Synthetic and Mechanistic Studies into the Rearrangement of Spirocyclic Indolenines into Quinolines
Synthetic and Mechanistic Studies into the Rearrangement of Spirocyclic Indolenines into Quinolines
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DOI：
10.1002/ejoc.201900798
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发表时间：
2019-09-01
影响因子：
2.8
通讯作者：
Lynam, Jason M.
中科院分区：
文献类型：
--
作者：
Epton, Ryan G.;Clarke, Aimee K.;Lynam, Jason M.
一个密度泛函理论（DFT）的方法已被用来阐明最近发现的重排反应的螺环吲哚到环戊酮稠合喹啉的转换机制。这种不寻常的重排反应的一种新的碱介导的变体也被开发出来，它在比类似的酸性反应所需的温度低得多的温度下操作。DFT研究表明，酸和碱介导的变体都通过烯醇/烯醇化物中间体进行，并且这种关键中间体形式的容易程度似乎在解释动力学结果方面至关重要。
A Density functional theory (DFT) approach has been used to shed light on the mechanism of a recently discovered rearrangement reaction for the conversion of spirocyclic indolenines into cyclopentanone-fused quinolines. A new base-mediated variant of this unusual rearrangement reaction has also been developed, that operates at much lower temperatures than those required in the analogous acidic reactions. The DFT study suggests that both the acid and base-mediated variants proceed via an enol/enolate intermediate, and the ease with which this key intermediate forms appears to be crucial in explaining the kinetic outcomes.