和循环为立体四度中心的合成构件
Elias Picazo1, Sarah M Anthony1, Maude Giroud1
1Department of Chemistry and Biochemistry , University of California , Los Angeles , California 90095 , United States.
Journal of the American Chemical Society
|May 3, 2018
概括
这项研究引入了一种新方法,用于使用应变中间体和β-基体来创建立体定义的四元中心. 这一过程有效地产生了性胺,从而产生了高度化或化产品.
科学领域:
- 有机化学
- 不对称的合成
- 反应方法
背景情况:
- 四级碳中心在药品和天然产品中普遍存在.
- 四级中心的立体选择性合成仍然是有机化学的一个重大挑战.
- 现有的β-基托和化方法往往缺乏立体控制.
研究的目的:
- 开发一种简单且立体选择性的方法,从β-基衍生基质合成四元中心.
- 研究在不对称转换中使用arines和相关的应变中间体.
- 为β-基托的反选择性化/化提供溶液.
主要方法:
- 将β-基托转化为性胺.
- 性酶胺与现场产生的压力或循环的反应.
- 在水溶性处理中获得化或化产品.
- 计算研究以阐明性转移的机制.
主要成果:
- 成功合成具有高反选择性 (高达96% ee) 的立体定义四元中心.
- 一种对β-基子进行反选择性α-arylation的方法的演示.
- 识别N结合的性辅助物作为性转移的来源.
- 通过奇拉核友来捕捉基的第一个理论研究,用于立体中心生成.
结论:
- 开发的方法提供了有效和立体选择的途径,以获得有价值的化和化化合物.
- 这项工作解决了含有四元立体中心的复杂有机分子合成中的关键差距.
- 这些发现提供了对不对称的体化学和体辅助控制反应的基本见解.
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