连接物控制的Ir-催化区域分离氧化未激活基的氧化
Honghui Lei1, John H Conway1, Caleb C Cook1
1Department of Chemistry , Columbia University , New York , New York 10027 , United States.
Journal of the American Chemical Society
|July 17, 2019
概括
这项研究引入了催化氧胺反应,用于从未激活的基中产生有价值的乳酸和乳. 该过程允许通过可调整的复合体,对不同大小的环进行受控合成.
科学领域:
- 有机金属化学 有机金属化学
- 合成有机化学 合成有机化学
- 催化剂是一种催化剂.
背景情况:
- 内分子氧化胺反应对于合成异环化合物至关重要.
- 开发非活化基的区域选择性方法仍然是一个合成挑战.
- 催化为C-H功能化和相关转换提供了独特的反应性.
研究的目的:
- 开发一种新型的未激活基的分子内氧胺化方法.
- 为了实现γ-乳酸,γ-乳酸和δ-乳酸的区域分离合成.
- 阐明反应机制并确定关键中间体.
主要方法:
- 使用了由 (III) 复合体催化的分子内氧化化策略.
- 采用电子调节的环二烯 (Cyclopentadienyl iridium) 复合物来控制区域选择性.
- 研究的反应途径,包括5-exo和6-endo循环.
主要成果:
- 从未被激活的基中成功合成了有价值的γ-乳酸,γ-乳酸和δ-乳酸.
- 通过调整催化剂,证明了对氧氨化过程的区域选择控制.
- 提出了一种反应机制,其中涉及一种主要的 [3.1.0] 双循环中间体,该中间体来自于一种 ((V) 烯.
结论:
- 开发了一种多用途的Ir(III) 催化区分氧氨基化方法,用于获取多种乳和乳结构.
- 区域选择性通过催化剂设计得到有效控制,使得可以使用不同尺寸的环.
- 拟议的机制强调了新型双循环中间体的形成,促进了对Ir-催化转换的理解.
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