过渡金属钯、镍和锌双催化的两种羰基化合物反应机理的密度泛函研究
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摘要
本工作应用量子化学密度泛函B3LYP方法,分别对钯催化炔丙基醋酸盐分子内重排反应,镍和锌双过渡金属催化丁间醇醛环化反应的机理进行了研究,找到了各反应中主要的过渡态,详细的讨论了这些反应的机理。
1.钯催化炔丙基醋酸盐分子内重排的理论研究
用密度泛函(DFT)方法对钯催化炔丙基醋酸盐分子内重排进行了理论研究。结果表明,在反应中钯遵循18电子规则。优势反应通道经历如下几个步骤:催化剂与炔基键配位提高其活性,羰基氧与炔基之间的S_N2反应,醋酸根的重排形成五元环阳离子,通过利用环内4π电子的环化作用的反应路径达到目标产物。催化剂催化作用的本质在于钯与端炔基配位,降低反键轨道π_((C1-C2))~*与羰基氧2p-LP轨道的能级差。
2.镍、锌双过渡金属催化环化丁间醇醛反应的机理研究
用密度泛函(DFT)的方法研究了双过渡金属镍、锌催化丁间醇醛发生分子内的环化反应机理。结果表明,该反应是放热的,主要经过了催化剂的配位,质子氢的转移,分子内的成环的几个步骤。分子内成环是整个反应的速率控制步骤。通过计算还发现,在催化过程中,双金属中的镍可以作为活性催化剂催化整个反应,而且以镍为活性催化剂催化时,和以锌作为活性催化剂相比能降低速控步骤的能垒,使反应更容易发生。理论预测的产物是和实验相一致的。
In present paper,the density functional method(B3LYP) is employed to study the reaction mechanism of Palladium(Ⅱ)-catalyzed rearrangements of propargyl acetates,and Ni and Zn-catalyzed intermolecular cyclization of aldol.The main transition states of these reactions are found out.The mechanisms of these asymmetric cyclized reactions are discussed in detail.
1.Theoretical study on Palladium(Ⅱ)-catalyzed intermolecular rearrangements of propargyl acetates
The mechanisms of Palladium(Ⅱ)-catalyzed rearrangements of propargyl acetates are investigated using density functional theory with B3LYP methods.It reveal that the coordination of the triple bond of 1 to PdCl_2(MeCN)_2 enhances the electrophilicity of alkyne,and the sunsequent nucleophilic attack of the carbonyl oxygen to the electron-deficient alkyne form ate complex IM2,whick would occurs rearrangements of acetic acid radical,the object production is produced by the reaction path of 4π-electrocyclization.It is suggested that the terminal alkynal is activated by the decrease in theπ~*_((C1-C2)) orbital energy.Throughout the reaction,all Pd~(11) complexes obey the 18-electron-rule.
2.DFT study on the mechanism of Ni and Zn-Catalyzed Aldol cyclization reation
The reaction mechanism of the Ni and Zn-catalyzed intermolecular cyclization of aldol,was studied using density functional theory(DFT) calculations at the B3LYP level.The calculations indicate that the intermolecular cyclization is the rate-determining step,and that the coordination of catalyzer and the transfer of proton are favorable.Ni as the active catalyst can decrease the energy barrier than Zn.All of the theoretical results are consistent with the experiment.
1.钯催化炔丙基醋酸盐分子内重排的理论研究
用密度泛函(DFT)方法对钯催化炔丙基醋酸盐分子内重排进行了理论研究。结果表明,在反应中钯遵循18电子规则。优势反应通道经历如下几个步骤:催化剂与炔基键配位提高其活性,羰基氧与炔基之间的S_N2反应,醋酸根的重排形成五元环阳离子,通过利用环内4π电子的环化作用的反应路径达到目标产物。催化剂催化作用的本质在于钯与端炔基配位,降低反键轨道π_((C1-C2))~*与羰基氧2p-LP轨道的能级差。
2.镍、锌双过渡金属催化环化丁间醇醛反应的机理研究
用密度泛函(DFT)的方法研究了双过渡金属镍、锌催化丁间醇醛发生分子内的环化反应机理。结果表明,该反应是放热的,主要经过了催化剂的配位,质子氢的转移,分子内的成环的几个步骤。分子内成环是整个反应的速率控制步骤。通过计算还发现,在催化过程中,双金属中的镍可以作为活性催化剂催化整个反应,而且以镍为活性催化剂催化时,和以锌作为活性催化剂相比能降低速控步骤的能垒,使反应更容易发生。理论预测的产物是和实验相一致的。
In present paper,the density functional method(B3LYP) is employed to study the reaction mechanism of Palladium(Ⅱ)-catalyzed rearrangements of propargyl acetates,and Ni and Zn-catalyzed intermolecular cyclization of aldol.The main transition states of these reactions are found out.The mechanisms of these asymmetric cyclized reactions are discussed in detail.
1.Theoretical study on Palladium(Ⅱ)-catalyzed intermolecular rearrangements of propargyl acetates
The mechanisms of Palladium(Ⅱ)-catalyzed rearrangements of propargyl acetates are investigated using density functional theory with B3LYP methods.It reveal that the coordination of the triple bond of 1 to PdCl_2(MeCN)_2 enhances the electrophilicity of alkyne,and the sunsequent nucleophilic attack of the carbonyl oxygen to the electron-deficient alkyne form ate complex IM2,whick would occurs rearrangements of acetic acid radical,the object production is produced by the reaction path of 4π-electrocyclization.It is suggested that the terminal alkynal is activated by the decrease in theπ~*_((C1-C2)) orbital energy.Throughout the reaction,all Pd~(11) complexes obey the 18-electron-rule.
2.DFT study on the mechanism of Ni and Zn-Catalyzed Aldol cyclization reation
The reaction mechanism of the Ni and Zn-catalyzed intermolecular cyclization of aldol,was studied using density functional theory(DFT) calculations at the B3LYP level.The calculations indicate that the intermolecular cyclization is the rate-determining step,and that the coordination of catalyzer and the transfer of proton are favorable.Ni as the active catalyst can decrease the energy barrier than Zn.All of the theoretical results are consistent with the experiment.
引文
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