芳香溶剂对螺旋式乙基烯寡合物的展开速度有显著的影响
Hiroki Sugiura1, Yasuko Nigorikawa, Yuto Saiki
1Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Aoba, Sendai 980-8578, Japan.
Journal of the American Chemical Society
|November 13, 2004
概括
光学活跃的乙烯寡合物形成螺旋结构,在溶液中展开. 展开速度高度依赖于芳香溶剂的特性,与溶剂的软度相关.
科学领域:
- 有机化学 有机化学
- 超分子化学 超分子化学
- 频谱学是一种光谱学.
背景情况:
- 亚环基乙烯类寡合物是使用Sonogashira合和脱保护合成的.
- 像圆形二重化 (CD) 光谱这样的奇罗普特性,对于描述螺旋结构至关重要.
研究的目的:
- 为了合成光学活跃的非循环乙烯寡合物.
- 为了研究螺旋和随机线圈形状之间的结构过渡.
- 确定影响各种溶剂中螺旋结构展开速度的因素.
主要方法:
- 涉及索诺加希拉合和脱保护的双向合成.
- 循环二重化 (CD) 光谱分析螺旋和随机线圈结构.
- 蒸汽压度测量用于研究寡合体聚合状态.
主要成果:
- 获得了光学活跃的环状乙烯基寡合物的高产量.
- 具有七个或更多螺旋体的寡合体形成了螺旋结构,而较短的则采用了随机的线圈形状.
- 螺旋式七重体展开到形式的随机卷轴,展开的速度高度依赖于芳香溶剂替代剂,差异为七个数量级.
- 展开速度与烯溶剂的绝对硬度相关,较软的烯促进了更快的展开.
- 蒸汽压力测量表明,在某些溶剂中有二维螺旋结构,在其他溶剂中有单体随机线圈结构.
- 在随机卷轴溶液的度下观察到螺旋结构的再生.
结论:
- 光学活跃的非循环乙烯寡合物表现出基于长度的明显的螺旋和随机线圈结构.
- 溶剂特性,特别是芳香替代剂的电子和硬质因素,显著影响螺旋结构的稳定性和展开动态.
- 观察到的结构-溶剂相互作用为响应性分子系统的设计提供了洞察力.
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