidoyl chlorides. In the presence of silver hexafluorophosphate, arenes and imidoyl chlorides couple in a regioselective fashion.