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)

doi:10.6023/cjoc202203012

Abstract

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

Cite this article

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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Fig. & Tab. 6

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

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)

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

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

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

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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