通过氧cyclopentadienyl鲁丁化减少的imine的立体化学
Charles P Casey1, Galina A Bikzhanova, Ilia A Guzei
1Department of Chemistry, University of Wisconsin, Madison, WI 53706, USA. casey@chem.wisc.edu
Journal of the American Chemical Society
|February 16, 2006
概括
从鲁复合物转移到N-aryl imines的转移主要是跨立体特异性,形成氨基复合物. 然而,由于更快的可逆性,转移到N-基胺是立体随机的.
科学领域:
- 有机金属化学 有机金属化学
- 立体化学是一种立体化学.
- 反应机制 反应机制
背景情况:
- 复合物是有机合成中的多功能催化剂.
- 了解转移机制对于开发高效的催化过程至关重要.
- 转移的立体化学结果可以受到基质结构的影响.
研究的目的:
- 为了研究从特定的鲁复合物转移到不同的 imine基质的转移的立体化学.
- 阐明控制这些反应中的立体特异性的机械路径.
主要方法:
- 二化物复合物的合成 [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4) COD) ] Ru(CO) ((2) D.
- 鲁复合物的与N-和N-基胺的反应.
- 分析所产生的氨基复合物的立体化学结果.
主要成果:
- 将转移到N-aryl imines的过程具有很高的转变立体特异性.
- 一个拟议的机制涉及到一个协调不和的中间体和快速氨基协调的形成.
- 将转移到N-基因胺产生了立体随机产物,这表明可逆性比氨基协调更快.
结论:
- 催化转移的立体化学结果高度依赖于胺基基质.
- 氨基产物的快速协调是保持与N-aryl imines的立体特异性的关键.
- 转移的可逆性在确定N-胺基因的立体选择性方面发挥着至关重要的作用.
相关概念视频
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Imine formation involves the addition of carbonyl compounds to a primary amine. It begins with the generation of carbinolamine through a series of steps involving an initial nucleophilic attack and then several proton transfer reactions. The second part includes the elimination of water, as a leaving group, to give the imine.
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If the pH is low or the solution is too acidic, the reaction slows down in the...


