铜催化电化学C-H氨基化与二次氨基
Qi-Liang Yang1,2, Xiang-Yang Wang1, Jia-Yan Lu1
1State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis , Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Lu , Shanghai 200032 , China.
Journal of the American Chemical Society
|August 31, 2018
概括
这项研究引入了使用未分裂细胞的铜催化电化学C-H氨化,为合成亚利胺提供了一种环保的方法. 该反应使用氧化还原介质,并通过涉及高价值铜物种的单电子转移机制进行.
科学领域:
- 绿色化学
- 有机合成
- 电化学
背景情况:
- 传统的C-H功能化通常依赖于恶劣的化学物质和贵金属.
- 电化学方法提供了一个对环境无害的替代方案,但通常仅限于分裂细胞和昂贵的催化剂.
- 开发高效和可持续的C-H功能化策略对于现代有机合成至关重要.
研究的目的:
- 在室温下使用未分割的细胞进行第一个铜催化电化学C-H氨基化.
- 提供一种实用且可持续的合成有价值的胺化合物的方法.
- 阐明反应机制,包括氧化还原媒介和活性铜物种的作用.
主要方法:
- 铜催化电化学C-H氨基化.
- 使用未分割的电化学电池和室温条件.
- 使用n-Bu4NI作为关键的氧化还原媒介.
- 进行了机理学研究,包括动力分析,同位素效应,循环电压测量和激素抑制试验.
主要成果:
- 在未分裂细胞中首次成功演示了铜催化电化学C-H氨化.
- 在温和的室温条件下实现胺合成.
- 确定了n-Bu4NI作为转化所必需的关键氧化还原介质.
- 机械研究表明单电子转移 (SET) 途径涉及高价值Cu (III) 中间体.
结论:
- 这项工作在过渡金属催化电化学C-H功能化方面取得了重大进展.
- 开发的方法提供了一种可持续和实用的阿里胺合成方法,避免贵金属和细胞分裂.
- 机械学见解为设计由氧化还原催化剂介导的新型电化学C-H功能化反应铺平了道路.
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