Synthesis of Biaryls via Decarbonylative Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of Carboxylic Acids
Synthesis of Biaryls via Decarbonylative Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of Carboxylic Acids
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DOI：
10.1016/j.isci.2019.08.021
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发表时间：
2019-09-27
期刊：
影响因子：
5.8
通讯作者：
Szostak, Michal
中科院分区：
文献类型：
--
作者：
Liu, Chengwei;Ji, Chong-Lei;Szostak, Michal
联芳基基序是许多药物、农用化学品和材料中的结构单元，因此它作为合成靶标是非常理想的。从普遍存在的羧酸合成联芳基的最先进工艺是涉及二氧化碳（CO2）损失的脱羧交叉偶联。然而，这些方法的范围受到严重限制，主要是由于促进脱羧所需的特定取代。本报告实施了一种脱羰基版本，损失一氧化碳（CO），其能够直接使羧酸参与Suzuki-Miyaura交叉偶联以产生联芳基，作为使用明确定义的Pd（0）/（II）催化循环的具有高交叉偶联选择性的通用方法。该方案显示出非常广泛的范围（>80个实例），并且在不存在外源性无机碱的情况下进行。在更广泛的背景下，该方法显示出通过仔细控制普遍羧酸的脱羰基来合成联芳基化合物的常规应用的前景。
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.