Mechanism of the asymmetric autocatalytic Soai reaction studied by density functional theory.
Mechanism of the asymmetric autocatalytic Soai reaction studied by density functional theory.
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密度泛函理论研究不对称自催化Soai反应机理。
DOI：
10.1002/chem.200902543
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发表时间：
2010
期刊：
影响因子：
--
通讯作者：
G. Ercolani
中科院分区：
文献类型：
--
作者：
L. Schiaffino;G. Ercolani
在M05-2X/6- 31 G（d）水平上，通过考虑十条能量不同的反应路径，对Soai反应的机理进行了深入的研究.研究表明，全手性二聚体的完全对映选择性催化循环是主要的反应机理。另外两个催化循环都是重要的正确理解Soai反应。它们是异手性二聚体的催化循环和纯手性二聚体的非对映选择性催化循环。前者已被证明是不是真正的竞争与主循环，所需的Soai反应，以体现手性放大，而后者，这是只有轻微的竞争与主要的，很好地解释了实验中观察到的对映体选择性的反应2-甲基嘧啶-5-甲醛。该研究还证明了B3 LYP泛函对于Soai反应机理研究的不足。
The mechanism of the Soai reaction has been thoroughly investigated at the M05-2X/6-31G(d) level of theory, by considering ten energetically distinct paths. The study indicates the fully enantioselective catalytic cycle of the homochiral dimers to be the dominant mechanism. Two other catalytic cycles are shown to both be important for correct understanding of the Soai reaction. These are the catalytic cycle of the heterochiral dimer and the non-enantioselective catalytic cycle of the homochiral dimers. The former has been proved to be not really competitive with the principal cycle, as required for the Soai reaction to manifest chiral amplification, whereas the latter, which is only slightly competitive with the principal one, nicely explains the experimental enantioselectivity observed in the reaction of 2-methylpyrimidine-5-carbaldehyde. The study has also evidenced the inadequacy of the B3LYP functional for mechanistic investigations of the Soai reaction.