Mechanistic Studies of Palladium-Catalyzed Aminocarbonylation of Aryl Chlorides with Carbon Monoxide and Ammonia.
Mechanistic Studies of Palladium-Catalyzed Aminocarbonylation of Aryl Chlorides with Carbon Monoxide and Ammonia.
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DOI：
10.1021/jacs.8b04073
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发表时间：
2018-06-27
影响因子：
15
通讯作者：
Hartwig, John F.
中科院分区：
文献类型：
--
作者：
Wang, Justin Y.;Strom, Alexandra E.;Hartwig, John F.
一个可靠的，钯催化的氨羰基化芳基氯与氨的机理信息的报告。该反应以乙烯配合物1为催化剂进行，通过分离催化中间体和动力学测量获得了反应机理信息，包括在CO存在下芳基氯与钯（0）配合物氧化加成的第一个反应机理数据。合成了芳基钯和苯甲酰钯卤化物中间体，并对这些中间体的形成和反应进行了动力学测量，以确定芳基溴和氯化物与Pd（0）的氧化加成反应机理。本文还讨论了氨与Pd（II）苯甲酰甲基络合物反应生成苯甲酰胺的机理。芳基氯和芳基溴的氧化加成被确定为发生卤代芳烃与带有双齿膦和一个CO配体的三配位Pd（0）物种的限速反应。一个主要的13 C动力学同位素效应表明，这一步涉及裂解的碳-卤素键。我们的数据表明，苯甲酰甲基钯卤化物配合物与氨的反应形成苯甲酰胺发生的途径涉及可逆的置换氯从苯甲酰甲基钯氯化物配合物由氨，脱质子化的结合氨形成苯甲酰甲基钯酰胺络合物，和还原消除形成的C-N键。与该机理一致，芳基钯酰胺基络合物与CO的反应形成相应的伯苯甲酰胺。还阐明了涉及Pd（I）二聚体形成的催化剂失活途径。
Mechanistic information on a reliable, palladium-catalyzed aminocarbonylation of aryl chlorides with ammonia is reported. The reaction occurs with ethylene complex 1 as catalyst, and mechanistic information was gained by isolation of catalytic intermediates and kinetic measurements, including the first mechanistic data on the oxidative addition of aryl chloride to a palladium(0) complex in the presence of CO. Arylpalladium and phenacylpalladium halide intermediates were synthesized, and kinetic measurements of the formation and reactions of these intermediates were undertaken to determine the mechanism of the oxidative addition of aryl bromides and chlorides to a Pd(0) dicarbonyl compound in the presence of CO and the mechanism of the reaction of ammonia with a Pd(II) phenacyl complex to form benzamide. The oxidative addition of aryl chlorides and aryl bromides was determined to occur with rate-limiting reaction of the haloarene with a three-coordinate Pd(0) species bearing a bidentate phosphine and one CO ligand. A primary 13C kinetic isotope effect suggested that this step involves cleavage of the carbon–halogen bond. Our data show that the formation of benzamide from the reaction of phenacylpalladium halide complexes with ammonia occurs by a pathway involving reversible displacement of chloride from a phenacylpalladium chloride complex by ammonia, deprotonation of the bound ammonia to form a phenacylpalladium amido complex, and reductive elimination to form the C–N bond. Consistent with this mechanism, the reaction of an aryl palladium amido complex with CO formed the corresponding primary benzamide. A catalyst deactivation pathway involving the formation of a Pd(I) dimer also was elucidated.
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