The reluctance of gold to achieve oxidative addition reaction is considered as an intrinsic limitation for the development of gold-catalyzed cross-coupling reactions with simple and ubiquitous aryl halide electrophiles. Here, we report the rational construction of a Au(I)/Au(III) catalytic cycle involving a sequence of Csp²-X oxidative addition, Csp²-H auration and reductive elimination, allowing a gold-catalyzed direct arylation of arenes with aryl halides. Key to this discovery is the use of Me-Dalphos, a simple ancillary (P,N) ligand, that allows the bottleneck oxidative addition of aryl iodides and bromides to readily proceed under mild conditions. The hemilabile character of the amino group plays a crucial role in this transformation, as substantiated by density functional theory calculations.Catalysis involving Au(I)/Au(III) cycles are notoriously hampered by the reluctance of Au(I) towards oxidative addition. Here, the authors show that an hemilabile bidentate ligand promotes oxidative addition of aryl halides to Au(I) and the catalytic formation of biaryl coupling products.

中文翻译：

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催化性Au（I）/ Au（III）芳基化反应的合理开发，其中涉及芳基卤化物的轻度氧化加成。

金不愿实现氧化加成反应被认为是开发具有简单且普遍存在的芳基卤化亲电试剂的金催化交叉偶联反应的固有限制。在这里，我们报告Au（I）/ Au（III）催化循环的合理构建，涉及一系列Csp ² -X氧化加成，Csp ²-H氧化和还原消除，允许金催化将芳烃与芳基卤化物直接芳基化。该发现的关键是使用Me-Dalphos（一种简单的辅助（P，N）配体），它允许在温和条件下容易地进行芳基碘和溴化物的瓶颈氧化加成。正如密度泛函理论计算所证实的那样，氨基的半不稳定特性在这种转变中起着至关重要的作用。众所周知，Au（I）/ Au（III）循环的催化作用因Au（I）不愿意进行氧化加成而受到阻碍。在这里，作者表明，半不稳定的二齿配体促进芳基卤化物向Au（I）的氧化加成和联芳基偶合产物的催化形成。