Palladium-Catalyzed Butoxycarbonylation of Polybromo(hetero)arenes: A Practical Method for the Preparation of (Hetero)arenepolycarboxylates and -carboxylic Acids

Abstract

The palladium-catalyzed alkoxycarbonylation of (N-hetero)aryl multibromides were investigated systematically. The results show that cheap and readily available in-situ Pd(OAc)2/rac-BINAP catalyst can catalyze butoxycarbonylation of various (N-hetero)aryl multibromides efficiently, and obtain esters with moderate to high yield (59-94% yield). from which, two new compounds (4,4ꞌ-dibutoxycarbonyl-1,1ꞌ-bi-2-naphthol and Di-n-butyl [2,2'-bipyrimidine]-5,5'-dicarboxylate were first reported in this work. In addition, the gram scale preparation of carboxylate and carboxylic acids have be done successful by butoxycarbonylation and hydrolysis reaction. which indicated that the wide scope of substrates and practical applications of the Pd(OAc)2/rac-BINAP catalytic system. Moreover, these carboxylic acids and carboxylate can be used as ligands or structural units to construct MOFs, metal complexes, and COFs etc.

Polyimide covalent organic frameworks bearing star-shaped electron-deficient polycyclic aromatic hydrocarbon building blocks: molecular innovations for energy conversion and storage

“…Considering that the reaction went through a series of intermediates, the addition product was isolated with a small yield of 11.9%. Recently, Ji et al 34 found a novel approach to prepare triphenylene-2,3,6,7,10,11-hexacarboxylate via the palladium-catalyzed butoxycarbonylation of 2,3,6,7,10,11-hexabromotriphenylene (Scheme 1b). The synthesis route to triphenylene ester derivative was merely one step and the yield reached up to 60%, greatly improving the synthesis efficiency.…”