Palladium-Catalyzed Reductive Conversion of Acyl Fluorides via Ligand-Controlled Decarbonylation

Abstract

Ligand-controlled non-decarbonylative and decarbonylative conversions of acyl fluorides were developed using a Pd(OAc)/EtSiH combination. When tricyclohexylphosphine (PCy) was used as the ligand, aldehydes were obtained as simple reductive conversion products. The use of 1,2-bis(dicyclohexylphosphino)ethane (CyP(CH)PCy, DCPE) as the ligand, however, favored the formation of hydrocarbons, which are decarbonylative reduction products.

Acid Fluorides in Transition‐Metal Catalysis: A Good Balance between Stability and Reactivity

“…[14] Soon after, the same group reported an ickel-catalyzed decarbonylative borylation of acid fluorides 4 (Scheme 5). [17] In the presence of the monodentate PCy 3 ligand (L2), acid fluorides 1 were converted into the corresponding aldehydes 14 without decarbonylation. Ther eaction proceeds in moderate to excellent yields with good functional group tolerance;for example,anester group in para position remained untouched.…”

Synthesis of Arylstannanes via Palladium‐Catalyzed Decarbonylative Coupling of Aroyl Fluorides

“…With the optimized condition in hand (entry 16 in Table ), the substrate scope was surveyed (Scheme ). Acyl fluorides were readily prepared from the corresponding carboxylic acids or acyl chlorides . It was found that acyl fluorides with an extended‐conjugated system ( 1 a , c , d ) reacted without difficulty, providing stannylation products in 77–89% isolated yields.…”

Säurefluoride in der Übergangsmetallkatalyse: Balance von Stabilität und Reaktivität

“…Bemerkenswert ist, dass das im Laufe des Prozesses gebildete Fluorid als milde Base wirkt und die Organoboronat-Zwischenstufen aktiviert. [17] In Gegenwart des einzähnigen PCy 3 -Liganden (L2)w urden die Säurefluoride 1 ohne Decarbonylierung in die entsprechenden Aldehyde 14 umgewandelt. Eine ähnliche Strategie wurde fürd ie decarbonylierende Methylierung und Ethylierung von Säurefluoriden mit Lewis-saurem Tr imethyl-oder Tr iethylboran und einem sehr ähnlichen Katalysesystem (Ni-(cod) 2 /dppe) angewendet, allerdings mit geringerer Anwendungsbreite.…”