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Absolute configurations of endoperoxides determined by vibrational circular dichroism (VCD) |
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| Authors: | Kenji Monde Tohru Taniguchi Charles S. Vairappan |
| Affiliation: | a Laboratory for Bio-Macromolecular Chemistry, Division of Biological Sciences, Graduate School of Science, Frontier Research Center for Post-Genomic Science and Technology, Hokkaido University, Kita-ku, Sapporo 001-0021, Japan b Sun Microsystems Laboratory of Computational Molecular Life Science, Division of Biological Sciences, Graduate School of Science, Frontier Research Center for Post-Genomic Science and Technology, Hokkaido University, Kita-ku, Sapporo 001-0021, Japan c Laboratory of Natural Products Chemistry, Institute for Tropical Biology and Conservation, Universiti Malaysia Sabah, 88999 Kota Kinabalu, Sabah, Malaysia |
| Abstract: | Diastereomeric mixture on the peroxide portion of an endoperoxide acetylmajapolene A (1) was efficiently separated by HPLC on a chiral column, submitting to vibrational circular dichroism (VCD) investigation. The ab initio theoretical VCD and IR calculations of 1a and 1b were performed by density functional theory (DFT) using the B3PW91/6-31G(d,p) level of theory. Focusing on an isolated characteristic peroxide vibrational band, absolute configurations of 1a and 1b were unambiguously determined as (1R,4R,7S,10S) and (1S,4S,7S,10S), respectively. This is the first VCD application to endoperoxides which exist abundantly in nature. |
| Keywords: | Peroxide Absolute configuration Vibrational circular dichroism VCD DFT calculation |
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