Theoretical Study of the Mechanism of an Inverse-Demand Diels–Alder Reaction
DOI: 10.1007/S13369-011-0167-0
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摘要: Quantum mechanical calculations (AM1, PM3, ab initio HF/3-21G, DFT(B3LYP/6-31G*) and MP2//(B3LYP/6-31G*) have been used to study the inverse-demand synchronous concerted Diels–Alder reactions between dimethyl-1,2,4,5-tetrazine-3,6-dicarboxylate (diene) a variety of dienophiles (ethylene, cyclopentadiene, 1-hexene, cyclohexene). All molecular structures (reactants, transition states, intermediates adducts) were optimized using semi-empirical AM1 method. The calculated energies volumes showed that cycloaddition reaction followed mechanism involving formation an intermediate, elimination N2, 1,3-hydrogen shift adduct. systems obtained by good agreement with experimental data. In contrast, DFT (B3LYP/6-31G*) MP2//(B3LYP/6-31G* in poor Compared data, activation overestimated AM1, PM3 while they underestimated MP2//(B3LYP/6-31G*).
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