"Back-to-Front" Indole Synthesis Using Silver(I) Catalysis: Unexpected C-3 Pyrrole Activation Mode Supported by DFT
"Back-to-Front" Indole Synthesis Using Silver(I) Catalysis: Unexpected C-3 Pyrrole Activation Mode Supported by DFT
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DOI：
10.1021/acscatal.8b00745
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发表时间：
2018-08-01
期刊：
影响因子：
12.9
通讯作者：
Unsworth, William P.
中科院分区：
文献类型：
--
作者：
Clarke, Aimee K.;Lynam, Jason M.;Unsworth, William P.
报道了一种高效的银(I)催化方法，通过酸性炔活化合成取代吲哚，尤其是5-羟基衍生物。大多数制备吲哚的方法涉及苯前体的环化，但本文报道的方法在使用吡咯前体方面是不寻常的。密度泛函理论（DFT）研究表明，这些反应是通过吡咯C-3位置的初始活化进行的，然后再进行随后的重排，这与传统的观点相矛盾，即吡咯通过C-2更亲核。
An efficient silver(I)-catalyzed method is reported for the synthesis of substituted indoles, most notably 5-hydroxy-derivatives, via pi-acidic alkyne activation. Most methods for the preparation of indoles involve annulation of a benzene precursor, but the method reported herein is unusual in that pyrrole precursors are used. Density Functional Theory (DFT) studies suggest that these reactions proceed via initial activation of the pyrrole C-3 position before undergoing subsequent rearrangement, contradicting the conventional wisdom that pyrroles are more nucleophilic through C-2.