在光化学不对称合成中使用奇拉修饰的化石和晶体
Kenneth C W Chong1, J Sivaguru, Tetsuya Shichi
1Department of Chemistry, University of British Columbia, Vancouver, Canada V6T 1Z1.
Journal of the American Chemical Society
|March 21, 2002
概括
研究人员探索了使用西奥利特和晶体中的奇拉辅助物进行 cis-to-trans 光异构化不对称的诱导. 在固态中的离子性辅助方法实现了99%的反选择性,为控制立体化学提供了洞察力.
科学领域:
- 有机化学 有机化学
- 摄影化学的使用.
- 材料科学 材料科学 材料科学
背景情况:
- 不对称的诱导对于合成性分子至关重要.
- 光异构化反应为分子转变提供了独特的途径.
- 控制循环衍生物中的立体化学是具有挑战性的.
研究的目的:
- 调查三种不同的方法,用于非对称的诱导在光异构化1--2,3-二cyclopropane衍生物.
- 在cis-to-trans光异构化中实现高水平的异构选择性.
- 阐明控制立体化学控制的机制.
主要方法:
- 在MY热质体内使用性感应器和性性辅助器.
- 在晶体环境中使用离子奇拉辅助剂.
- 分析二聚体过量及其对热酸盐 (M+) 的依赖.
主要成果:
- 实现了高不对称的诱导水平,高达71%的共价辅助物在石中.
- 使用固态离子性辅助方法证明了99%的显著的反选择性.
- 鉴定了热酸盐类型作为影响二聚体过剩的重要因素.
结论:
- 固态离子性辅助方法为光异构化提供了异常的反选择性.
- 基基与环基环相对的固定方向决定了晶体中的反选择性.
- 研究结果为对抗选择性反应的理论研究提供了宝贵的见解.
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