鲁丁催化醇反应中的机械二分法:一种新型的水化二烯循环化
Barry M Trost1, Michael T Rudd
1Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. bmtrost@stanford.edu
Journal of the American Chemical Society
|September 18, 2003
概括
催化剂有助于二烯醇循环形成循环基. 一种涉及添加水的新途径产生1-环基,证明了对五和六个成员环合成的广泛应用.
科学领域:
- 有机金属化学 有机金属化学
- 有机合成 有机合成
- 催化剂是一种催化剂.
背景情况:
- 众所周知,催化剂可以调节二烯的循环异构反应.
- 现有的机制通常涉及鲁塞纳cyclopentadiene中间体.
- 假设一个潜在的竞争途径涉及水添加到初级酒精基板.
研究的目的:
- 调查水添加途径在催化二烯醇循环中可行性的研究.
- 探索这种新的水性循环过程的范围和选择性.
- 阐明基于酒精替代的机制细节,区分基于酒精替代的反应途径.
主要方法:
- 在水的存在下,各种二烯醇基质的催化反应.
- 产品的合成和特征使用技术,如NMR光谱学.
- 机理学研究探讨反应路径和选择性.
主要成果:
- 通过水利循环化证明了一种通过水利循环化形成五个和六个成员的1-环基的通路.
- 在不对称的二烯酸中观察到化学选择性水添加到不太受阻碍的基.
- 在竞争中的甲基与乙基替代基之间表现出高选择性,并保留双键和环氧化物.
结论:
- 在催化二烯醇循环中,有两种不同的反应多元体运行,这取决于酒精替代.
- 液化循环提供了一条通往功能化循环基的多功能途径.
- 该反应对区域选择性和立体化学表现出了显著的控制.
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