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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
通过共结晶和固态机械化学过程进行二重选择性罗塔合成
Keisuke Wada1, Kiichi Yasuzawa1, Shixin Fa1,2
1Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
由于二聚体之间的能量差异很小,合成性罗塔克桑具有挑战性. 这项研究引入了使用联合结晶的固体相方法,以在轮合成中实现高选择性.
科学领域:
- 超分子化学
- 有机合成
- 立体化学
背景情况:
- 由于其独特的相互连接的性结构,性罗塔克桑很重要.
- 当 diastereomers 具有很小的能量差异时,现有的 diastereoselective 合成方法会出现困难.
研究的目的:
- 开发一种用于奇拉性罗塔克桑的新型二重选择性合成方法.
- 为了克服二元体之间的低能量差异的合成罗塔克桑的局限性.
主要方法:
- 通过共结晶形成固体相二重选择性 [3] 伪多多.
- 在无溶剂条件下进行机械化学固体阶段封闭反应.
- 使用立体动力平面形柱[5]和定制轴.
主要成果:
- 在固态 [3] 伪多素形成中达到高体过量 (92%).
- 在溶液中观察到显著较低的二聚体过量 (10%).
- 成功合成了从伪托克桑中间体中保持高 stereoselectivity 的奇拉罗塔克桑.
结论:
- 固态共结晶通过增加有效的度和能量差异来增强二重选择性.
- 机械化学的终端封闭保持了在伪多素形成过程中获得的高 diastereoselectivity.
- 这种方法为合成复杂的性罗塔克桑提供了可靠的策略.
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