继电器PHOS:在不对称的帕拉催化基化中具有流动性性性体
Regina C So1, Hariharaputhiran Subramanian1, Carter R Kuehn1
1Department of Chemistry and Biochemistry, North Dakota State University, Fargo, North Dakota 58108-6050, United States.
研究人员开发了一种用于新型P,N配体的模块化合成,该配体在皮拉核上具有流动组. 这些连接体在催化基化中表现出高的enantioselectivity,随着流动性群体大小的增加,选择性增加.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 连接体设计 连接体设计
背景情况:
- 开发新的- (P,N) 配体对于推进非对称催化非常重要.
- 皮拉索林支架为联结体构造提供了一个多功能平台.
- 流动组可以影响催化反应中的立体化学结果.
研究的目的:
- 建立一个模块化合成路径,为P,N配体,在一个pyrazoline核心的流动性组的特点.
- 评估这些新型配体在催化非对称基化中的有效性.
- 为了研究连接体结构,特别是流动性组,和选择性之间的关系.
主要方法:
- 从商业上可获得的乙中合成血性P,N配体的三步合成.
- 通过半准备性性高性能液体染色学和性enantioselective相转移催化,对enantiopure连接物的分离.
- 用烯酸乙酸二和二甲基烯酸乙酸作为基质的烯酸催化基化中的联体性能评估.
主要成果:
- 在总产量的18-76%中合成的 Racemic 配体.
- 通过性分离和不对称催化,成功获得了性的配体.
- 优化的催化基化实现了98%的产量和94%的异构过量 (ee) 与二乙和二甲基酸盐.
- 观察到连接体的流动组大小与由此产生的反选择性之间存在正相关性.
结论:
- 已经建立了一个模块化和高效的新型P,N配体与可调节的流动群的合成策略.
- 合成的配体在催化不对称的基化中表现出高效.
- 结合较大的流动性群体的配体设计是实现催化转换中优异的反选择性的一种有希望的方法.
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