CuCl催化苯腙和丙炔酸甲酯Michael加成反应的机理研究
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摘要
本文采用密度泛函理论(DFT)中的M05方法针对性的研究了以CuCl为催化剂催化苯腙和丙炔酸甲酯发生Michael加成的微观反应机理.采用Gaussian09程序,使用6-31+G*(Cu采用赝势基组LanL2DZ)对化学反应过程中的反应物、中间体、过渡态分子的几何构型进行了优化,同时进行了频率计算,所有过渡态都有唯一虚频,中间体和过渡态分子结构的合理性得到了确认.通过自然键轨道(NBO)理论分析了分子轨道间的相互作用.通过理论计算发现CuCl催化苯腙和丙炔酸甲酯发生Michael加成反应的位点在苯腙的N原子上,反应的速控步骤活化能为34.86 kcal/mol,相关的理论研究结果与实验反应现象相吻合.
Using the density functional theory(DFT) M05 method, we studied the reaction mechanism of the Michael addition reaction of phenylhydrazone and methyl propiolate catalyzed by CuCl. Under the basis set level of 6-31+G*(Cu using the pseudo potential basis set of LanL2DZ), we optimized the configuration of all the reactants, transition states and intermediates of Michael addition reaction with phenylhydrazone and methyl propiolate catalyzed. Meanwhile, we calculated the frequency and found out that all the transient states have the only imaginary frequency; moreover, we confirmed the rationality of intermediates and transient states. We analyzed the interaction among molecular orbits via natural bond orbital(NBO). Theoretical calculations showed that the reaction site of the Michael addition reaction of phenylhydrazone and methyl propiolate catalyzed by CuCl is the N atom of phenylhydrazone. And the results showed that the reaction rate-determining energy is 34.86 kcal/mol. The final result of our theory study agrees with the experimental data.
Using the density functional theory(DFT) M05 method, we studied the reaction mechanism of the Michael addition reaction of phenylhydrazone and methyl propiolate catalyzed by CuCl. Under the basis set level of 6-31+G*(Cu using the pseudo potential basis set of LanL2DZ), we optimized the configuration of all the reactants, transition states and intermediates of Michael addition reaction with phenylhydrazone and methyl propiolate catalyzed. Meanwhile, we calculated the frequency and found out that all the transient states have the only imaginary frequency; moreover, we confirmed the rationality of intermediates and transient states. We analyzed the interaction among molecular orbits via natural bond orbital(NBO). Theoretical calculations showed that the reaction site of the Michael addition reaction of phenylhydrazone and methyl propiolate catalyzed by CuCl is the N atom of phenylhydrazone. And the results showed that the reaction rate-determining energy is 34.86 kcal/mol. The final result of our theory study agrees with the experimental data.
引文
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[2] Ying A G, Wu C L, Fu Y Q, et al. Progress in the application of organocatalysis to asymmetric Michael additions [J]. Chin. J. Org. Chem., 2012, 32: 1587 (in Chinese) [应安国, 武承林, 付永前, 等. 有机小分子不对称催化 Michael 加成的研究进展[J]. 有机化学, 2012, 32: 1587]
[3] Guo H, Li X, Wang J L,et al. Acidic ionic liquid [NMP] H2PO4 as dual solvent-catalyst for synthesis of β-alkoxyketones by the oxa-Michael addition reactions [J]. Tetrahedron, 2010, 66: 8300.
[4] Krishna P R, Sreeshailam A, Srinivas R.. Recent advances and applications in asymmetric aza-Michael addition chemistry [J]. Tetrahedron, 2009, 65: 9657.
[5] Zhai Z W, Wang Q, Shen Z H, et al. Synthesis and biological activity of 1,2,4-triazole thioether derivatives containing pyrazole moiety [J]. Chin. J. Org. Chem., 2017, 37: 232 (in Chinese) [翟志文, 汪乔, 沈钟华, 等. 新型含吡唑的三唑硫醚类化合物的合成与生物活性研究[J]. 有机化学, 2017, 37: 232]
[6] Tan C X, Shen D L, Weng J Q, et al. Synthesis, structure and biological activities of substituted pyrazol-5-yl-carbonyl-heterocycles [J]. Chin. J. Org. Chem., 2005, 25: 1268 (in Chinese) [谭成侠, 沈德隆, 翁建全, 等. 取代吡唑-5-酰基杂环衍生物的合成、结构与生物活性[J]. 有机化学, 2005, 25: 1268]
[7] Xia Q C, He Q Z, Xu D F, et al. Synthesis, characterization and antibacterial of five-membered heterocycles [J]. Acta Chim. Sin. , 2010, 68: 2414 (in Chinese) [夏庆春, 何其庄, 许东芳, 等. 吡唑三杂环化合物的制备表征及生物活性的研究 [J]. 化学学报, 2010, 68: 2414]
[8] Miller Z, Kim K S, Lee D M,et al. Proteasome inhibitors with pyrazole scaffolds from structure-based virtual screening. [J]. J. Med. Chem., 2015, 58: 2036.
[9] Fricero P, Bialy L, Brown A W, et al. Synthesis and modular reactivity of pyrazole 5trifluoroborates: intermediates for the preparation of fully functionalized pyrazoles. [J]. J. Org. Chem., 2017, 82: 1688.
[10] Li Y F, Huang J W, Gu J C, et al. Sequential three-component reactions for the assembly of functionalized pyrazoles [J]. Chin. J. Org. Chem., 2016, 36: 520 (in Chinese) [李玉峰, 黄佳维, 顾嘉超, 等. 串联式三组分反应构建取代吡唑杂环 [J]. 有机化学, 2016, 36: 520]
[11] Wang X L, Xu M Y, Hu Q Q, et al. Theoretical investigation on the cross-coupling reaction mechanism of rhodium aromatic compounds with nitrogen-containing aryl halides [J]. J. At. Mol. Phys., 2015, 32: 903 (in Chinese) [Rh的芳基化合物与含氮芳基卤代物交叉偶联反应机理研究 [J]. 原子与分子物理学报, 2015, 32: 903]
[12] Li L C, Peng D, Zhou H P.et al. Investigation on the mechanisms for the selective hydrogenation reaction of cinnamaldehyde catalyzed by Pt10 clusters [J]. J. At. Mol. Phys., 2016, 33: 79 (in Chinese) [李来才, 彭丹, 周红平, 等. Pt10团簇催化肉桂醛选择性加氢反应机理的研究 [J]. 原子与分子物理学报, 2016, 33: 79]
[13] Becke A D. Density-functional thermochemistry. III. The role of exact exchange [J]. J. Chem. Phys., 1993, 98: 5648.
[14] Lee C, Yang W, Parr R G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density [J]. Phys. Rev. B, 1988, 37: 785.
[15] Zhao Y, Schultz N E, Truhlar D G. Exchange-correlation functional with broad accuracy for metallic and nonmetallic compounds, kinetics, and noncovalent interactions[J]. J. Chem. Phys., 2005, 123.
[16] Gonzalez C, Schlegel H B. An improved algorithm for reaction path following [J]. J. Chem. Phys., 1989, 90: 2154.
[17] Gonzalez C, Schlegel H B. Reaction path following in mass-weighted internal coordinates [J]. J. Phys. Chem. C, 1990, 94: 5523.
[18] Reed A E,Weinhold F,Curtiss L A,et al. Intermolecular interactions from a natural bond orbital, donor- acceptor viewpoint [J] . J. Phys. Chem., 1986,84: 5687.
[19] Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 09, Rev. A 02. Wallingford CT: Gaussian, Inc., 2009.