Prevalence of the Alkyl/Phenyl-Folded Conformation in Benzylic Compounds C_6H_5CH_2-X-R (X = O, CH_2, CO, S, SO, SO_2): Significance of the CH/pi Interaction as Evidenced by High-Level Ab Initio MO Calculations

Osamu Takahashi; Yuji Kohno; Ko Saito; Motohiro Nishio

首页> 外文期刊>Chemistry: A European journal >Prevalence of the Alkyl/Phenyl-Folded Conformation in Benzylic Compounds C_6H_5CH_2-X-R (X = O, CH_2, CO, S, SO, SO_2): Significance of the CH/pi Interaction as Evidenced by High-Level Ab Initio MO Calculations

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Prevalence of the Alkyl/Phenyl-Folded Conformation in Benzylic Compounds C_6H_5CH_2-X-R (X = O, CH_2, CO, S, SO, SO_2): Significance of the CH/pi Interaction as Evidenced by High-Level Ab Initio MO Calculations

机译：苄基化合物C_6H_5CH_2-X-R（X = O，CH_2，CO，S，SO，SO_2）中烷基/苯基折叠构象的普遍性：CH / pi相互作用的意义由高水平的从头算MO证明

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Ab initio MO calculations were carried out to examine the conformational energies of various benzylic compounds C_6H_5CH_2XR (X = O, CH_2, CO, S, SO, SO_2; R = CH_3, C_2H_5, iC_3H_7, tC_4H_9) at the MP2/6-311G(d,p)//MP2/6-21G(d) level. Rotamers with R/Ph in gauche relationship are generally more stable than the R/Ph anti rotamers. In these stable geometries, the interatomic distance in the interaction of alpha-or beTa-CH in the alkyl group and the ipso-carbon atom of the phenyl ring is short. The computational results are consistent with experimental data from supersonic molecular jet spectroscopy on 3-n-propyltoluene and NMR and crystallographic data on structurally related ketones, sulfoxides, and sulfones. In view of this, alkyl/phenyl-congested conformation of these compounds has been suggested to be a general phenomenon, rather than an exception. The attractive CH/pi interaction has been suggested to be a dominant factor in determining the conformation of simple aralkyl compounds.

机译：进行了从头算MO的计算，以检查MP2 / 6-311G（C = 6H_5CH_2XR（X = O，CH_2，CO，S，SO，SO_2; R = CH_3，C_2H_5，iC_3H_7，tC_4H_9）的构象能d，p）// MP2 / 6-21G（d）级别。具有R / Ph关系的旋转子通常比R / Ph反旋转子更稳定。在这些稳定的几何形状中，烷基中的α-或beTa-CH与苯环的ipso-碳原子相互作用的原子间距离短。计算结果与3-n-丙基甲苯和NMR的超音速分子喷射光谱实验数据以及与结构相关的酮，亚砜和砜的晶体学数据一致。鉴于此，已经提出这些化合物的烷基/苯基-拥挤构象是普遍现象，而不是例外。在确定简单的芳烷基化合物的构象中，有吸引力的CH / pi相互作用被认为是主导因素。

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《Chemistry: A European journal》 |2003年第3期|共7页
作者
Osamu Takahashi; Yuji Kohno; Ko Saito; Motohiro Nishio;
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正文语种 eng
中图分类化学;应用化学;
关键词
ab initio calculations; conformational analysis; hdyrogen bonds; noncovalent interactions; pi interactions;

机译：从头算;构象分析;氢键;非共价相互作用;pi相互作用;

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1. Prevalence of the Alkyl/Phenyl-Folded Conformation in Benzylic Compounds C_6H_5CH_2-X-R (X = O, CH_2, CO, S, SO, SO_2): Significance of the CH/pi Interaction as Evidenced by High-Level Ab Initio MO Calculations [J] . Osamu Takahashi, Yuji Kohno, Ko Saito, Chemistry: A European journal . 2003,第3期

机译：苄基化合物C_6H_5CH_2-X-R（X = O，CH_2，CO，S，SO，SO_2）中烷基/苯基折叠构象的普遍性：CH / pi相互作用的意义由高水平的从头算MO证明
2. General Preference fof Alkyl/Phenyl Folded Conformations. Relevance of the CH/pi~# and CH/O Interactions to Stereochemistry as Evidenced by Ab Initio MO Calculations [J] . Osamu Takahashi, Yuji Kohno, Yoshinobu Gondoh, Bulletin of the Chemical Society of Japan . 2003,第2期

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Prevalence of the Alkyl/Phenyl-Folded Conformation in Benzylic Compounds C_6H_5CH_2-X-R (X = O, CH_2, CO, S, SO, SO_2): Significance of the CH/pi Interaction as Evidenced by High-Level Ab Initio MO Calculations

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