Density functional theory calculations have been performed to probe the detailed mechanisms of Brønsted‐acid‐catalyzed ring‐opening reactions of donor‐acceptor cyclopropanes. The reaction model without consideration of the explicit solvation effect was characterized by a high activation free energy of 29.5 kcal/mol, while inclusion of the explicit solvation effect in calculations lowered the activation free energy to 20.5 kcal/mol, which demonstrated the cooperative role of HOTf and HFIP in facilitating the ring‐opening step. Additionally, we put forward two distinct reaction mechanisms, including the nucleophile‐induced mechanism and the protonation‐induced mechanism, for the ring‐opening step of donor‐acceptor cyclopropanes. Computational results revealed that modulation of the reaction conditions could result in the shift of the reaction mechanisms.

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HOTf / HFIP协同系统如何催化环丙烷的开环反应？DFT研究

已经进行了密度泛函理论计算，以探索供体受体环丙烷的布朗斯台德酸催化开环反应的详细机理。不考虑显式溶剂化作用的反应模型的特征在于29.5 kcal / mol的高活化自由能，而计算中包含显式溶剂化作用则将活化自由能降低至20.5 kcal / mol，这证​​明了其的协同作用。 HOTf和HFIP有助于开环步骤。此外，对于供体-受体环丙烷的开环步骤，我们提出了两种不同的反应机理，包括亲核试剂诱导的机理和质子诱导的机理。