Theoretical Investigation On The Reaction Mechanism Of Domino Reaction Catalyzed By Cu(Ⅰ)

Abstract:The concept of sustainable development guides the activity of science and technology, which becomes research focus. In the area of organic synthesis, the concept of sustainable development can be expressed as:the more moderate reaction condition, higher yield, higher selectivity to the target compound, and reduces the energy consumption and formation of by-products. Therefore sustainable development is the development of inexpensive, efficient and environmentally metal catalyst in metal organic chemistry and researching and developing continuous reaction process.In this paper, The reaction mechanism of the Cu(Ⅰ)-catalytic reaction" one-pot" synthesis of6H-azepin compounds and Domino reaction synthesis indole have been investigated by density functional theory (DFT) at the B3LYP/6-31+G(d) computational level. The geometric configurations of reactants, intermediates, transition states and products have been optimized and their vibration frequency have been also calculated, which proved the authenticities of the intermediates and the transition states. The analysis of the calculated results would make a better understanding of these reactions.The reaction mechanism of Cu(Ⅰ)-catalytic "one-pot " synthesis of6H-azepin compounds and the reaction rate controlling step have been studied in the first part of this article. The reaction activation energy is247.33kJ/mol without Cu(Ⅰ)-catalytic, and the reaction activation energy is151.38kJ/mol with Cu(Ⅰ)-catalytic, which reduced95.95kJ/mol compared to without Cu(Ⅰ)-catalytic. The research proves the Cu (Ⅰ)-catalyst beneficial to promoting the rate of the reaction, which is consistent with experimental findings that the actual reaction without catalyst cannot be carried out. We find ten intermediates and six transition states in the study of reaction mechanism.The situation of indole compounds and some the classic name reaction mechanism about indole have been introduced in the second part of this article, which focused on the transition metal catalyzed reaction mechanism. Based on previous works, we have studied the synthesis of indole reaction mechanism with single Cu(I)-catalyst by density functional theory (DFT). The C-C coupling was reacted in acetylenic copper between halogen of N-(2-bromophenyl)-2,2,2-trifluoroacetamide, which obtained catalytic stable intermediate. Then the addition reaction is carried out via electron transfer by metallic hydrogen absorption. We find six intermediates and three transition states in the study of reaction mechanism. The reaction mechanism have been described detailedly, which explained the role of the catalyst Cu(I).