Theoretical insight into the zinc(ii)-catalyzed synthesis of 2-indolyltetrahydroquinolines from N-propargylanilines and indoles: cross-dehydrogenative coupling with temporally separated catalytic activity†,Catalysis Science & Technology

当前位置： X-MOL 学术 › Catal. Sci. Technol. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Theoretical insight into the zinc(ii)-catalyzed synthesis of 2-indolyltetrahydroquinolines from N-propargylanilines and indoles: cross-dehydrogenative coupling with temporally separated catalytic activity†
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2018-03-05 00:00:00 , DOI: 10.1039/c8cy00181b
Hongliang Wang _{1,

2,

3,

4,

5} , Mengmeng Dong _{1,

2,

3,

4,

5} , Chengbu Liu _{1,

2,

3,

4,

5} , Dongju Zhang _{1,

2,

3,

4,

5}

Affiliation

A DFT study has been carried out to provide insight into the molecular mechanism of the zinc(II)-catalyzed cross-dehydrogenative coupling of N-propargylanilines with indoles developed by Nakamura et al. (Angew. Chem., Int. Ed., 2016, 55, 6758–6761). The proposed catalytic cycle consists of two subcycles, through which three C–H bonds (two sp² and one sp³) are activated sequentially. One subcycle carries out the transformation of N-propargylaniline to the intermediate product (IMP), N-benzyl-1,4-dihydroquinoline, and another realizes the transformation of IMP with indole into the final product. Different from general knowledge, the activation of C(sp³)–H is found to be easier than C(sp²)–H activation. The reaction is demonstrated to be an abnormal catalytic cascade reaction, which features the temporal separation of the multiple catalytic activities of the zinc(II) catalyst. The cascade characteristic illuminated in the present work is instructive for developing controlled and efficient syntheses of various products from catalytic cascade reactions. A cascade reaction can be designed so well that the catalyst can sequentially show its multiple catalytic activities, allowing for the controlled efficient synthesis of desired intermediates and products. The present work also rationalizes the experimental observation from a deuterium labeling study.

中文翻译：

用锌（ii）催化从N-炔丙基苯胺和吲哚合成2-吲哚基四氢喹啉的理论见解：具有暂时分离的催化活性的交叉脱氢偶联†

已经进行了DFT研究以提供对由Nakamura等人开发的锌（II）催化的N-炔丙基苯胺与吲哚的交叉脱氢偶联的分子机理的见解。（Angew化学杂志，诠释。编，2016年，55，6758-6761）。拟议的催化循环包括两个子循环，通过这些子循环，三个C–H键（两个sp ²和一个sp ³）被依次激活。一个子循环将N-炔丙基苯胺转化为中间产物（IMP）N-苄基-1,4-二氢喹啉，另一个子循环实现IMP的转化与吲哚一起进入最终产品。从一般知识不同，C的活化（SP ³）-H被发现是比C更容易（SP ²）-H活化。该反应被证明是异常的催化级联反应，其特征是锌的多种催化活性在时间上分离（II）催化剂。在本工作中阐明的级联特性对开发由催化级联反应控制的各种产物的有效合成具有指导意义。可以很好地设计级联反应，以使催化剂可以顺序显示其多种催化活性，从而实现所需中间体和产物的受控有效合成。目前的工作还合理化了氘标记研究的实验观察。

更新日期：2018-03-05

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11