Biaryl synthesis via Pd-catalyzed decarboxylative coupling of aromatic carboxylates with aryl halides
Biaryl synthesis via Pd-catalyzed decarboxylative coupling of aromatic carboxylates with aryl halides
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DOI：
10.1021/ja068993
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发表时间：
2007-04-18
影响因子：
15
通讯作者：
Levy, Laura M.
中科院分区：
文献类型：
--
作者：
Goossen, Lukas J.;Rodriguez, Nuria;Levy, Laura M.
提出了一种区域特异性构建不对称双芳基的新策略，该策略将容易获得的羧酸盐原位脱羧，使芳基金属在与芳基卤化物的催化交叉偶联反应中充当亲核组分。催化剂体系由铜-菲罗啉配合物和钯配合物组成，铜-菲罗啉配合物催化芳香族羧酸盐挤压CO2生成芳基铜，钯配合物催化这些中间体与芳基卤化物交叉偶联。这种双金属系统允许各种芳基、杂芳基或乙烯基羧酸与芳基或杂芳基碘化物、溴化物或氯化物在160℃下在温和的碱（如碳酸钾）存在下直接偶联。42种双芳基化合物的合成证明了该反应的范围和潜在的经济影响，其中一些具有重要的工业意义。讨论了新转型的剩余挑战和未来前景。
A new strategy for the regiospecific construction of unsymmetrical biaryls is presented, in which easily available salts of carboxylic acids are decarboxylated in situ to give arylmetal species that serve as the nucleophilic component in a catalytic cross-coupling reaction with aryl halides. The catalyst system consists of a copper phenanthroline complex that mediates the extrusion of CO2 from aromatic carboxylates to generate arylcopper species, and a palladium complex that catalyzes the cross-coupling of these intermediates with aryl halides. This bimetallic system allows the direct coupling of various aryl, heteroaryl, or vinyl carboxylic acids with aryl or heteroaryl iodides, bromides, or chlorides at 160 degrees C in the presence of a mild base such as potassium carbonate. The present scope and potential economic impact of the reaction are demonstrated by the synthesis of 42 biaryls, some of which are of substantial industrial relevance. Remaining challenges and future perspectives of the new transformation are discussed.