Acyl Fluorides in Late‐Transition‐Metal Catalysis

Abstract

In this Review, we summarize the current state of the art in late‐transition‐metal‐catalyzed reactions of acyl fluorides, covering both their synthesis and further transformations. In organic reactions, the relationship between stability and reactivity of the starting substrates is usually characterized by a trade‐off. Yet, acyl fluorides display a very good balance between these properties, which is mostly due to their moderate electrophilicity. Thus, acyl fluorides (RCOF) can be used as versatile building blocks in transition‐metal‐catalyzed reactions, for example, as an “RCO” source in acyl coupling reactions, as an “R” source in decarbonylative coupling reactions, and as an “F” source in fluorination reactions. Starting from the cleavage of the acyl C−F bond in acyl fluorides, various transformations are accessible, including C−C, C−H, C−B, and C−F bond‐forming reactions that are catalyzed by transition‐metal catalysts that contain the Group 9–11 metals Co, Rh, Ir, Ni, Pd, or Cu.

Nickel-Catalyzed Decarbonylative Stannylation of Acyl Fluorides under Ligand-Free Conditions

“…Conventionally, transition metal-catalyzed transformations of acyl fluorides with organometallic reagents (Zn, Si, and B) have focused on the synthesis of biaryl ketones in a carbonyl-group retentive manner [4,5,6]. In a sharp contrast, recently, decarbonylative transformations of carboxylic acid derivatives [7,8], especially acyl fluorides have been studied intensively [9]. Sakai and Ogiwara have disclosed that the auxiliary ligand of the palladium catalyst can control the reaction type of reduction of acyl fluorides [10].…”

Palladium‐Catalyzed Annulation of Acyl Fluorides with Norbornene via Decarbonylation and CO Reinsertion

“…When the mixture was stirred for 24 ha t 120 8C, the corresponding indanone product, 1,2,3,4,4a,9a-hexahydro-1,4-methanofluoren-9-one( 3), was obtained in 4% yield as determined by gas chromatography (GC) (entry 1). The use of electron-rich phosphine ligands, such as P(4-MeOC 6 H 4 ) 3 or JohnPhos instead of PPh 3 furnished 3 in 49 %a nd 20 % yield, respectively (entries 2a nd 3). The most effective electron-richl igand was PCy 3 ,w hich afforded 3 in 76 %y ield (entry 4).…”

“…[1,2] Recently,t he use of acyl fluorides in these transformations has become the subjecto fi ntense research effort, [3][4][5][6][7][8][9][10][11][12] as acyl fluorides are versatile acyl electrophiles with good stability and high reactivity toward nucleophiles. [3,4] One striking aspect of using acyl fluorides in CÀCb ondforming reactionsi st hat they functiona sa na cyl electrophile to give the corresponding ketone (Scheme 1A). [5] Whenu sing these substrates in decarbonylative coupling reactions, biaryl compounds are obtainede fficiently (Scheme 1B).…”

Enhancing stability by trapping palladium inside N-heterocyclic carbene-functionalized hypercrosslinked polymers for heterogeneous C-C bond formations

“…However, to the best of our knowledge, carbonylation of C-H bonds to acid halides has not been reported. Compared with the acid chlorides (C-Cl bonds, ~78 kcal/mol), acid uorides are more thermodynamically stable (C-F bonds, ~105 kcal/mol) and can be readily handled for further transformation under simple conditions 55 . We herein select carbonylation of indole to corresponding acid uoride as model reaction to investigate the catalytic activity and stability of KAP-Pd-PEPPSI, and this one-pot transformation is designed to proceed via oxidative iodination of C-H bond rst and then carbonylation.…”