无痕电氨酸用于合成未受保护的循环β-氨基酸
Jin-Sheng Yu1, Miguel Espinosa1, Hidetoshi Noda1
1Institute of Microbial Chemistry (BIKAKEN), Tokyo , 3-14-23 Kamiosaki , Shinagawa-ku , Tokyo 141-0021 , Japan.
Journal of the American Chemical Society
|June 13, 2019
概括
使用循环氧胺的Rh催化电氨化使循环β-氨基酸的高效合成成为可能. 这种无痕,氧化还原中性方法为有机合成提供了改进的原子经济和独特的机械洞察力.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 催化剂是一种催化剂.
背景情况:
- 电友性氨基化提供了一个独特的通过的合成策略.
- 具有O替代的基胺已经推进了电友性氨基化研究.
- 由于激活群体产生的浪费,原子经济是一个挑战.
研究的目的:
- 开发一种新型的Rh催化异-5-one的电友氨化.
- 用于合成未受保护的循环β-氨基酸与化或螺旋循环支架.
- 为了解决电友氨化反应中的原子经济问题.
主要方法:
- 使用替代的异-5-作为Rh催化氨基化的基质.
- 员工设计的循环氧胺可以保留和氧的功能.
- 进行机械学实验以阐明反应路径.
主要成果:
- 成功合成未受保护的循环β-氨基酸,具有所需的支架.
- 实现了无痕迹,氧化还原中性过程,具有高原子经济性.
- 已证明高效的催化剂在格拉姆尺度上的Rh催化剂负荷低至0.1mol%.
- 确定了一种独特的反应途径,涉及螺旋循环和骨重组.
结论:
- 开发了一种高效和原子经济的合成循环β-氨基酸的方法.
- 循环胺的使用提高了产品的功能,减少了浪费.
- 阐明了一种涉及Rh-nitrenoid中间体和骨重组的新反应机制,进步了对电友芳香替代物的理解.
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