Synthesis of Biaryls via Decarbonylative Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of Carboxylic Acids

Abstract

Summary The biaryl motif is a building block in many drugs, agrochemicals, and materials, and as such it is highly desirable as a synthesis target. The state-of-the-art process for biaryl synthesis from ubiquitous carboxylic acids is decarboxylative cross-coupling involving loss of carbon dioxide (CO 2 ). However, the scope of these methods is severely limited, mainly due to specific substitution required to promote decarboxylation. The present report implements a decarbonylative version with loss of carbon monoxide (CO) that enables to directly engage carboxylic acids in a Suzuki-Miyaura cross-coupling to produce biaryls as a general method with high cross-coupling selectivity using a well-defined Pd(0)/(II) catalytic cycle. This protocol shows a remarkably broad scope (>80 examples) and is performed in the absence of exogenous inorganic bases. In a broader context, the approach shows promise for routine applications in the synthesis of biaryls by carefully controlled decarbonylation of prevalent carboxylic acids.

Ni/Pd-catalyzed Suzuki–Miyaura cross-coupling of alcohols and aldehydes and C–N cross-coupling of nitro and aminesviadomino redox reactions: base-free, hydride acceptor-free

“…The coupling product is formed aer several intermediates and the catalyst returns to the cycle by removing B(OH) 2 (CH 2 OH). [27][28][29] Control experiments (Table 5) were performed to help understand this mechanism. Elimination of any of the catalytic centers ( Table 5, entries 1, 2, 8 and 9) and removal of oxygen ( Table 5, entry 10) caused the catalytic activity to stop.…”

Bimetallic Cooperative Catalysis for Decarbonylative Heteroarylation of Carboxylic Acids via C‐O/C‐H Coupling

“…In 2019, we reported the palladium‐catalyzed decarbonylative Suzuki–Miyaura cross‐coupling of carboxylic acids with boronic acids as arylating reagents (Figure 1 D). [40] While the protocol showed broad scope, prefunctionalization to form boronic acids is required for the cross‐coupling [41–43] . With the continuous evolution of the field and the high demand for biaryl heterocycles, we anticipated that the direct implementation of heteroarenes as nucleophiles without prefunctionalization or directing groups in decarbonylative cross‐coupling of carboxylic acids via C−O/C−H bond activation would allow for a broad range of heterobiaryls to be accesses from abundant carboxylic acid as electrophilic cross‐coupling partners (Figure 1 D, bottom).…”

Heterogeneous Non‐noble Catalyst for Highly Selective Production of Linear α‐Olefins from Fatty Acids: A Discovery of NiFe/C

“…The detailed reaction conditions are summarized in the caption of Figure . The choice of Ac 2 O is ascribed to its excellent promoting effect on decarbonylative reactions, based on the work from Szostak and co‐workers . Prior to the determination of the efficiency of our representative bimetallic catalyst, a preliminary experiment was first conducted to determine the optimized ratio of Ni and Fe in the bimetallic catalyst.…”