第一个用简单的α,β不和子进行的通用酶选择性催化迪尔斯-阿尔德反应
Alan B Northrup1, David W C MacMillan
1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.
Journal of the American Chemical Society
|March 14, 2002
概括
研究人员开发了一种新的iminium催化方法,用于使用简单的子进行对抗选择性迪尔斯-阿尔德反应. 这种有机催化方法可以访问以前具有高立体控制的具有挑战性的循环添加.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 不对称的合成方法
背景情况:
- 迪尔斯-阿尔德反应是有机合成中的一个基本的 [4 + 2] 循环添加.
- 选择性催化对于合成性分子至关重要.
- 简单的二烯醇在对抗选择性迪尔斯-阿尔德反应中具有挑战性.
研究的目的:
- 开发了第一个使用简单二烯的Diels-Alder反应的一般enantioselective催化方法.
- 为了使迪尔斯-阿尔德反应变体能够获得前所未有的Del-Alder反应变体,以奇拉的易斯酸催化剂.
主要方法:
- 开发一种用于iminium催化物的新型性氨基催化剂.
- 催化剂在 [4 + 2] 循环添加中与各种循环和非循环和二烯一起应用.
- 使用计算建模来理解观察到的enantioinduction.
主要成果:
- 用简单的二烯基分子对迪尔斯-阿尔德反应进行了成功的酶选择性催化.
- 证明了催化剂能够适应广泛的循环和非循环和二烯基底.
- 在循环加法反应中达到高水平的反诱导.
结论:
- 一种新的有机催化物催化方法为用简单子对酶选择性迪尔斯-阿尔德反应提供了一种通用方法.
- 这种方法扩大了对enantioselective的Diels-Alder循环添加的范围.
- 开发的催化剂和计算模型在不对称合成方面取得了重大进展.
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