金鸡纳碱类催化剂催化的几种不对称加成反应的理论研究
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摘要
近年来，随着具有高效和高选择性的有机催化剂的不断研发，其中金鸡纳碱类催化剂催化不对称加成反应在有机催化化学中发挥着至关重要的作用。在本文中，我们采用了密度泛函理论（DFT）计算和从头算（ab initio）方法详细的研究了金鸡纳碱催化的这几个不对称加成反应。我们详细的讨论了这几个催化剂的活化机制，有助于了解催化反应的反应机理。预测了可能的产物及其立体选择性，依据相应的连接关系，给出了可能的反应通道。同时现有的实验结果为进一步的实验研究提供了理论依据。我们的主要研究内容如下：
1.金鸡纳碱衍生伯胺催化β-硝基苯乙烯与异丁醛的不对称Michael加成反应
目前，金鸡纳碱衍生伯胺作为催化剂，苯甲酸作为辅助催化剂，硝基苯乙烯和异丁醛的Michael加成已经被广泛研究，然而我们对这个机理的理解还远远不够。金鸡纳碱衍生伯胺催化β-硝基苯乙烯与异丁醛的不对称Michael加成机理的理论研究中，我们采用了密度泛函理论及从头算方法并得出了一个详细的机理。计算表明这个过程包括了四部分（1）亚胺离子中间体的形成；（2）亚胺离子与β-硝基苯乙烯的加成；（3）质子迁移；和（4）水解及催化剂的还原。这个反应的速率决速步骤和产物的立体选择性都被控制在第二个质子转移阶段。计算结果提供了大致的理论模型来解释了标题反应机理以及产物的立体选择性。
2.金鸡纳碱催化二甲基丙二酸酯与β-硝基苯乙烯的不对称加成反应
我们采用密度泛函理论及从头算方法来研究金鸡纳碱QD-4作为有机催化剂催化二甲基丙二酸酯与β-硝基苯乙烯的不对称加成反应机理。这个反应有六个不同的反应路径分别对应于反应物β-硝基苯乙烯对二甲基丙二酸酯不同的进攻模式。计算表明反应过程是一个双官能团的催化机理，其中催化剂上的叔胺氮作为布朗斯特碱激活了反应物二甲基丙二酸酯，同时催化剂中的羟基基团作为布朗斯特酸激活了反应物β-硝基苯乙烯。这个反应的决速步骤是从催化剂的叔胺氮到β-硝基苯乙烯的α碳的质子迁移过程。对比这六条反应路径的能量和机理使我们了解到在这个体系中催化剂QD-4表现出了很好的催化活性，计算结果也说明了QD-4上的C9-OH基团在这个体系中不涉及任何激活作用，而且所得到的产物的立体选择性也符合实验上观察到的结果。
3.9-氨基奎宁催化剂催化1-溴代硝基甲烷与亚苄基丙酮的共轭加成反应
由金鸡纳碱类催化剂9-氨基奎宁作为有机催化剂和苯甲酸作为辅助催化剂催化1-溴代硝基甲烷与亚苄基丙酮的不对称共轭加成反应已经被广泛研究。然而，具体的反应机理我们还不够了解。通过密度泛函理论B3LYP和M062X和从头算MP2方法计算，我们给出了详细的标题反应机理。这个反应过程包括三个主要阶段：（I）亚胺离子中间体的形成；（II）亚胺离子与1-溴代硝基甲烷的亲核加成；以及（III）水解并伴随催化剂的还原。计算结果不仅解释了苯甲酸加合物在亚胺离子形成过程中所起的重要作用，而且提供了一般反应模型去帮助理解这个共轭加成反应的反应机理和对映选择性。我们认为反应结果会对类似的共轭加成反应的机理研究有所帮助。
Recently, the organocatalysts have been developed with high efficiency and highselectivity. Among them, the asymmetry reactions catalyzed by the cinchona alkaloidcatalyst play an important role in organocatalysis chemistry. In this paper, the reactionmechanisms of several asymmetry addition reactions catalyzed by cinchona alkaloidcatalyst have been investigated using density functional theory and ab initiocalculations. The investigation on the activation of different organocatalysts couldfacilitate understanding of catalytic reaction mechanism, some important informationsuch as geometries and energies of the reactant, intermediates, transition states andproducts are obtained. On the basis of the relation of the reactant, intermediates,transition states and products, the possible reaction channels as well as theenantioselectivity also were provided. All the results obtained in this paper can shedsome light on the future experimental investigations of these kinds of reactions. Themain results are summarized as follows:
1. Asymmetric Michael addition of trans-1-nitro-2-phenylethylene to2-methylpropionaldehyde catalyzed by a Cinchona Alkaloid Derived Primary Amine.At present，using cinchona alkaloid-derived primary amine as catalyst and benzoicacid as co-catalyst, Michael-type addition reactions between enolizable carbonylcompounds and nitroalkenes have been extensively studied, however, ourunderstanding of the mechanism is far from complete. A theoretical study is presentedfor the Michael addition reaction between trans-1-nitro-2-phenylethylene and2-methylpropionaldehyde catalyzed by9-epi-QDA and benzoic acid. By performingDFT and ab initio calculations, we have identified a detailed mechanism. Thecalculations indicated that four continuous steps are involved in the overall reaction:1)the formation of an iminium intermediate,2) an addition reaction between theiminium and trans-1-nitro-2-phenylethylene,3) the proton transfer process, and4)hydrolysis and regeneration of the catalyst. The rate determining step is the proton transfer from the amine group to β-carbon of trans-1-nitro-2-phenylethylene, and theenantioselectivity is also controlled by this step. The calculated results provide ageneral model that explains the mechanism and enantioselectivity of the title reaction.
