阿斯巴提尔β-Turn-Based Dirhodium ((II) 金属对基C ((sp3) -H氨基化:反选择性和X射线结构分析
Naudin van den Heuvel1, Savannah M Mason1, Brandon Q Mercado1
1Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
Journal of the American Chemical Society
|May 22, 2023
概括
新的基于的二催化剂可实现C sp 3 -H键的高度选择性氨基化,克服了复杂分子合成现有系统的局限性.
科学领域:
- 有机化学
- 催化剂
- 超分子化学
背景情况:
- 氨基化C(sp3) -H键对于将纳入有机分子至关重要.
- 在氨化反应中实现位点和酶控制仍然是一个重大挑战.
- 现有的催化剂系统与复杂的分子结构作斗争.
研究的目的:
- 开发一种新型的性二催化剂,用于选择性C-sp3H氨基化.
- 创建一个模块化平台来生成多种催化剂库.
- 研究这些新催化剂的结构和催化性能.
主要方法:
- 从含有酸的四聚体合成基于的二复合物.
- 创建一个38个不同的性催化剂库.
- 用X射线结晶学来确定二二酸复合物的结构.
- 测试催化剂在对抗选择性基C ((sp3) -H氨基化和分子间N-化氨基化中的性能.
主要成果:
- 建立了一个快速催化剂库生成的模块化系统.
- 一个二 (II) 四酸复合物的第一个晶体结构显示了保留的β-转变形状和不等价的中心.
- 即使在具有挑战性的基质中,在基化中也获得了最先进的抗选择性 (高达95.5:4.5er).
- 催化剂在产生1,1-二胺的N-胺的分子间氨基化中表现出有效性.
结论:
- 基于的二 (II) 复合物提供了一个强大的多功能平台,用于选择性C (sp3) -H氨基化.
- 这些催化剂的独特结构特征有助于它们的高选择性和反应性.
- 这种方法促进了含有的复杂有机分子的合成.
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