通过由电荷转移相互作用驱动的C(sp2) -C(sp2/sp) 合反应合成NIR-II光体
Jie Li1, Xin-Xin Liu2, Ling-Ya Peng2
1Key Laboratory of Radiopharmaceuticals, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing, 100875, P. R. China.
Angewandte Chemie (International ed. in English)
|February 12, 2025
概括
一种新的C-C合反应利用电子捐赠者-接受者 (EDA) 复合形成来降低激活能量,使新的近红外光体能够高效合成.
科学领域:
- 有机化学 有机化学
- 材料科学 材料科学 材料科学
- 超分子化学 超分子化学
背景情况:
- 在有机合成中,C-C合反应是基本的.
- 电子捐赠-接受器 (EDA) 相互作用可以影响反应通路.
- 近红外 (NIR-II) 光体在生物成像和材料领域有应用.
研究的目的:
- 报告一个由电荷转移驱动的新的C(sp2) -C(sp2/sp) 合反应.
- 为了阐明这种EDA复杂介导反应的机制.
- 通过这种方法合成新的NIR-II光体.
主要方法:
- 光谱分析 (吸收光谱,1H NMR)
- 单晶X射线衍射的X射线衍射方法
- 动力学研究 (H/D 和 12C/13C KIE)
- 高层次的理论计算.
主要成果:
- 通过实验和计算方法证实了稳定的EDA复合物的形成.
- 降低了C-C键形成的激活屏障 (Ea=9.17 kcal/mol),这是速度限制的步骤.
- 成功合成了单替代和二替代产品,包括基于BBTD的新型NIR-II光体.
结论:
- 在EDA复合体内的电荷转移相互作用对合反应至关重要.
- 反应机制涉及EDA复合体的形成,促进限制速率的C-C键的形成.
- 这种新的合反应为合成各种NIR-II光体提供了一种多功能途径.
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