一个结合实验和计算研究的带控制的兰合硫胺的硫胺
Kaiming Han1,2, Hong Liu1, Madeline E Rotella3
1Research Center for Chemical Biology and Omics Analysis, Department of Chemistry, Southern University of Science and Technology, 1088 Xueyuan Blvd., Shenzhen, Guangdong, P. R. China.
Nature communications
|June 4, 2024
概括
这项研究引入了一种化学选择性的Chan-Lam合,用于合成N-arylated硫胺. 一种特定的配体指导反应,增强所需的C-N键的形成,而不是C-S键.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 药用化学 医学化学
背景情况:
- 硫胺具有独特的S(II) -N键,具有显著的立体化学特性和工业应用.
- 开发用于修改硫胺的选择性方法对于获取各种化学结构至关重要.
研究的目的:
- 为了呈现一种化学选择性的Chan-Lam合反应,用于合成N-arylated硫胺.
- 阐明这种转换中化学选择性的机制和控制.
主要方法:
- 利用三酸盐的pybox连接体,在铜催化Chan-Lam合中指导化学选择性.
- 采用UV-Vis光谱和电子磁共振 (EPR) 技术来描述催化剂的静止状态和中间体.
- 进行了计算力学研究,以了解反应路径和选择性.
主要成果:
- 在硫胺二烯酸结合中实现了化学选择性C-N键形成,而不是C-S键形成.
- 通过使用光谱方法,包括15N标记,识别并确认了由Cu (II) 衍生的静止状态和关键中间体.
- 计算研究表明,N-arylation在动力学和热力学上受到青,在减少性消除之前进行deprotonation.
结论:
- 皮博克斯配体在控制化学选择性方面发挥着关键作用,通过防止不必要的S,N-bis-chelation和有利于C-N键形成来控制化学选择性.
- 体-基质相互作用决定了竞争的S-arylation和N-arylation通路的能量格局.
- 这种方法提供了一条可靠的途径,以获得具有高选择性的N-arylated硫胺.
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