2. Theoretical Study on Mechanism of Cinchona alkaloids catalyzed asymmetricconjugate addition of dimethyl malonate to β-nitrostyrene. The mechanism andenantioselectivity of the asymmetric conjugate addition of dimethyl malonate toβ-nitrostyrene catalyzed by cinchona alkaloid QD-4as organic catalyst areinvestigated using DFT and ab initio methods. Six different reaction pathways,corresponding to the different approach modes of β-nitrostyrene to dimethyl malonateare considered. Calculations indicate that the reaction process through a dualactivation mechanism, in which the tertiary amine of cinchona alkaloid QD-4firstworks as a Br nsted base to promote the activation of the dimethyl malonate bydeprotonation, and then the hydroxyl group of QD-4acts as Br nsted acid to activatethe β-nitrostyrene. The rate determining step is the proton transfer process from thetertiary amine of QD-4to α-carbon of β-nitrostyrene. The comparison of themechanisms and energies of the six reaction channels enable us to learn the fact thatQD-4has good catalytic activities for the system, and implies C9-OH in QD-4maynot be involved in the activation. These calculation results accounts well for theobservations in experiments.
3. The conjugate addition of1-bromonitromethane to benzylidene acetonecatalyzed by9-amino-9-deoxyepiquinine. Asymmetric conjugate addition of1-bromonitromethane to benzylidene acetone catalyzed by9-amino-9-deoxyepiquinine as organic catalyst and benzoic acid as co-catalyst has beenextensively studied. However, in-depth understanding of the detailed mechanism is farfrom complete. By performing density functional theory (B3LYP and M062X) and abinitio calculations (MP2), we have identified a detailed mechanism of the title reaction.The reaction process includes three major stages:(I) the formation of an iminium ionintermediate;(II) the nucleophilic addition between the iminium and1-bromonitromethane; and (III) hydrolysis and recovery of catalyst. The calculatedresults not only explain benzoic acid as acidic additive plays an important role in the formation of the key reaction iminium intermediate, but also provide a general modelto help explain the mechanism and enantioselectivity of the conjugate additionreaction.
1.金鸡纳碱衍生伯胺催化β-硝基苯乙烯与异丁醛的不对称Michael加成反应
目前，金鸡纳碱衍生伯胺作为催化剂，苯甲酸作为辅助催化剂，硝基苯乙烯和异丁醛的Michael加成已经被广泛研究，然而我们对这个机理的理解还远远不够。金鸡纳碱衍生伯胺催化β-硝基苯乙烯与异丁醛的不对称Michael加成机理的理论研究中，我们采用了密度泛函理论及从头算方法并得出了一个详细的机理。计算表明这个过程包括了四部分（1）亚胺离子中间体的形成；（2）亚胺离子与β-硝基苯乙烯的加成；（3）质子迁移；和（4）水解及催化剂的还原。这个反应的速率决速步骤和产物的立体选择性都被控制在第二个质子转移阶段。计算结果提供了大致的理论模型来解释了标题反应机理以及产物的立体选择性。
2.金鸡纳碱催化二甲基丙二酸酯与β-硝基苯乙烯的不对称加成反应
我们采用密度泛函理论及从头算方法来研究金鸡纳碱QD-4作为有机催化剂催化二甲基丙二酸酯与β-硝基苯乙烯的不对称加成反应机理。这个反应有六个不同的反应路径分别对应于反应物β-硝基苯乙烯对二甲基丙二酸酯不同的进攻模式。计算表明反应过程是一个双官能团的催化机理，其中催化剂上的叔胺氮作为布朗斯特碱激活了反应物二甲基丙二酸酯，同时催化剂中的羟基基团作为布朗斯特酸激活了反应物β-硝基苯乙烯。这个反应的决速步骤是从催化剂的叔胺氮到β-硝基苯乙烯的α碳的质子迁移过程。对比这六条反应路径的能量和机理使我们了解到在这个体系中催化剂QD-4表现出了很好的催化活性，计算结果也说明了QD-4上的C9-OH基团在这个体系中不涉及任何激活作用，而且所得到的产物的立体选择性也符合实验上观察到的结果。
3.9-氨基奎宁催化剂催化1-溴代硝基甲烷与亚苄基丙酮的共轭加成反应
由金鸡纳碱类催化剂9-氨基奎宁作为有机催化剂和苯甲酸作为辅助催化剂催化1-溴代硝基甲烷与亚苄基丙酮的不对称共轭加成反应已经被广泛研究。然而，具体的反应机理我们还不够了解。通过密度泛函理论B3LYP和M062X和从头算MP2方法计算，我们给出了详细的标题反应机理。这个反应过程包括三个主要阶段：（I）亚胺离子中间体的形成；（II）亚胺离子与1-溴代硝基甲烷的亲核加成；以及（III）水解并伴随催化剂的还原。计算结果不仅解释了苯甲酸加合物在亚胺离子形成过程中所起的重要作用，而且提供了一般反应模型去帮助理解这个共轭加成反应的反应机理和对映选择性。我们认为反应结果会对类似的共轭加成反应的机理研究有所帮助。
Recently, the organocatalysts have been developed with high efficiency and highselectivity. Among them, the asymmetry reactions catalyzed by the cinchona alkaloidcatalyst play an important role in organocatalysis chemistry. In this paper, the reactionmechanisms of several asymmetry addition reactions catalyzed by cinchona alkaloidcatalyst have been investigated using density functional theory and ab initiocalculations. The investigation on the activation of different organocatalysts couldfacilitate understanding of catalytic reaction mechanism, some important informationsuch as geometries and energies of the reactant, intermediates, transition states andproducts are obtained. On the basis of the relation of the reactant, intermediates,transition states and products, the possible reaction channels as well as theenantioselectivity also were provided. All the results obtained in this paper can shedsome light on the future experimental investigations of these kinds of reactions. Themain results are summarized as follows:
