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Pd催化的配体导向C—H键官能化反应已经成为有机化学中一种重要的合成手段.我们用B3PW91密度泛函方法研究了Pd催化的配体导向C—H键乙酰化反应中催化剂和底物配合步骤以及C—H键活化步骤中的热力学性质.研究发现,具有不同导向基团的反应物之间竞争反应的选择性取决于导向基团与Pd(OAc)2的配合步骤,配合反应稳定常数大的较容易生成乙酰化的产物.另一方面,反应的选择性与C—H键的活化步骤无关,并且与导向基团的配位原子的气相碱性、原子上的电荷密度以及最高占据轨道能量都没有相关性.
Pd-catalyzed ligand-directed C-H bond functionalization has become an important synthesis method in organic chemistry.We used B3PW91 density functional theory to study the effects of Pd-catalyzed ligand-directed C-H bond acetylation Substrate coordination step and C-H bond activation step.The selectivity of competitive reactions between reactants with different guiding groups was found to be dependent on the coordination of the targeting group with Pd (OAc) 2, Reaction stability constant large easier to generate acetylated products.On the other hand, the selectivity of the reaction and the C-H bond activation step has nothing to do with the gas and basicity of the coordinating atoms of the guide group, the atomic charge density As well as the highest occupied orbital energy.