基于甲的3 - 氨基-1,2 - 双醇区域体的立体选择性合成和催化应用
Márton Benedek Háznagy1,2, Antal Csámpai3, Imre Ugrai2
1Institute of Pharmacognosy, University of Szeged, H-6720 Szeged, Hungary.
International journal of molecular sciences
|April 27, 2024
概括
从单二烯衍生出的基拉尔氨基二醇被合成并用作添加甲到甲的催化剂. 这些催化剂实现了良好的酶选择性,选择性在环闭时逆转为1,3-oxazines.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 立体化学是一种立体化学.
背景情况:
- 性氨基醇在不对称合成中是有价值的合成物.
- 单烯为性构建块提供了一种可再生的来源.
- 开发高效的性催化剂对于酶选择性转换至关重要.
研究的目的:
- 合成一个基于regioisomeric monoterpene的aminodiols的库.
- 为了评估它们作为合催化剂在添加二甲到甲中的有效性.
- 调查立体化学结果并探索结构-活动关系.
主要方法:
- 通过还原性氨基化和Overman重组合成氨基醇.
- 使用四氧化 (OsO4) /N-甲基摩尔福林N-氧化 (NMO) 的立体选择性二氧化.
- 分离二聚异构体并转化为二次衍生物.
- 作为催化剂在不对称的二甲添加到甲中的应用.
- 稳定性分析的理论建模研究.
主要成果:
- 一个基于regioisomeric monoterpene的aminodiols的库已经成功合成.
- 催化剂在甲添加到甲时,表现出中等到良好的反选择性 (高达94% ee).
- 单独形成的N-基替代氨基的环闭性 1,3-氧.
- 在二次氨基醇和它们的1,3-oxazine类似物之间观察到性选择性的逆转.
结论:
- 基于单二烯的氨基醇是不对称合成的有效性催化剂.
- 催化剂的区域化学和立体化学显著影响了酶选择性.
- 1,3-氨酸衍生物提供了一个具有反向立体化学控制的替代催化系统.
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