金(I)催化丙二烯基化合物构建螺环[4,5]癸烷骨架的计算研究

采用B3LYP-D3(BJ)计算方法研究了金催化丙二烯基化合物合成螺环4,5]癸烷骨架的反应机理。通过SMD模型在实验对应的CH3CN溶剂体系中进行单点能量计算得出更准确的能量。计算研究表明，该反应包括三个主要的步骤：烯丙基和乙烯基端基碳原子的分子内环加成、四元环重构为五元环的半频哪醇重排过程、消除反应释放催化剂并得到产物。结果显示第一步是反应的决速步骤，其活化自由能相对较低为70.18 kJ/mol，表明金催化的合成反应在室温条件下能够发生。

A computational study on the synthesis of spiro[4,5]decaneframework from allenylcompounds catalyzed by gold(I) complexes

The B3LYP-D3(BJ) calculation method was used to study the reaction mechanism of gold-catalyzed synthesis of spiro4,5]decane from allenyl compounds. Through the SMD model, a more accurate energy can be obtained by single-point energy calculation in the corresponding CH3CN solvent system of the experiment. Calculation studies have shown that the reaction includes three main steps: the intramolecularcycloaddition of allyl and vinyl end group carbon atoms, the semipinacolrearrangement process in which the four-membered ring is reconstructed into a five-membered ring,elimination of formation product and release the catalyst.The results show that the first step is the rate-determining step of the reaction, and its activation free energy is relatively low (70.18 kJ/mol),indicating that the gold-catalyzed synthesis reaction can occur at room temperature.