Acid Fluorides as Acyl Electrophiles in Suzuki–Miyaura Coupling

Abstract

The first palladium‐catalyzed construction of ketones through Suzuki–Miyaura reaction by using acid fluorides is described. In contrast to typical acyl electrophiles such as acid chlorides, acid fluorides are uncommon acyl electrophiles to use in boron‐based coupling reactions, probably due to a high level of stability toward nucleophiles. This first attempt to use acid fluorides as a coupling partner with boronic acids allowed highly functional group tolerance and a wide substrate scope while affording various ketones in effective yields.

Catalytic C−H/C−F Coupling of Azoles and Acyl Fluorides

“… Transition‐metal‐catalyzed construction of aromatic ketones using acyl fluorides. [m]=ZnAr, SiF 3 , or B(OH) 2 …”

“…Mechanistic studies suggest that the cleavage of the aromatic CÀHb ond, promoted by a copper-phosphine species, is not the rate-limiting step of this acylation.Scheme1.Transition-metal-catalyzed construction of aromatic ketones using acyl fluorides.[m] = ZnAr, [14] SiF 3 , [15] or B(OH) 2 . [16] [a] Dr.…”

“…Transition-metal-catalyzed cross-couplingreactions of acyl electrophiles with aryl nucleophilesr epresent ap owerful and reliable synthetic strategy for the introductiono fa cyl fragments into aromatic rings to provide aromatick etones, and al arge variety of carboxylic acid derivatives are currently used as acyl electrophiles. [1][2][3][4][5][6][7][8][9][10][11][12][13] Amongt hese, acyl fluorides have recently gained much attention as valuablec arbon-based electrophiles in cross-couplingreactions, especially in acyl coupling [14][15][16][17] and decarbonylative coupling reactions. [17][18][19][20][21][22] Due to the moderate electrophilicity of acyl fluorides,t hey exhibit ag ood balance between stability and reactivity with respectt ot heir compatibility under nucleophilic conditions, that is, they are more stable than the commonly employed acyl chlorides, [4] yet more reactive than the corresponding esters [9, 13b] and amides.…”

Carbonsäurefluoride in der Katalyse durch späte Übergangsmetalle

“…Eine erste praktische,P alladium-katalysierte Acylkupplung von Carbonsäurefluoriden wurde 2017 von unserer Gruppe entwickelt und nutzt Boronsäuren als Nucleophile in einer Suzuki-Miyaura-Kupplung. [62] Fürd iese borbasierte Kupplung wiesen Kombinationen von Pd(OAc) 2 /P(4-MeOC 6 H 4 ) 3 oder Pd(OAc) 2 /PCy 3 gute katalytische Aktivität bei breitem Substratspektrum auf.I nS chema 23 sind repräsentative Ergebnisse der Acylkupplung von Carbonsäurefluoriden mit Boronsäuren abgebildet.…”

Säurefluoride in der Übergangsmetallkatalyse: Balance von Stabilität und Reaktivität

“…(2)]. [10] Die erste decarbonylierende Kupplung von Säurefluoriden gelang Schoenebeck und Mitarbeitern durch eine Tr ifluormethylierung mit Tr iethyl(trifluoromethyl)silan (Schema 3). Im Vergleich zur Hiyama-Kreuzkupplung [Gl.…”