Rh (I) 催化分子间酸化:化物和胺酸的对抗选择性交叉合
Kevin G M Kou1, Diane N Le, Vy M Dong
1Department of Chemistry, University of California , Irvine, California 92697, United States.
Journal of the American Chemical Society
|June 18, 2014
概括
这项研究引入了一种新型的催化α-基胺与化的酸化,产生α-酸胺. 在这个重要的有机合成反应中,一种新的Josiphos连接体实现了高原子经济性和酶选择性.
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:
- α-基托胺是多功能合成中间体.
- 分子间酸化反应对于C-C键的形成至关重要.
- 在有机合成中,开发酶选择性催化方法仍然是关键的挑战.
研究的目的:
- 开发一种新型的 (((I) 催化α-基胺与亚利法性化的分子间氧化.
- 在合成α-acyloxyamides中实现高原子经济性和酶选择性.
- 为了阐明反应机制,并建立一个立体化学模型,以诱导.
主要方法:
- 使用 ((I) 催化剂与新设计的约西福斯配体.
- 进行了α-基托胺基与各种阿利法性化物之间的分子间酸化.
- 进行了机械和动力学研究,以了解反应途径.
- 开发了一个立体化学模型来解释enantioselectivity.
主要成果:
- 在Rh (I) 催化下,成功实现了α-基托胺与阿利法性化物之间的分子间化.
- 新设计的Josiphos配体使得能够获得具有高原子经济性的α-acyloxyamides.
- 在α-acyloxyamides的形成中观察到高的enantioselectivity.
- 机理学研究显示,在化激活中具有双重作用,用于交叉合.
结论:
- 开发了一种高效和选择性方法,通过催化酸化合成α-酸胺.
- 设计的Josiphos连接体对不对称合成有效,提供高原子经济性.
- 拟议的机制和立体化学模型为催化循环和酶诱导提供了有价值的见解.
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