Palladium-catalyzed annulative π-extension of o-halobiphenyls with o-chloropyridinecarboxylic acids to access azatriphenylenes

Abstract

A palladium-catalyzed bay-region annulative π-extension reaction of o-halobiphenyls with o-chloropyridinecarboxylic acids was developed. The reaction was carried out with 1:1 ratio of substrates. A variety of azatriphenylene derivatives could be...

Palladium-Catalyzed Annulative π-Extension of Bay-Iodinated Triphenylenes to Access Polycyclic Aromatic Compounds

“…1:√3:√4 in the small-angle region. These signals can be assigned as the (10), (11), and (20) diffractions of a hexagonal columnar phase. Taken together, the characterization data indicate that compound 6 exhibits hexagonal columnar mesophases in a wide temperature range.…”

“…o -Chloroaromatic carboxylic acids are excellent π-extension reagents in APEX reactions due to their numerous advantages. , First, they provide high yields with low substrate usage required. Second, they exhibit excellent tolerance toward various functional groups, even those with strong electron-withdrawing groups like electron-poor o -chloropyridinecarboxylic acids.…”

“…According to the previous reports, − a possible reaction mechanism using aryl iodides as π-extension reagents was proposed as illustrated in Scheme . Initially, the 1-iodotriphenylene 1a reacts with Pd(0) through oxidative addition, resulting in the formation of Pd­(II) complex A .…”

“…10 Moreover, the successful construction of azatriphenylenes was accomplished through a palladium-catalyzed APEX reaction of o-iodobiphenyls with o-chloropyridinecarboxylic acids. 11 Although numerous APEX reactions of o-halogenbiaryls have been developed to construct various PACs, the APEX reactions of bay-halogenated PACs have not yet been explored to build larger PACs. The synthesis of larger PACs is important in the field of materials chemistry as they exhibit stronger π−π interactions, which can enhance the columnar order and charge mobility of discotic liquid crystals.…”

“…Phenanthrol derivatives were successfully synthesized via a palladium-catalyzed APEX reaction of o -iodobiphenyls with aliphatic anhydrides . Moreover, the successful construction of azatriphenylenes was accomplished through a palladium-catalyzed APEX reaction of o -iodobiphenyls with o -chloropyridinecarboxylic acids . Although numerous APEX reactions of o -halogenbiaryls have been developed to construct various PACs, the APEX reactions of bay-halogenated PACs have not yet been explored to build larger PACs.…”