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伪四面体的多合体作为性探针:合成,分离和绝对配置
Peter R Schreiner1, Andrey A Fokin, Oliver Lauenstein
1Institut für Organische Chemie der Justus-Liebig-Universität, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany. prs@chem.uga.edu
Journal of the American Chemical Society
|November 7, 2002
概括
研究人员使用相转移催化合成了新型化阿达曼坦. 这项研究展示了实验和理论方法的强大组合,用于赋予绝对配置,即使在复杂的分子中.
科学领域:
- 有机化学 有机化学
- 立体化学是一种立体化学.
- 频谱学是一种光谱学.
背景情况:
- 稳定,性化碳化合物是有价值的合成标.
- 赋予复杂分子的绝对配置可能是具有挑战性的.
研究的目的:
- 为了合成新的形状和配置稳定的化阿达曼坦.
- 为了分离和确定这些化合物的绝对配置.
- 展示结合实验和计算方法在立体化学赋值中的实用性.
主要方法:
- 阶段转移催化化用于合成.
- 高性能液体染色学 (HPLC) 在性静止相上进行反体分离.
- 循环二元化 (CD) 光谱 (实验和计算) 用于绝对配置的确定.
- 核磁共振 (NMR) 光谱和X射线晶体学用于结构阐明.
主要成果:
- 成功合成了1--3--5--阿达曼坦和1--3--5--7-阿达曼坦.
- 对于1--3--5--阿达曼坦的光学反极体,实现了>99%的反极体过量 (ee).
- 1 - - 3 - - 5 - - 7 - - - 阿达曼坦是第一种含有所有稳定的素的奇拉性亚利法性碳化合物.
- 使用NMR和X射线晶体学确认的结构.
- 通过CD光谱学证明了成功的绝对配置赋值,即使对于光学旋转较弱且缺乏典型染色体的分子.
结论:
- 阶段转移催化是制备复杂化阿达曼坦的有效方法.
- 基拉式HPLC和CD光谱是分离和绝对配置分配的强大工具.
- 实验数据和理论计算的结合为具有挑战性的分子提供了强大的立体化学确定.
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