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

• Published in: iScience Vol. 19; pp. 749 - 759
• Main Authors: Liu, Chengwei, Ji, Chong-Lei, Qin, Zhi-Xin, Hong, Xin, Szostak, Michal
• Format: Journal Article
• Language: English
• Published: United States Elsevier Inc 27.09.2019; Elsevier
• Subjects: Catalysis; Chemistry; Organic Chemistry; Chemistry; Catalysis; Organic Chemistry
• ISSN: 2589-0042; 2589-0042
• DOI: 10.1016/j.isci.2019.08.021

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 (CO2). 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. [Display omitted] •First decarbonylative Suzuki cross-coupling of carboxylic acids via Pd catalysis•Rapid synthesis of functionalized biaryls from ubiquitous carboxylic acids•Mechanistic insights from DFT studies point at the origin of high selectivity•CO loss as a strategy for expanding access to aryl metals (cf. CO2 loss) Chemistry; Catalysis; Organic Chemistry