Palladium‐Catalyzed Ligand‐Controlled Selective Synthesis of Aldehydes and Acids from Aryl Halides and Formic Acid

Abstract

Selective synthesis is in the core of modern organic chemistry. In this communication, a novel ligand‐dependent palladium‐catalyzed carbonylation procedure for the divergent synthesis of aldehydes and carboxylic acids from easily available aryl halides was established. Under the same reaction conditions, the reaction pathway could be controlled by the ligands applied to give formylated and carboxylated products selectively. Sterically hindered monodentate ligands facilitated the reductive carbonylation and provided aldehydes, whereas bidentate ligands preferred the carboxylation reaction and produced carboxylic acids. A wide range of functional groups were tolerated, and the products were, in general, obtained in moderate to excellent yields.

PdO nanoparticles supported on triazole functionalized porous triazine polymer as an efficient heterogeneous catalyst for carbonylation of aryl halides

“…In order to investigate, the plausible mechanism for carbonylation of arylhalide catalyzed by PdO@TTAS heterogeneous catalyst was proposed in Scheme , which consisted with previous reported literature . In the first step the oxidative addition of aryl halide interact with palladium nanoparticles to form the Pd complex II and then followed by insertion of carbon monoxide from in‐situ generated HCOOH/EDC.HCl in the presence of triethylamine to generate in‐situ CO gas.…”

“…Recently, Xiao‐Feng Wu et al . reported the selective synthesis of aldehydes and acids from aryl halides, formic acid as a CO source in the presence of palladium catalysed and ligands controlled . Mohammad Mahdavi et al .…”

Ligand‐ and Solvent‐Controlled Regio‐ and Chemodivergent Carbonylative Reactions

“…[27b] From am echanistic point of view,t he difference in the reaction rate between the phenol iridium complex intermediate with CO and the internal alkyne might be responsible for the selectivity.A ne lectronrich phosphine ligand and higher CO pressure facilitate the reaction of the phenol iridium complex with CO prior to the internal alkyne.R ecently,a ne fficient iridium-catalyzed carbonylation for the straightforward synthesis of quinolin-2(1H)-ones was developed, with anilines as the substrates,by the same group. [28] By using formic acid as ag reen CO source,b oth formylation and carboxylation products could be synthesized selectively by controlling the reaction pathways through appropriate choice of the ligand. [28] By using formic acid as ag reen CO source,b oth formylation and carboxylation products could be synthesized selectively by controlling the reaction pathways through appropriate choice of the ligand.…”

“…[27c] Thef ormylation and carboxylation of the CÀXb ond are two important reactions.R ecently,t he group of Wu developed an ovel ligand-controlled carbonylation procedure for the divergent synthesis of aldehydes and carboxylic acids from aryl halides (Scheme 13). [28] By using formic acid as ag reen CO source,b oth formylation and carboxylation products could be synthesized selectively by controlling the reaction pathways through appropriate choice of the ligand. Forinstance,the sterically hindered monodentate ligand PCy 3 facilitates the reductive carbonylation and provides aldehydes,whereas the large bidentate ligand Xantphos facilitates the carboxylation reaction.…”

Liganden‐ und lösungsmittelkontrollierte regio‐ und chemodivergente Carbonylierungen

“…Vor kurzem entwickelten Wu et al. eine ligandenkontrollierte Carbonylierungsvorschrift für die divergente Synthese von Aldehyden und Carbonsäuren aus Arylhalogeniden (Schema ) . Mit Ameisensäure als grüner CO‐Quelle konnten sowohl die Produkte der Formylierung als auch die der Carboxylierung selektiv über eine Kontrolle der Reaktionswege mittels geeigneter Auswahl des Liganden synthetisiert werden.…”