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

Niti Ngamsomprasert; Gautam Panda; Shuhei Higashibayashi; Hidehiro Sakurai

doi:10.1021/acs.joc.6b02046

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

Niti Ngamsomprasert, Gautam Panda, Shuhei Higashibayashi, Hidehiro Sakurai

Research output: Contribution to journal › Article

10 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	11978-11981
Number of pages	4
Journal	Journal of Organic Chemistry
Volume	81
Issue number	23
DOIs	https://doi.org/10.1021/acs.joc.6b02046
Publication status	Published - 2016 Dec 2
Externally published	Yes

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ASJC Scopus subject areas

Organic Chemistry

Cite this

Ngamsomprasert, N., Panda, G., Higashibayashi, S., & Sakurai, H. (2016). Synthesis of Hydroxysumanene and Substituent Effect of Hydroxy Group on Bowl Inversion Dynamics and Electronic Structure. Journal of Organic Chemistry, 81(23), 11978-11981. https://doi.org/10.1021/acs.joc.6b02046

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AU - Sakurai, Hidehiro

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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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10.1021/acs.joc.6b02046