在晚期的金属-碳键中插入胺基,形成稳定的胺复合体
Christopher Krug1, John F Hartwig
1Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
Journal of the American Chemical Society
|March 5, 2004
概括
一个新的烯 ((I) 复合物与烯胺反应,形成稳定的胺插入产物. 进一步的反应揭示了复杂的途径,包括β-消除和循环金属化,产生氨基和胺.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 合成化学 合成化学
背景情况:
- ((I) 复合物是多用途的催化剂.
- 了解连接体的反应性对于开发新的合成方法至关重要.
研究的目的:
- 为了合成和表征一种新型的烯 ((I) 复合物.
- 为了研究这个复合体与各种aryl imines的反应性.
- 阐明反应机制并确定关键中间体.
主要方法:
- 使用有机试剂和前体合成一个烯 ((I) 复合物.
- 复合物的与不同胺的反应.
- 使用单晶X射线衍射的产品的表征.
- 涉及产品分析和中间隔离的机制研究.
主要成果:
- 一个稳定的烯 ((I) 复合物的分离, (DPPE) Rh ((C5H5N) ((p-tol).
- 观察因胺插入Rh-aryl键,形成Rh胺产物.
- 确定一种反应途径,涉及对电子中性和电子丰富的 imines 的β-消除和循环金属化.
- 金属循环中间体的分离和表征.
结论:
- 烯 ((I) 复合物表现出与烯胺的多样反应性.
- 一个涉及插入,消除和循环金属化的多步机制控制了产品的形成.
- 结构性表征提供了对反应中间体和途径的洞察.
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