Pd(0)催化1-R-3-苯基亚丙基环丙烷(R=Me/H)与呋喃甲醛[3＋2]环加成反应机理的密度泛函理论研究

doi:10.6023/cjoc202203012

摘要/Abstract

结合相对论赝势, 用密度泛函理论方法M06优化了用模型Pd(PH₃)₂模拟的Pd(PPh₃)₄催化两个标题反应路径中各驻点的几何结构, 并计算相应的热力学函数, 结合能量跨度(Energetic span)分析, 以探讨其机理. 结果表明, 两个催化反应主要经历三个步骤: (1)亚烷基环丙烷与Pd(PH₃)₂催化剂的氧化加成, 形成钯环丁烷中间体; (2)钯环丁烷与呋喃甲醛的羰基经过分步加成, 形成六元氧杂金属环化合物; (3) Pd(PH₃)₂催化剂经过还原消去从六元氧杂金属环化合物解离, 得到最终的亚甲基四氢呋喃取代产物. 能量跨度分析表明, 两个反应中TOF(转换频率)决速过渡态(TDTS)都是还原消去步的过渡态, 但二者中TOF决速中间体(TDI)不同. 在呋喃甲醛溶剂中R=Me时自由能垒(能量跨度δ_E)比R=H时的低9.5 kJ/mol, 估算得到120 ℃下两个催化循环的TOF之比TOF_Me/TOF_H约为18, 表明在相同条件下, Pd(PH₃)₂对R=Me的反应的催化效率要远高于对R=H的反应, 可以很好地解释120 ℃、Pd(PPh₃)₄催化下, R=Me时比R=H时反应有高得多的产率的实验观察.

关键词: 亚烷基环丙烷, [3＋2]环加成, 反应机理, 密度泛函理论(DFT), 四氢呋喃, 转换频率(TOF), 决速态, 能量跨度

The optimal geometric structures and thermodynamic properties for all stationary points (reactants, intermediates, transition states, and products) on each pathway of the [3＋2] cycloaddition reactions between 1-R-3-phenylpropylidenecyclo- propane (R=Me/H) and furfural with model catalyst Pd(PH₃)₂ have been computed by using density functional theory (DFT) method with M06 functional combined with Stuttgart/Dresden relativistic effective core potential for exploring the mechanisms of the reactions catalyzed by Pd(PPh₃)₄. Based on the obtained free energy curves, energetic span analyses were carried out. The calculated results show that both reactions go through three steps: (1) Pd(PH₃)₂ catalyst oxidatively added to methylenecyclopropanes, in which Pd inserted into the distal carbon-carbon bond of methylenecyclopropanes ternary ring to form palladium cyclobutane intermediate; (2) six-membered oxa-metal ring compounds were formed by stepwise additions of palladium cyclobutane intermediate with the carbonyl of furan formaldehyde; (3) Pd(PH₃)₂catalyst dissociates from the six-membered oxy-hetero-metal ring compound through reductive elimination, and the five-membered-ring final products, methylene tetrahydrofurans were obtained. In addition, with the energetic span model proposed by Kozuch and Shaik, the calculated turnover frequency (TOF)-determining transition states (TDTS) for both catalytic cycles with R=Me/H are the same as the transition state (TS) of the reductive elimination step, however the TOF-determining intermediate (TDI) in each catalytic cycle is different from each other. As a result, the apparent free energy barrier (energetic span, δ_E) for the catalytic cycle with R=Me is 9.5 kJ/mol lower than that for the catalytic cycle with R=H, and the estimated TOF at 120 ℃ for the catalytic cycle with R=Me is ca 18 times larger than that for the catalytic cycle with R=H. These indicate that Pd(PPh₃)₄ is more effective for catalytic cycle with R=Me, which accounts well for the previous experimental observation that the yield for the reaction with R=Me is much higher than that for the reaction with R=H under the catalysis of Pd(PPh₃)₄ at 120 ℃.

Key words: methylenecyclopropanes, [3＋2] cycloaddition, reaction mechanism, density functional theory (DFT), tetrahydrofuran, turnover frequency (TOF), rate-determining state, energetic span

引用此文

刘悦灵, 钟欣欣, 张干兵. Pd(0)催化1-R-3-苯基亚丙基环丙烷(R=Me/H)与呋喃甲醛[3＋2]环加成反应机理的密度泛函理论研究[J]. 有机化学, 2023, 43(2): 660-667.

Yueling Liu, Xinxin Zhong, Ganbing Zhang. Density Functional Theory Study for Exploring the Mechanisms of the [3＋2] Cycloaddition Reactions between 1-R-3-Phenylpropylidenecyclopropane (R=Me/H) and Furfural Catalyzed by Pd(0)[J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 660-667.

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图/表 6

图式1. Pd(PH3)4催化1-R-3-苯基亚丙基环丙烷(R=Me/H)与呋喃甲醛[3＋2]环加成反应的催化循环

Scheme 1. Catalytic cycles of [3＋2] cycloaddition reaction between 1-R-3-phenylpropylidenecyclopropane(R=Me/H) and furfural catalyzed by Pd(PH3)4

图1. M06/6-311G**/SDD水平下反应a/b中反应物、产物和决速态的优化几何结构(键长单位: 0.1 nm)

Figure 1. Optimized geometric structures of reactant, product and TOF-determined states in reactions a/b at M06/6-311G**/SDD level (unit of bond length: 0.1 nm)

图2. 反应a在呋喃甲醛溶剂中的自由能(ΔG)曲线

Figure 2. Free energy (ΔG) profile of reaction a in furfural solvent

图3. 反应b在呋喃甲醛溶剂中的自由能(ΔG)曲线

Figure 3. Free energy (ΔG) profile of reaction b in furfural solvent

图4. COM1-A、COM1-B中主要相互作用的Donor和Acceptor NBO轨道对及对应的二级微扰能E(2) (kJ/mol)

Figure 4. Main Donor-Acceptor NBO pairs and second order perturbation energy E(2) (kJ/mol) in COM1-A and COM1-B

图5. COM2-A、COM2-B中主要相互作用的Donor和Acceptor NBO对及二级微扰能E(2) (kJ/mol)

Figure 5. Main Donor-Acceptor NBO pairs and second order perturbation energy E(2) (kJ/mol) in COM2-A and COM2-B

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