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Investigation of the Dynamic Behavior of Bisumanenyl
Author(s) -
Shrestha Binod Babu,
Karanjit Sangita,
Higashibayashi Shuhei,
Amaya Toru,
Hirao Toshikazu,
Sakurai Hidehiro
Publication year - 2015
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201402226
Subject(s) - diastereomer , chemistry , conformational isomerism , rotation (mathematics) , inversion (geology) , computational chemistry , stereochemistry , crystallography , molecule , organic chemistry , paleontology , geometry , mathematics , structural basin , biology
The behavior of bisumanenyl is dynamic as a result of inversion of each of its sumanene bowls and rotation between the two bowls. This behavior was fully elucidated by a combination of NMR experiments and density functional theory calculations. The MM (or PP ) and MP diastereomers are in thermodynamic equilibrium at room temperature and the MM ( PP ) diastereomer is 1.4–1.9 kcal mol −1 more stable than MP diastereomer. The calculated energy for inversion between the two forms of the bowl is 19.2 kcal mol −1 . The MM ( PP ) and MP diastereomers have two rotational stable conformers that rapidly interconvert as a result of the low rotational energy barriers, which were calculated to be 3.9 and 8.9 kcal mol −1 , respectively.