[2,3]-sigmatropic rearrangements of hydrogen and alkyl 3-propenyl sulfoxides: A computational study
[2,3]-sigmatropic rearrangements of hydrogen and alkyl 3-propenyl sulfoxides: A computational study
复制标题
DOI：
10.1002/qua.21067
复制
发表时间：
2006-09-01
影响因子：
2.2
通讯作者：
Valencia, Diego O., Jr.
中科院分区：
文献类型：
--
作者：
Freeman, Fillmore;Bathala, Radha M.;Valencia, Diego O., Jr.
氢和烷基3-丙烯基亚砜的[2，3]-σ迁移重排用HF、MP2和B3 LYP方法研究了6- 31 G（d），6-31+ G（d，p），6 - 311 +G（d，p），6 -311+G（2d，2 p），6 - 311 + G（3d，2 p），6 - 311 + G（3d，2 p），6-311+G（和cc-pVTZ基组。相应的异构亚砜和次磺酸盐的相对能量（E-rel）是敏感的理论水平和电子相关性。亚磺酸盐在气相中更稳定，极性更强的亚砜在水介质中更稳定。重排是一致的，并且endo和exo五元过渡态在能量上非常接近（Δ E =
The [2,3]-sigmatropic rearrangements of hydrogen and alkyl 3-propenyl sulfoxides (R = H, CH3, CF3, CCl3) to the corresponding 3-propenyl sulfenates have been examined computationally using HF, MP2, and B3LYP with the 6-31G(d), 6-31+G(d,p), 6-311+G(d,p), 6-311+G(2d,2p), 6-311+G(3d,2p), and cc-pVTZ basis sets. The relative energies (E-rel) of the respective isomeric sulfoxides and sulfenates are sensitive to the level of theory and to electron correlation. The sulfenate is more stable in the gas phase, and the more polar sulfoxide is more stable in aqueous medium. The rearrangements are concerted, and the endo and exo five-membered transition states are very close in energy (Delta E =