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首页> 外文期刊>RSC Advances >The theoretical chemical calculations clarify the mechanism of beta-alkylation of 1-phenylethanol with benzyl alcohol catalyzed by iron(II) acetylacetonate methods
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The theoretical chemical calculations clarify the mechanism of beta-alkylation of 1-phenylethanol with benzyl alcohol catalyzed by iron(II) acetylacetonate methods

机译：理论化学计算阐明了通过铁（II）乙酰丙酮方法催化的苄醇的1-苯基乙醇的β-烷基化的机制

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摘要

Iron(II) acetylacetonate was suggested to be a better catalyst of the beta-alkylation of 1-phenylethanol with benzyl alcohol to form 1,3-diphenyl-1-propanol. DFT calculations have been performed to study the internal mechanism, the structures of intermediates and transition states, and the exchange of electronic density in detail. The energetic results show that this beta-alkylation reaction proceeds via the hydrogen autotransfer mechanism and the catalytic cycle includes three sequential stages: (1) alcohol oxidation to produce aldehyde associated with hydride anion transfer, (2) cross-aldol condensation to form a chalcone and (3) chalcone reduction with multi-step hydrogenation. In order to study whether the only by-product, water, has clearly influenced the reaction, eight catalyst hydrogenation pathways and four catalyst dehydrogenation pathways have been studied. We are delighted to find that the presence of the only by-product, water, can significantly increase the reduction energy barrier of dihydrochalcone. The energy barrier of the catalyst's hydrogenation is less than 6 kcal mol(-1). Our calculation results are fundamentally coincident with the experimental detections, and suggest that the crossing-coupling reaction occurs through a reliable mechanism. Two dihydrochalcone catalysts were designed on the basis of how the beta-alkylation reaction proceeds.
机译：建议乙酰丙酮酸酯是1-苯基乙醇与苄醇的β-烷基化的更好催化剂，以形成1,3-二苯基-1-丙醇。已经进行了DFT计算以研究内部机制，中间体和过渡状态的结构，以及详细交换电子密度。能量结果表明，该β-烷基化反应通过氢固体转器机制进行，催化循环包括三个顺序阶段：（1）醇氧化，得到与氢化物阴离子转移相关的醛，（2）交叉醛缩合以形成醌缩合以形成醌。 （3）用多步氢化降低螯合酶。为了研究是否唯一的副产品，水已经清楚地影响了反应，已经研究了八种催化剂氢化途径和四种催化剂脱氢途径。我们很高兴地发现，唯一的副产品，水，可以显着增加二羟基丙酮的减少能量屏障。催化剂氢化的能量屏障小于6千卡（-1）。我们的计算结果与实验检测根本值一致，并表明交叉偶联反应通过可靠的机制发生。基于β-烷基化反应如何进行，设计了两种二羟基酮催化剂。

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  • 来源
    《RSC Advances》 |2018年第43期|共12页
  • 作者

    Feng Wei; Zhao Junfeng; Wei Aiwen; Zhang Dandan; Liu Huiling; Huang Xuri; Sun Kai;

  • 作者单位

    Jilin Univ Inst Theoret Chem Lab Theoret &

    Computat Chem Technol Bldg Jilin Univ Liutiao Rd 2 Changchun 130023 Jilin Peoples R China;

    Yantai Nanshan Univ Sch Technol Dept Mat Longkou 265713 Shandong Peoples R China;

    Jilin Univ Inst Theoret Chem Lab Theoret &

    Computat Chem Technol Bldg Jilin Univ Liutiao Rd 2 Changchun 130023 Jilin Peoples R China;

    Jilin Univ Inst Theoret Chem Lab Theoret &

    Computat Chem Technol Bldg Jilin Univ Liutiao Rd 2 Changchun 130023 Jilin Peoples R China;

    Jilin Univ Inst Theoret Chem Lab Theoret &

    Computat Chem Technol Bldg Jilin Univ Liutiao Rd 2 Changchun 130023 Jilin Peoples R China;

    Jilin Univ Inst Theoret Chem Lab Theoret &

    Computat Chem Technol Bldg Jilin Univ Liutiao Rd 2 Changchun 130023 Jilin Peoples R China;

    Jilin Univ Sch Pharmaceut Sci Changchun 130021 Jilin Peoples R China;

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