从1,2,2-triarylcyclopropanecarboxylate连接体中获得的D2-对称二催化剂:设计,合成和应用
Changming Qin1, Vyacheslav Boyarskikh, Jørn H Hansen
1Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
迪罗四氧化 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - (Rh (Rh) 是一种新型性催化剂,用于高度选择性循环和并联反应. 这种催化剂提供了简单的合成和与各种基质和溶剂的兼容性.
科学领域:
- 有机金属化学 有机金属化学
- 不对称的催化剂.
- 有机合成 有机合成
背景情况:
- 基拉尔催化剂对于酶选择性合成至关重要.
- 迪罗复合物在循环化反应中被广泛使用.
- 开发高效和多用途的性催化剂仍然是有机化学的一个关键挑战.
研究的目的:
- 评估Dirhodium tetrakis- ((R) - ((1- ((4-bromophenyl) --2,2-diphenylcyclopropanecarboxylate) (Rh(2) ((R-BTPCP) ((4)) 作为一种性催化剂的疗效.
- 探索其在酶选择性循环和相关反应中的应用.
- 通过计算研究来理解催化机制.
主要方法:
- 合成性迪罗催化剂Rh ((2) ((R-BTPCP) ((4).
- 使用阿里尔和 styryldiazoacetates 的 enantioselective 循环化反应.
- 协同循环化/Cope重组和C-H功能化/Cope重组反应.
- 计算建模以阐明催化剂的结构和机制.
主要成果:
- 在循环化反应中,R-BTPCP (Rh) 显示出高的反抗选择性.
- 成功实现了双重循环化/Cope重新排列和C-H功能化/Cope重新排列.
- 催化剂表现出易于合成,耐受群大小和与二甲的兼容性.
- 计算研究揭示了动态带旋转以适应基质结合.
结论:
- Rh2 (R-BTPCP) 是各种反选择性转化的一种高效的性催化剂.
- 它的实用优势,包括合成和兼容性,使其成为有机合成的宝贵工具.
- 催化剂的结构灵活性对其反应性和选择性起着至关重要的作用.
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