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

被引：13

作者：

Ngamsomprasert, Niti ^{[1
]}

Panda, Gautam ^{[2
]}

Higashibayashi, Shuhei ^{[3
]}

Sakurai, Hidehiro ^{[1
]}

机构：

[1] Osaka Univ, Grad Sch Engn, Div Appl Chem, 2-1 Yamadaoka, Suita, Osaka 5650871, Japan

[2] CSIR Cent Drug Res Inst, Med & Proc Chem Div, BS 10-1,Jankipuram Extens,Sitapur Rd, Lucknow 226031, Uttar Pradesh, India

[3] Inst Mol Sci, Res Ctr Integrat Mol Syst, Okazaki, Aichi 4448787, Japan

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2016年 / 81卷 / 23期

关键词：

SUMANENE; BUCKYBOWLS; PACKING; COMPLEX;

D O I：

10.1021/acs.joc.6b02046

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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.

引用

页码：11978 / 11981

页数：4

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