A manganese-catalyzed highly site- and enantioselective benzylic C–H azidation of indolines has been described. The practical method is applicable for azidation of a tertiary benzylic C–H bond with good functional group tolerance, allowing facile access to structurally diverse tertiary azide-containing indolines in high efficiency with excellent site-, chemo-, and enantioselectivity. The generality of the method was further demonstrated by site- and enantioselective azidation of the secondary benzylic C–H bond for a range of secondary azide-containing indolines. The benzylic C–H azidation method allows to straightforwardly and enantioselectively install a variety of nitrogen-based functional groups and diverse bioactive molecules at the C³ position of indoline frameworks through post-azidation manipulations. Gram-scale synthesis was also demonstrated, further highlighting the synthetic potential of the method. Mechanistic studies by combined experiments and computations elucidated the reaction mechanism and origins of stereoselectivity.

中文翻译：

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二氢吲哚的位点和对映选择性锰催化苄基 C-H 叠氮化

已经描述了二氢吲哚的锰催化的高度位点和对映选择性苄基 C-H 叠氮化。该实用方法适用于具有良好官能团耐受性的叔苄基 C-H 键的叠氮化，允许以优异的位点选择性、化学选择性和对映选择性轻松获得结构多样的含叔叠氮二氢吲哚。该方法的通用性通过仲苄基 C-H 键的位点选择性和对映选择性叠氮化进一步证明了一系列含仲叠氮化物的二氢吲哚。^{苄基 C-H 叠氮化方法允许直接和对映选择性地在 C 3}上安装各种基于氮的官能团和不同的生物活性分子通过叠氮化后操作来定位二氢吲哚框架。还展示了革兰氏规模的合成，进一步突出了该方法的合成潜力。通过结合实验和计算的机理研究阐明了立体选择性的反应机理和起源。