Study on the Catalytic Behavior of Bifunctional Hydrogen-Bonding Catalysts Guided by Free Energy Relationship Analysis of Steric Parameters.
Study on the Catalytic Behavior of Bifunctional Hydrogen-Bonding Catalysts Guided by Free Energy Relationship Analysis of Steric Parameters.
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基于空间参数自由能关系分析的双功能氢键催化剂催化行为研究。
DOI：
10.1002/chem.201605666
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Jin‐Pei Cheng
中科院分区：
文献类型：
--
作者：
Chen Yang;Jie Wang;Yang Liu;Xiang Ni;Xin Li;Jin‐Pei Cheng
用自由能关系(FER)研究了(S，S)-环己烷-1，2-二胺衍生硫脲、金鸡纳生物碱衍生硫脲和(S，S)-环己烷-1，2-二胺衍生方酰胺等双功能叔胺氢键催化剂在Michael反应中的空间构型参数与催化性能的关系，发现N-取代基体积较小的催化剂更有利于催化反应。所观察到的FERS与手性支架和氢键给体无关，加深了对当前双功能氢键催化剂的理解。此外，DFT计算解释了观察到的取代基体积较小的硫脲类化合物的高反应性。特别是，计算结果表明了苄基硫脲催化剂的优越性，其中催化剂和底物之间额外的CH⋅⋅⋅π相互作用是关键因素。
Free energy relationship (FER) studies to correlate steric parameters with the enantiocatalytic performance of bifunctional tertiary-amine hydrogen-bonding catalysts, including (S,S)-cyclohexane-1,2-diamine-derived thioureas, Cinchona alkaloid derived thioureas, and (S,S)-cyclohexane-1,2-diamine-derived squaramides, in Michael reactions revealed that the reactions are much favored by catalysts with less bulky N-substituents. The observed FERs are independent of the chiral scaffold and hydrogen-bond donor, and deepen the understanding of current bifunctional hydrogen-bonding catalysts. Moreover, DFT calculations were performed to interpret the observed high reactivities of thioureas with less bulky substituents. In particular, the computations demonstrated the advantage of a benzyl thiourea catalyst, in which an extra CH⋅⋅⋅π interaction between catalyst and substrate is the key factor.
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