Biaryl Ketones by Suzuki–Miyaura Cross‐Coupling of Organotrifluoroborates and Acyl Chlorides

Abstract

A procedure for the synthesis of biaryl ketones by a palladium‐catalyzed Suzuki–Miyaura cross‐coupling reaction between phenyltrifluoroborates and benzoyl chlorides is described. Organotrifluoroborates are unique to other cross‐coupling reagents as they have a high functional‐group tolerance and are moisture‐stable. Moderate to excellent yields were obtained for all substrates tested.

Ligand-Controlled Chemoselective C(acyl)–O Bond vs C(aryl)–C Bond Activation of Aromatic Esters in Nickel Catalyzed C(sp2)–C(sp3) Cross-Couplings

“…Therefore, a user-friendly synthetic operation which can produce solely ketone products is highly desired. Transition-metal-catalyzed Suzuki–Miyaura cross-coupling is an ideal platform for such transformations and progress in acylation reactions was accomplished by using reactive acylating reagents such as acid chlorides, acid anhydrides and thioesters . In addition, amide C–N bond cleavage became a recent topic; however, the reaction outcome is highly dependent on the protecting group on the amide moiety.…”

N-Acylsaccharins: Stable Electrophilic Amide-Based Acyl Transfer Reagents in Pd-Catalyzed Suzuki–Miyaura Coupling via N–C Cleavage

“…The incorporation of the acyl group into organic molecules is a fundamental transformation in biological and synthetic chemistry. , In this context, the transition-metal-catalyzed acylation of organometallic reagents has emerged as a powerful strategy to produce functionalized ketones with numerous applications in pharmaceutical, dye, and agrochemical industries. , A number of methods and reagents have been developed over the past years, including palladium- and nickel-catalyzed cross-coupling reactions of acyl chlorides, thioesters, and anhydrides . By contrast, the transition-metal-catalyzed acylation by N–C cleavage in amides represents a significant challenge due to n N → π CO * conjugation and the resulting partial double bond character of the amide bond .…”

“…N -Acylsaccharins serve as new, highly reactive, bench-stable, economical, amide-based, electrophilic acyl transfer reagents for C–C bond forming reactions via acyl-metal intermediates by selective N–C bond cleavage. This finding opens the door for using N -acylsaccharins in a wide range of transition-metal-catalyzed reaction manifolds. − …”

RUCY‐XylBINAP Catalyzed and Autoclave Assisted Rapid Enantioselective Synthesis of Benzhydrols

“…Due to importance of benzhydrol derivatives, asymmetric hydrogenation in organic chemistry and the special role of chiral molecules in pharmacology, a rapid auto clave assisted asymmetric hydrogenation of biaryl ketones to benzhydrols is proposed by utilizing RUCY-XylBINAP catalyst in excellent yield and enantioselectivities (Scheme 3) based on Ohkuma and coworkers study. [11] The starting material required for benzhydrol derivatives was obtained by cross-coupling protocol (Table 1, entry 9) utilizing Pd(PPh 3 ) 4 , K 2 CO 3 in Toluene-H 2 O (10 : 1) at 90°C for 12 h [12] (Scheme 2, Table 1).…”

“…The starting material required for benzhydrol derivatives was obtained by cross‐coupling protocol (Table , entry 9) utilizing Pd(PPh 3 ) 4 , K 2 CO 3 in Toluene‐H 2 O (10 : 1) at 90 °C for 12 h (Scheme , Table ).…”