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

摘要

class="head no_bottom_margin" id="sec1title">IntroductionThe biaryl motif is a privileged subunit in chemical science (, , ). The importance of biaryls is highlighted by the wide presence in pharmaceuticals, functional materials, and natural products in both industrial and academic research (, ). The biaryl architecture is at the heart of widely prescribed antihypertensive and anticancer agents, which, in addition to the huge economic benefit, save the lives of millions of patients annually (A) (). The tremendous success of the conventional Suzuki-Miyaura cross-coupling of aryl halides has provided multiple avenues to generate biaryl architectures of key significance to the chemical industry (, , , ). Since the 2010 Nobel Prize in Chemistry (), more than 12,000 publications address the improvements to the conventional Suzuki-Miyaura cross-coupling, signifying the great advantage of implementing this transformation (). Although effective, the conventional Suzuki-Miyaura cross-coupling of aryl halides suffers from major limitations, including (1) the use of less available aryl halides, (2) the requirement for stoichiometric inorganic base to trigger transmetallation, and (3) generation of toxic halide waste.class="figpopup" href="/pmc/articles/PMC6731188/figure/fig1/" target="figure" rid-figpopup="fig1" rid-ob="ob-fig1">Figure 1Background and Reaction Development(A) Examples of top-selling pharmaceuticals containing the biaryl structure.(B) Enzymatic decarbonylation in nature.(C) Decarboxylative cross-coupling of carboxylic acids (loss of CO2): current state of the art.(D) Proposed decarbonylative cross-coupling of carboxylic acids (loss of CO).(E) Mechanism of the classic and decarbonylative Suzuki cross-coupling.(F) Development of decarbonylative Suzuki cross-coupling. Dppb, 1,4-bis(diphenylphosphino)butane; PCy3, tricyclohexylphosphine; piv, pivaloyl.