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Direct Determination of Absolute Configuration of Methyl-Substituted Phenyloxiranes: Combined Experimental and Theoretical Approach

Supporting Info

Peter Fristrup,*^† Peter R. Lassen,^‡ Christian Johannessen,^‡ David Tanner,^§ Per-Ola Norrby,^§ K. J. Jalkanen,^‡ and Lars Hemmingsen^‡

Center for Sustainable and Green Chemistry, Department of Chemistry, Technical University of Denmark, Building 201 Kemitorvet, DK-2800 Kgs. Lyngby, Denmark, The Quantum Protein Centre, Department of Physics, Technical University of Denmark, Building 309, DK-2800 Kgs. Lyngby, Denmark, Department of Chemistry, Technical University of Denmark, Building 201 Kemitorvet, DK-2800 Kgs. Lyngby, Denmark, Department of Natural Sciences, The Royal Veterinary and Agricultural University, Thorvaldsensvej 40, DK-1871 Frederiksberg C, Denmark, and Nanochemistry Research Institute, Department of Applied Chemistry, Curtin University of Technology, GPO Box U1987, Perth WA 6845, Australia

J. Phys. Chem. A, 2006, 110 (29), pp 9123–9129

DOI: 10.1021/jp060154m

Publication Date (Web): July 6, 2006

Corresponding author. E-mail: pf@kemi.dtu.dk.

†

Center for Sustainable and Green Chemistry, Department of Chemistry, Technical University of Denmark.

‡

The Quantum Protein Centre, Department of Physics, Technical University of Denmark.

Department of Chemistry, Technical University of Denmark.

Nanochemistry Research Institute, Department of Applied Chemistry, Curtin University of Technology.

The Royal Veterinary and Agricultural University.

Abstract

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.

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