亚齐里丁与复合物的相互作用:氧化添加和减少消除反应,破坏并形成C-N键
Beatrice L Lin1, Christopher R Clough, Gregory L Hillhouse
1Searle Chemistry Laboratory, Department of Chemistry, The University of Chicago, Chicago, IL 60637, USA.
Journal of the American Chemical Society
|March 21, 2002
概括
复合物促进N-托西拉齐里丁的氧化添加,形成亚甲. 随后的氧化触发了减少性消除,通过立体化学反转再生亚齐里丁.
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
背景情况:
- N-托西拉齐里丁是多功能的三分子异环.
- 复合物是众所周知的各种有机转变的催化剂.
- 氧化添加是许多催化循环中的关键步骤.
研究的目的:
- 为了研究N-tosiylaziridines与复合物的反应.
- 为了描述由此产生的亚甲环butan复合物.
- 探索反应和随后的转换的立体化学结果.
主要方法:
- N-托西拉齐里丁与 (bpy) Ni(cod) 或 (bpy) NiEt2.2 的反应.
- 隔离和特征的亚甲环丁复合物.
- 使用单酸亚齐里丁和NMR光谱学的立体化学分析.
- 亚甲环butan复合物的氧化,以研究减少性消除.
主要成果:
- 在50-70%的产量中形成亚甲环butan复合物 (bpy) Ni (((NTosCHRCH2).
- 一个代表性复合体的结构性表征,揭示了带有反形状的的四个成员环.
- 立体化学研究表明,在氧化添加过程中,甲基烯碳的反转率>95%.
- 氧化导致减少性消除,再生亚齐里丁与高立体化学反转 (约. 92%) 的情况.
结论:
- 复合物介导N-托西拉齐里丁的氧化添加,形成稳定的亚甲.
- 在C-N键裂解和形成过程中,随着可预测的立体化学逆转而进行.
- 这种方法通过介导的转换提供了一条通往功能化的亚齐里丁的途径.
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