TY - JOUR
T1 - Synthesis of Hydroxysumanene and Substituent Effect of Hydroxy Group on Bowl Inversion Dynamics and Electronic Structure
AU - Ngamsomprasert, Niti
AU - Panda, Gautam
AU - Higashibayashi, Shuhei
AU - Sakurai, Hidehiro
PY - 2016/12/2
Y1 - 2016/12/2
N2 - Hydroxysumanene was synthesized from acylsumanenes by Baeyer-Villiger oxidation. DFT calculation predicted the higher bowl inversion energy and deeper bowl structure of hydroxysumanene than those of pristine sumanene. The bowl inversion energy of hydroxysumanene was experimentally determined by 2D-EXSY NMR measurement as 21.2 kcal/mol. The energy was larger than that of pristine sumanene (20.3 kcal/mol), which agreed with the calculation result. Electrochemical measurement indicated the higher HOMO level of hydroxysumanene than that of sumanene, which confirmed the electron-rich character of the phenolic function in the bowl skeleton.
AB - Hydroxysumanene was synthesized from acylsumanenes by Baeyer-Villiger oxidation. DFT calculation predicted the higher bowl inversion energy and deeper bowl structure of hydroxysumanene than those of pristine sumanene. The bowl inversion energy of hydroxysumanene was experimentally determined by 2D-EXSY NMR measurement as 21.2 kcal/mol. The energy was larger than that of pristine sumanene (20.3 kcal/mol), which agreed with the calculation result. Electrochemical measurement indicated the higher HOMO level of hydroxysumanene than that of sumanene, which confirmed the electron-rich character of the phenolic function in the bowl skeleton.
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U2 - 10.1021/acs.joc.6b02046
DO - 10.1021/acs.joc.6b02046
M3 - Article
AN - SCOPUS:85001029975
VL - 81
SP - 11978
EP - 11981
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 23
ER -