1. Asymmetric Michael addition of trans-1-nitro-2-phenylethylene to2-methylpropionaldehyde catalyzed by a Cinchona Alkaloid Derived Primary Amine.At present，using cinchona alkaloid-derived primary amine as catalyst and benzoicacid as co-catalyst, Michael-type addition reactions between enolizable carbonylcompounds and nitroalkenes have been extensively studied, however, ourunderstanding of the mechanism is far from complete. A theoretical study is presentedfor the Michael addition reaction between trans-1-nitro-2-phenylethylene and2-methylpropionaldehyde catalyzed by9-epi-QDA and benzoic acid. By performingDFT and ab initio calculations, we have identified a detailed mechanism. Thecalculations indicated that four continuous steps are involved in the overall reaction:1)the formation of an iminium intermediate,2) an addition reaction between theiminium and trans-1-nitro-2-phenylethylene,3) the proton transfer process, and4)hydrolysis and regeneration of the catalyst. The rate determining step is the proton transfer from the amine group to β-carbon of trans-1-nitro-2-phenylethylene, and theenantioselectivity is also controlled by this step. The calculated results provide ageneral model that explains the mechanism and enantioselectivity of the title reaction.
2. Theoretical Study on Mechanism of Cinchona alkaloids catalyzed asymmetricconjugate addition of dimethyl malonate to β-nitrostyrene. The mechanism andenantioselectivity of the asymmetric conjugate addition of dimethyl malonate toβ-nitrostyrene catalyzed by cinchona alkaloid QD-4as organic catalyst areinvestigated using DFT and ab initio methods. Six different reaction pathways,corresponding to the different approach modes of β-nitrostyrene to dimethyl malonateare considered. Calculations indicate that the reaction process through a dualactivation mechanism, in which the tertiary amine of cinchona alkaloid QD-4firstworks as a Br nsted base to promote the activation of the dimethyl malonate bydeprotonation, and then the hydroxyl group of QD-4acts as Br nsted acid to activatethe β-nitrostyrene. The rate determining step is the proton transfer process from thetertiary amine of QD-4to α-carbon of β-nitrostyrene. The comparison of themechanisms and energies of the six reaction channels enable us to learn the fact thatQD-4has good catalytic activities for the system, and implies C9-OH in QD-4maynot be involved in the activation. These calculation results accounts well for theobservations in experiments.
3. The conjugate addition of1-bromonitromethane to benzylidene acetonecatalyzed by9-amino-9-deoxyepiquinine. Asymmetric conjugate addition of1-bromonitromethane to benzylidene acetone catalyzed by9-amino-9-deoxyepiquinine as organic catalyst and benzoic acid as co-catalyst has beenextensively studied. However, in-depth understanding of the detailed mechanism is farfrom complete. By performing density functional theory (B3LYP and M062X) and abinitio calculations (MP2), we have identified a detailed mechanism of the title reaction.The reaction process includes three major stages:(I) the formation of an iminium ionintermediate;(II) the nucleophilic addition between the iminium and1-bromonitromethane; and (III) hydrolysis and recovery of catalyst. The calculatedresults not only explain benzoic acid as acidic additive plays an important role in the formation of the key reaction iminium intermediate, but also provide a general modelto help explain the mechanism and enantioselectivity of the conjugate additionreaction.
引文
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