Boomerang-type substitution reaction

Reactivity of fullerene epoxides and a halofullerenol

Zhenshan Jia, Xiang Zhang, Gaihong Zhang, Shaohua Huang, Hao Fang, Xiangqing Hu, Yuliang Li, Liangbing Gan, Shiwei Zhang, Daoben Zhu

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The Cs-symmetric fullerene chlorohydrin C60(Cl)(OH) (OOtBu)4 reacts with 4-dimethylaminopyridine (DMAP) and 1,4-diazabicyclo[2.2.2]octane (DABCO) to yield two isomers with the formula C60(O)-(OOfBu)4 in good yields. These isomers differ with respect to the location of the epoxy functionality. The one from DMAP is C s symmetric, whereas that from DABCO is C1 symmetric with the poxy group on the central pentagon. Two different mechanisms are proposed to explain the chemoselectivity of these reactions. The reaction with DMAP involves single-electron transfer as the key step; DMAP acts as the lectron donor. A combination of an oxygen-atom shift and SN2″ processes (boomerang substitution) are responsible for the formation of isomer with DACBO. Various related reactions support the proposed mechanisms. The structures of new fullerene derivatives were determined by spectroscopy, single-crystal X-ray analysis, and chemical correlation experiments.

Original languageEnglish (US)
Pages (from-to)290-300
Number of pages11
JournalChemistry - An Asian Journal
Volume2
Issue number2
DOIs
StatePublished - Jul 2 2007

Fingerprint

Chlorohydrins
Fullerenes
Epoxy Compounds
Isomers
Spectrum Analysis
Substitution reactions
X-Rays
Electrons
Oxygen
X ray analysis
Single crystals
Spectroscopy
Derivatives
Atoms
triethylenediamine
4-dimethylaminopyridine
diazabicyclo(2.2.2)octane
fullerene C60
Experiments

Keywords

  • Epoxides
  • Fullerenes
  • Halohydrins
  • Peroxides
  • Single-electron transfer

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry

Cite this

Boomerang-type substitution reaction : Reactivity of fullerene epoxides and a halofullerenol. / Jia, Zhenshan; Zhang, Xiang; Zhang, Gaihong; Huang, Shaohua; Fang, Hao; Hu, Xiangqing; Li, Yuliang; Gan, Liangbing; Zhang, Shiwei; Zhu, Daoben.

In: Chemistry - An Asian Journal, Vol. 2, No. 2, 02.07.2007, p. 290-300.

Research output: Contribution to journalArticle

Jia, Z, Zhang, X, Zhang, G, Huang, S, Fang, H, Hu, X, Li, Y, Gan, L, Zhang, S & Zhu, D 2007, 'Boomerang-type substitution reaction: Reactivity of fullerene epoxides and a halofullerenol', Chemistry - An Asian Journal, vol. 2, no. 2, pp. 290-300. https://doi.org/10.1002/asia.200600268
Jia, Zhenshan ; Zhang, Xiang ; Zhang, Gaihong ; Huang, Shaohua ; Fang, Hao ; Hu, Xiangqing ; Li, Yuliang ; Gan, Liangbing ; Zhang, Shiwei ; Zhu, Daoben. / Boomerang-type substitution reaction : Reactivity of fullerene epoxides and a halofullerenol. In: Chemistry - An Asian Journal. 2007 ; Vol. 2, No. 2. pp. 290-300.
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