通过通过分子内1,5或1,6原子转移通过以碳为中心的双基因通过可见光介导的远程C-H键的激活
Xintao Gu1, Jiahao Shen1, Ziyu Xu1
1State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, University of Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
Angewandte Chemie (International ed. in English)
|July 20, 2024
概括
我们开发了一种新的分子内原子转移 (HAT) 反应,用于合成亚齐丁丁,氧乙和印度衍生物. 这种方法利用激发的三重态来实现新的1,5-和1,6-HAT反应.
科学领域:
- 有机化学 有机化学
- 摄影化学的使用.
- 合成方法论 合成方法论
背景情况:
- 诺里什-反应是一个关键的光化学转化.
- 在药物化学中,开发用于合成小异环环的新方法,如亚二丁和氧乙,至关重要.
- 控制激素中间路径对于选择性化学反应至关重要.
研究的目的:
- 引入一种新的分子内原子转移 (HAT) 反应.
- 为了高效地合成亚齐丁丁,氧乙和印度衍生物.
- 为了探索前所未有的1,6-HAT反应.
主要方法:
- 使用激发的三重状态碳中心双根.
- 采用类似于诺里什-反应的碳模拟的机制.
- 进行范围评估,大规模合成和衍生研究.
- 执行控制实验,标记,动力学研究,循环电压测量,斯特恩-沃尔默实验和DFT计算.
主要成果:
- 能有效合成亚齐丁丁,氧乙和印度衍生物.
- 成功抑制1,4-比拉基中间体,以防止诺里什II型裂变.
- 开创了前所未有的1,6-HAT反应,由激发的三重状态基因启动.
- 证明了合成实用性和功能组兼容性.
结论:
- 新型分子内HAT反应是合成有价值的异环化合物的通用和高效方法.
- 该机制允许精确控制激素中间体,从而实现选择性转化.
- 这项工作扩大了光化学反应的范围,并为有机合成提供了强大的工具.
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