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首页> 外文期刊>Phosphorus, Sulfur, and Silicon and the Related Elements >A DFT study of NBO and NICS analysis of the allylic rearrangements (the Claisen and thio-Claisen rearrangements) of 3-(vinyloxy)prop-1-ene and allyl vinyl sulfide
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A DFT study of NBO and NICS analysis of the allylic rearrangements (the Claisen and thio-Claisen rearrangements) of 3-(vinyloxy)prop-1-ene and allyl vinyl sulfide

机译：DFT研究NBO和NICS分析3-（乙烯基氧基）丙-1-烯和烯丙基乙烯基硫醚的烯丙基重排（克莱森和硫代克莱森重排）

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摘要

Ab initio density functional theory (DFT) calculations have been performed on the 3,3-sigmatropic rearrangements of 3-(vinyloxy)prop-1-ene (Claisen) and allyl vinyl sulfide (thio-Claisen) in the gas phase. The barrier height of the Claisen rearrangement calculated at the B3LYP/6-311G** level of theory was in good agreement with the corresponding experimental value. Optimized transition states at the B3LYP/6-311G** level were used for calculating of nucleus independent chemical shift (NICS) and also natural bond orbital (NBO) analysis at the same level. Our results indicate that aromaticities of the transition states are controlled by the out-of-plane component and that the strongest aromatic character is for the chair-like transition state of the thio-Claisen rearrangement. Analysis of donor-acceptor (bonding and antibonding) interactions suggests that the aromatic character of TS structure in the allyl vinyl sulfide reaction (the thio-Claisen rearrangement) is more than the 3-(vinyloxy)prop-1-ene reaction (the Claisen rearrangement). The NBO results show that in these rearrangements, activation energies are controlled by resonance energies.
机译：从头算密度泛函理论（DFT）计算已在气相中进行了3-（乙烯基氧基）丙-1-烯（Claisen）和烯丙基乙烯基硫醚（thio-Claisen）的3,3-σ重排。在B3LYP / 6-311G **理论水平上计算的克莱森重排的势垒高度与相应的实验值高度吻合。在B3LYP / 6-311G **水平上优化的过渡态用于计算相同水平的原子核独立化学位移（NICS）和自然键轨道（NBO）分析。我们的结果表明，过渡态的芳香性受平面外成分控制，最强的芳香性是硫代克莱森重排的椅子状过渡态。供体-受体（键合和反键）相互作用的分析表明，烯丙基乙烯基硫醚反应（硫代克莱森重排）中TS结构的芳族特征大于3-（乙烯基氧基）丙-1-烯反应（克莱森）重新排列）。 NBO结果表明，在这些重排中，活化能由共振能控制。

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