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用密度泛函方法(DFT)研究了PdCl2催化炔酸烯丙酯环化反应的机理.在B3LYP/6-311G**水平上优化了各反应中间体和过渡态的结构.计算结果表明,反应是放热的,主要经历了炔键的卤钯化、烯烃对烯基钯的迁移插入以及β-杂原子消除等过程.烯烃的迁移插入是反应的手性决定步骤,β-杂原子消除是反应的速率控制步骤.理论预测的主要产物是与实验吻合的(Z,R)-α-亚烷基-γ-丁内酯.
The mechanism of the cyclization of allyl acetyleneate catalyzed by PdCl2 was studied by density functional theory (DFT). The structure of intermediate and transition state of each reaction was optimized at B3LYP / 6-311G ** level. The calculated results showed that the reaction Is exothermic and mainly undergoes the palladium-catalyzed alkyne bond, the transport and insertion of alkene to alkenyl palladium, and the elimination of β-heteroatoms etc. The migration of olefins is a chiral determinant of the reaction, β-heteroatom elimination is The rate-controlling step of the reaction The main product predicted theoretically was (Z, R) -alpha-γ-butyrolactone consistent with the experiment.