Fristrup Peter, Lassen Peter R, Johannessen Christian, Tanner David, Norrby Per-Ola, Jalkanen K J, Hemmingsen Lars
Center for Sustainable and Green Chemistry, Department of Chemistry, Technical University of Denmark, Building 201 Kemitorvet, DK-2800 Kgs. Lyngby, Denmark.
J Phys Chem A. 2006 Jul 27;110(29):9123-9. doi: 10.1021/jp060154m.
Three possible methyl-substituted phenyloxiranes have been synthesized in enantioenriched form (89-99% enantiomeric excess (ee)), and their vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra have been recorded. The experimental spectra are compared to theoretical spectra obtained from quantum mechanical calculations (density functional theory with the B3LYP hybrid exchange correlation functional with 6-31++G*, aug-cc-pVDZ, or aug-cc-pVTZ basis set) and related to the physical structure of the compounds. The absolute configuration could be established directly in each case by comparing experimental and theoretical spectra. In addition, we have been able to document the changes that occur both in structures and in the VA and VCD spectra due to substituent effects on the oxirane ring.
已合成出三种对映体富集形式（对映体过量率为89 - 99%）的甲基取代苯基环氧乙烷，并记录了它们的振动吸收（VA）和振动圆二色性（VCD）光谱。将实验光谱与通过量子力学计算（采用B3LYP混合交换相关泛函以及6 - 31++G*、aug-cc-pVDZ或aug-cc-pVTZ基组的密度泛函理论）得到的理论光谱进行比较，并与化合物的物理结构相关联。通过比较实验光谱和理论光谱，在每种情况下都能直接确定绝对构型。此外，我们还能够记录由于环氧乙烷环上的取代基效应而在结构以及VA和VCD光谱中发生的变化。
