过渡金属铑催化的环丙烷化以及脱羰偶联反应的机理研究

发布时间：2018-03-12 06:58

本文选题：过渡金属　切入点：密度泛函理论　出处：《暨南大学》2017年硕士论文　论文类型：学位论文

【摘要】：近年来,过渡金属铑催化C-H活化合成三元环化合物或者C-C活化扩展五元环化合物的研究已得到广泛发展,但反应过程中很多细节问题还不清楚。所以阐明反应机理,了解促进反应发生的原因及其反应的区域选择性和非对映选择性等等,将有助于我们更深入地理解复杂的实验结果。本文主要使用密度泛函理论(DFT)/M06计算方法对过渡金属Rh催化的C-H/C-C官能化反应进行了详细的机理研究。第三章主要进行了Rh(Ⅲ)催化N-烯氧基邻苯二甲酰亚胺和烯烃的环丙烷化反应的机理研究。主要研究了三条涉及Rh(Ⅰ)、Rh(Ⅲ)和Rh(V)中间体的反应机理及其非对映选择性。发现新颖的四元环Rh(V)中间体机理是最优的,通过扭曲/相互作用模型分析发现扭曲能在确定非对映选择性中起关键作用。第四章主要进行了Rh(Ⅰ)催化炔烃-靛红脱羰偶联反应的机理研究。计算结果证实了底物靛红进行C-C键活化而非C-H键活化。在导向基团的协助下底物靛红进行C3-C9键断裂,而不是更小键能的C2-C3键断裂。此外,导向基团上取代基的空间效应影响C-C活化产率,特别是靛红苯环上的取代基能控制C-C/C-H活化之间的转换。通过扭曲/相互作用模型和前线分子轨道分析发现相互作用能在区域选择性中起关键作用。
[Abstract]:In recent years, the transition metal rhodium catalyzed C-H activation synthesis of three membered rings or C-C extension of five membered ring compounds activation has been widely used, but a lot of details in the reaction process is not clear. So to clarify the reaction mechanism, to promote regional selective reasons and reaction occurred and diastereoselectivity and so on, will help us more in-depth understanding of the experimental results is complicated. This paper mainly using the density functional theory (DFT) calculation method of /M06 C-H/C-C functionalization reactions of transition metal catalyzed by Rh was studied in detail. The third chapter is the main mechanism of Rh (III) mechanism of cyclopropanation reaction catalyzed by N- ene oxy phthalate two phthalimide and olefins. Mainly on the three involved Rh (I), Rh (III) and Rh (V) intermediates in the reaction mechanism and diastereoselectivity. Found four membered ring Rh novel intermediates (V) machine Is the best, the distortion / interaction model analysis showed that the distortion can play a key role in determining the enantioselectivity. The fourth chapter is the Rh (I) on the catalytic mechanism of alkyne - isatin decarbonylation reaction. The results show that the substrate of isatin C-C activation but not C-H activation. With the help of group oriented C3-C9 substrate isatin bond cleavage, cleavage of C2-C3 bonds rather than a small can. In addition, effects of C-C spatial effect oriented groups of substituents on the activation yield, especially the substituent can control the activation of C-C/C-H conversion between the isatin benzene ring. By twisting / interaction model and frontier molecular orbital the analysis found that the interaction can play a key role in the regional selectivity.

【学位授予单位】：暨南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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