通过分子间阿扎-瓦克尔类反应对内醇进行反选择性N-化
Jamie R Allen1, Ana Bahamonde1, Yukino Furukawa1
1Department of Chemistry , University of Utah , 315 S 1400 E , Salt Lake City , Utah 84112 , United States.
Journal of the American Chemical Society
|May 24, 2019
概括
研究人员使用醇和醇开发了一种新的酶选择性阿扎-瓦克尔反应. 这种方法通过选择性地消除β-化物,避免胺副产品和保存立体中心来产生有价值的氨酸.
科学领域:
- 有机化学
- 不对称的催化
- 合成方法
背景情况:
- 瓦克尔反应是有机合成中形成碳-碳键的基本转化.
- 特别是在含有的化合物 (aza-Wacker反应) 中,研发能选择性变体仍然是一个重大挑战.
- 传统的阿扎-瓦克尔反应往往导致不必要的胺产物,使合成路径复杂化.
研究的目的:
- 开发一种新的分子间和酶选择性阿扎-瓦克尔反应.
- 作为源使用醇,作为合伙伴使用醇.
- 为了实现选择性β-化物消除,保持新形成的立体中心.
主要方法:
- 采用催化剂系统进行分子间合.
- 使用印醇和多种类型的醇作为基质.
- 进行同位素标记实验以阐明反应机制.
主要成果:
- 一个选性阿扎-瓦克尔反应的成功开发.
- 与具有各种功能组的合醇和同合醇的相容性已被证明.
- 在所需产品的形成中达到高的反选择性.
- 观察到对酒精部分的选择性β-化物排放,防止胺的形成.
结论:
- 开发的aza-Wacker反应提供了一种新的高效途径,以化胺丰富.
- 这种策略有效地通过控制消除途径来保护新形成的立体中心.
- 同位素标记研究支持合成氨基化机制,为这种催化循环提供了洞察力.
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