二甲四碳酸盐催化酶选择性循环化与阿里尔迪亚酸盐
Joshua K Sailer1, Jack C Sharland1, John Bacsa1
1Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, United States.
Organometallics
|August 18, 2023
概括
新的合性迪鲁催化剂为高度选性循环化产生碗形结构. 在非对称反应中,这些二,三四碳酸盐催化剂在异构反应中达到高达94%的异构过量 (ee).
科学领域:
- 有机金属化学 有机金属化学
- 不对称的催化剂.
- 合成有机化学 合成有机化学
背景情况:
- 状碗形的迪鲁四碳酸盐催化剂类似于迪罗的对应物.
- 这些催化剂自组装成C4对称结构.
研究的目的:
- 准备和评估用于不对称循环的状碗形二 (II,III) 四碳酸盐催化剂.
- 在类似的催化系统中研究第一排过渡金属同源 (Cu,Co) 的有效性.
主要方法:
- 合成性二 ((II,III) 四碳酸盐催化剂.
- 在使用捐赠/接受碳化合物的不对称循环化反应中对催化剂的评估.
- 计算研究以了解催化剂的行为和机制.
主要成果:
- 最优的催化剂,Ru2(S-TPPTTL) 4·BArF,在循环化中达到高达94%的反体过剩 (ee).
- 第一排的过渡金属催化剂 (Cu,Co) 几乎没有表现出不对称的诱导.
- 计算研究显示,由于连接体损失,Cu和Co碳化合物复合物的不稳定性.
结论:
- 化催化剂对不对称的循环化是有效的,产生高度反选择性的产品.
- 碗形结构对于不对称的感应至关重要,其在Cu/Co系统中的破坏解释了它们的性能差.
- 迪鲁催化剂为对抗选择性碳转移反应提供了一个有前途的替代方案.
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