Twofold and Threefold Sinusoidal Patterns in Coupled Molecular Motions of 184,025 Structures of Phenylethane, Nitroethane, and Carboxylate Derivatives
Twofold and Threefold Sinusoidal Patterns in Coupled Molecular Motions of 184,025 Structures of Phenylethane, Nitroethane, and Carboxylate Derivatives
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苯乙烷、硝基乙烷和羧酸衍生物的 184,025 种结构的耦合分子运动的双重和三重正弦模式
DOI：
10.1021/acs.joc.2c00443
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Tsuno Takashi
中科院分区：
文献类型：
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作者：
Brunner Henri;Ikeshita Masahiro;Tsuno Takashi
在剑桥结构数据库中搜索了14，169个在Cβ上有3个开配位的亚结构Cβ-CαH2-Ph的苯乙烷和150，568个在Cα上有另一个开配位X的亚结构Cβ-CαHX-Ph的苯乙烷。以Cα-C α为中心旋转360°时，旋转角θ = Cβ-Cα-C i-Co与旋光角θ = Co-Co′-C i-C α的相关性表现为三个最大值和三个最小值的正弦曲线，而旋转角θ与键角ω = Cβ-Cα-C i和键长d = Cβ-Cα的相关性表现为两个最大值和两个最小值的正弦曲线. 3993个硝基衍生物的亚结构Cβ-Cα HX-NO2证实了这一结果，并表明苯基化合物中的原子Ci/Co/Co′可以被原子N/O/O′取代而不改变二重和三重构型.在15，295个具有Cβ-CαHX-C′（CH 3 O）OMe亚结构的乙酸甲酯中，CαC′（CH 3 O）OMe基团的手性化导致具有四个不同角的手性平面四面体。四面体构型中的（Rθ）/（Sθ）选择性由从四面体中心Cα发出的键Cα-Cβ、Cα-H和Cα-X诱导。令人惊讶的是，像Cα-Cβ、Cα-H和Cα-X（X = H、C、N、O、S等）这样不同的键也是相同的。产生几乎相同的感应强度。
Scatter plot analyses for 14,169 phenylethanes of the substructure Cβ-CαH2-Ph with three open coordination positions at Cβand 150,568 phenylethanes of Cβ-CαHX-Ph with an additional open coordination position X at Cαhave been performed, based on searches in the Cambridge Structural Database. The correlation of rotation angle ψ = Cβ–Cα–Ci–Cowith a pyramidalization angle θ = Co–Co′–Ci–Cαin a 360° rotation about the bond Cα–Cireveals a sinusoidal pattern with three maxima and minima, whereas the correlation of rotation angle ψ with bond angle ω = Cβ–Cα–Ciand bond lengthd= Cβ–Cαresults in sinusoidal patterns with two maxima and minima. A total of 3993 nitro derivatives of the substructure Cβ-CαHX-NO2confirm the results and show that atoms Ci/Co/Co′in the phenyl compounds can be replaced by atoms N/O/O′ without any change in the two- and threefold patterns. In 15,295 methyl acetates of the substructure Cβ-CαHX-C′(═O)OMe, pyramidalization of the group CαC′(═O)OMe results in a chiral flat tetrahedron with four different corners. (Rθ)/(Sθ) selectivity in the configuration of the tetrahedron is induced by the bonds Cα–Cβ, Cα–H, and Cα–X, emanating from the tetrahedral center Cα. It is surprising that bonds as different as Cα–Cβ, Cα–H, and Cα–X (X = H, C, N, O, S, etc.) give almost the same induction intensities.