Synthesis of Hydroxysumanene and Substituent Effect of Hydroxy Group on Bowl Inversion Dynamics and Electronic Structure

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-E...

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Bibliographic Details
Published inJournal of organic chemistry Vol. 81; no. 23; pp. 11978 - 11981
Main Authors Ngamsomprasert, Niti, Panda, Gautam, Higashibayashi, Shuhei, Sakurai, Hidehiro
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 02.12.2016
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
PACKING
COMPLEX
BUCKYBOWLS
SUMANENE
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Summary: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.
Bibliography:ObjectType-Article-1
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content type line 23
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.6b02046