基于BINOL的组件中的立体和结合控制立体化学和自我分类
You-Quan Zou1, Dawei Zhang1, Tanya K Ronson1
1Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom.
Journal of the American Chemical Society
|June 14, 2021
概括
基于BINOL的二甲基中的结合控制了自组装成特定的状结构. 甲基化改变了自我排序行为,轴性性决定了金属中心的手性,从而使新的立体化学纯化物成为可能.
科学领域:
- 超分子化学
- 有机合成
- 协调化学
背景情况:
- 奇拉尔BINOL衍生物是超分子化学中的有价值的构建块.
- 在自我组装中控制立体化学对于创建功能分子架构至关重要.
- 了解自我排序行为是设计复杂多组件系统的关键.
研究的目的:
- 研究BINOL基二甲基的结能力和甲基化如何影响自我组装结果.
- 探索这些修改对线性联体的自我排序行为的影响.
- 通过控制度和组装来制备新的立体化学纯净的异构.
主要方法:
- 含有或不含甲基的基于BINOL的二甲子成分的合成.
- 在金属离子 (FeII,ZnII) 的存在下进行自组装研究.
- 使用NMR光谱和质谱等技术对自我分类行为的分析.
主要成果:
- 在二甲基上自由的基组促进一种二聚体合物形式,而甲基化则导致另一种.
- 当与线性二甲混合时, 甲基化将自我排序从自恋转变为整合性.
- BINOL单元的轴向性始终决定了螺旋金属中心的手性.
- 成功合成了新的立体化学纯粹的异构.
- 切换金属离子 (FeII到ZnII) 或使用较长的线性联结物有利于异质酸盐的形成.
结论:
- 在基于BINOL的系统中,结合和甲基化是控制立体化学和自我分类的关键因素.
- 在立体特异自组装过程中,轴性性转移是一种强大的特征.
- 这些发现使得新型立体化学纯粹的异体质螺旋体的合理设计和合成成为可能.
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