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Gold(I)-Catalyzed Dearomative [2+21-Cycloaddition of Indoles with Activated Allenes: A Combined Experimental-Computational Study

机译:金(I)催化的吲哚与活化的异戊烯的脱芳香[2 + 21-环加成反应:组合的实验计算研究

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摘要

The gold-catalyzed synthesis of methylidene 2,3-cyclobutane-indoles is documented through a combined experimental/computational investigation. Besides optimizing the racemic synthesis of the tricyclic indole compounds, the enantioselective variant is presented to its full extent. In particular, the scope of the reaction encompasses both aryloxyallenes and allenamides as electrophilic partners providing high yields and excellent stereochemical controls in the desired cycloadducts. The computational (DFT) investigation has fully elucidated the reaction mechanism providing clear evidence for a two-step reaction. Two parallel reaction pathways explain the regioisomeric products obtained under kinetic and thermodynamic conditions. In both cases, the dearomative C-C bond forming event turned out to be the rate-determining step.
机译:通过联合的实验/计算研究记录了金催化的亚甲基2,3-环丁烷-吲哚的合成。除了优化三环吲哚化合物的外消旋合成外,还全面展示了对映选择性变体。特别地,反应范围包括芳氧基烯丙二烯和烯丙酰胺作为亲电子伴侣,在所需的环加合物中提供高产率和优异的立体化学控制。计算(DFT)研究已经充分阐明了反应机理,为两步反应提供了明确的证据。两条平行的反应路径解释了在动力学和热力学条件下获得的区域异构产物。在这两种情况下,脱芳香性的C-C键形成事件被证明是决定速率的步骤。

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