Divergent Reactivity of Indole-Tethered Ynones with Silver(I) and Gold(I) Catalysts: A Combined Synthetic and Computational Study
Divergent Reactivity of Indole-Tethered Ynones with Silver(I) and Gold(I) Catalysts: A Combined Synthetic and Computational Study
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DOI：
10.1055/s-0037-1610181
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发表时间：
2018-12-01
影响因子：
2.6
通讯作者：
Unsworth, William P.
中科院分区：
文献类型：
--
作者：
Liddon, John T. R.;Rossi-Ashton, James A.;Unsworth, William P.
结合合成和计算（DFT）的研究已经进行，以说明不同的反应活性的吲哚系炔酮时，处理Ag（I）和Au（I）催化剂。这两种催化剂系统分别从相同的前体提供螺环吲哚啉和咔唑，其中反应结果被认为是关键脱金属步骤的速率差异的结果。一个开环/闭环异构化过程中提出，使螺环和C-2成环吲哚中间体的相互转化，在对比的1，2-迁移机制在以前的研究中初步提出。
A combined synthetic and computational (DFT) study has been performed to account for the divergent reactivity of indole-tethered ynones when treated with Ag(I) and Au(I) catalysts. The two catalyst systems deliver spirocyclic indolenines and carbazoles, respectively, from the same precursors, with the reaction outcomes believed to be a result of differences in the rates of a key protodemetalation step. A ring-opening/ ring-closing isomerisation process is proposed to enable the interconversion of spirocyclic and C-2 annulated indole intermediates, in contrast to the 1,2-migration mechanism tentatively proposed in previous studies.