A highly regio, diastereo- and enantioselective, scalable Ir-catalyzed hydroarylation of electron rich acyclic and tensioned cyclic olefins with heterobiaryls is described. The reaction of acyclic vinyl ethers, dihydrofuran and norbornenes with a variety of aryl isoquinoline, quinazo-line, and picoline derivatives takes place with simultaneous installation of central and axial chirality, reaching complete branched/linear or exo/endo ratios and excellent diastereo- and enantiomeric excesses when in situ formed [IrI/Tol-SDP] or [IrI/Tol-BINAP] complexes are used as the catalysts. Kinetic isotope effect (KIE) analyses and a comprehensive computational study suggest that, despite fast double bond migratory insertion into Ir-H, the reaction proceeds through a modified Chalk-Harrod mechanism, starting with selectivity-determining insertion into Ir-CAryl. The regioselectivity is controlled by the electron donating alkoxy group, whereas diastereo- and enanti-oselectivity have a complex origin, that depend on the relative orientation of the alkoxy group and the establishment of adequate π-π interactions between the biaryl and the phosphine.

中文翻译：

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杂二芳基的 Ir 催化 Atroposelective 去对称化：乙烯基醚和双环烯烃的加氢芳基化

描述了一种高度区域、非对映选择性和对映选择性、可扩展的 Ir 催化的富电子无环和张力环烯烃与杂二芳基的氢化芳基化。无环乙烯基醚、二氢呋喃和降冰片烯与各种芳基异喹啉、喹唑啉和甲基吡啶衍生物发生反应，同时安装中心和轴手性，达到完整的支链/线性或外/内比例以及优异的非对映和原位形成 [IrI/Tol-SDP] 或 [IrI/Tol-BINAP] 复合物时的对映体过量用作催化剂。动力学同位素效应 (KIE) 分析和综合计算研究表明，尽管双键迁移插入 Ir-H 中的速度很快，但该反应通过改进的 Chalk-Harrod 机制进行，从选择性决定插入 Ir-Caryl 开始。