Selective activation/functionalization of C−H bonds has emerged as an atom‐ and step‐economical process at the forefront of modern synthetic chemistry. This work reports palladium‐catalyzed exclusively para‐selective C−H activation/aryl–aryl bond formation with a preference over N‐arylation under the Buchwald–Hartwig amination reaction of 4‐phenylamino[2.2]paracyclophane. This innovative synthetic strategy allows a facile preparation of [2.2]paracyclophane derivatives featuring disparate para‐substitutions at C‐4 and C‐7 positions in a highly selective manner, gives access to a series of potential candidates for [2.2]paracyclophane‐derived new planar chiral ligands. The unprecedented behavior in reactivity and preferential selectivity of C−C coupling over C−N bond formation via C−H activation is unique to the [2.2]paracyclophane scaffold compared to the non‐cyclophane analogue under the same reaction conditions. Selective C−H activation/aryl–aryl bond formation and sequential C−N coupling product formation is evidenced unambiguously by X‐ray crystallography.

中文翻译：

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钯催化的4-苯基氨基[2.2]对环环烷的CH活化/芳基-芳基偶联中的区域选择性控制

在现代合成化学的最前沿，C H键的选择性活化/功能化已成为原子经济和分步经济的过程。这项工作报告钯催化只对-选择性C-H活化/芳基-芳基键的形成具有优先于Ñ 4-苯基[2.2]对环芳烷的Buchwald-Hartwig偶联反应反应下-arylation。这种创新的合成策略可轻松制备具有不同对位的[2.2]对环环烷衍生物以高度选择性的方式在C-4和C-7位置进行取代，可为[2.2]对环环烷衍生的新平面手性配体提供一系列潜在的候选物。在相同的反应条件下，与非环烷类似物相比，[2.2]对环环烷骨架具有前所未有的反应性和通过C H活化形成的C C偶联优先于C N键的选择性。X射线晶体学清楚地证明了选择性的CH活化/芳基-芳基键形成和连续的CN偶联产物形成。