Preparation of Covalent-Bound Iodofullerene through Selective Opening of Fullerene Epoxide To Form Halohydrin Fullerene Derivatives

Abstract

The epoxy moiety in a fullerene mixed peroxide can be opened regioselectively by various Lewis acids to form halohydrin fullerene derivatives. The first iodofullerene was obtained by treating the fullerene epoxide with triphenylphosphine and iodine. A single-crystal structure of the chlorohydrin derivative supports the results.

Key words

fullerene - halohydrin - epoxides - peroxide - Lewis acid

References and Notes

• 1a Hirsch A. The Chemistry of Fullerenes   Thieme Verlag; Stuttgart: 1994. 
• 1b Hirsch A. Brettreich M. Fullerenes: Chemistry and Reactions   Wiley-VCH; Weinheim: 2005. 
• 1c Taylor R. Lecture Notes on Fullerene Chemistry   Imperial College Press; London: 1999. 
• 2a Taylor R. Walton DRM. Nature (London)  1993,  363:  685 
• 2b Taylor R. Chem. Eur. J.  2001,  7:  4075 
• 2c Troyanov SI. Troshin PA. Boltalina OV. Ioffe IN. Sidorov LN. Kemnitz E. Angew. Chem. Int. Ed.  2001,  40:  2285 
• 2d Troyanov SI. Shustova NB. Popov AA. Sidorov LN. Kemnitz E. Angew. Chem. Int. Ed.  2005,  44:  432 ; and references cited therein
• 3a Zhu Q. Cox DE. Fisher JE. Kniaz K. McGhie AR. Zhou O. Nature (London)  1992,  355:  712 
• 3b Zenner T. Zabei H. J. Phys. Chem.  1993,  97:  8690 
• 4 Kissell K. Hartman K. der Heide PV. Wilson LJ. J. Phys. Chem. B  2005,  109:  5482 
• 5 Li Y. Zhang X. Li Q. Li W. J. Radioanal. Nucl. Chem.  2001,  250:  363 
• 6 Wharton T. Wilson LJ. Bioorg. Med. Chem.  2002,  10:  3545 
• 7a Gan LB. Huang SH. Zhang X. Zhang AX. Cheng BC. Cheng H. Li XL. Shang G. J. Am. Chem. Soc.  2002,  124:  13384 
• 7b Huang SH. Xiao Z. Wang FD. Gan LB. Zhang X. Hu XQ. Zhang SW. Lu MJ. Pan JQ. Xu L. J. Org. Chem.  2004,  69:  2442 
• 7c Huang SH. Xiao Z. Wang FD. Zhou J. Yuan G. Zhang SW. Chen ZF. Thiel W. Schleyer PR. Zhang X. Hu XQ. Chen BC. Gan LB. Chem. Eur. J.  2005,  11:  5449 
• 9a Palumbo G. Ferreri C. Caputo R. Tetrahedron Lett.  1983,  24:  1307 
• 9b Caputo R. Chianese M. Ferreri C. Palumbo G. Tetrahedron Lett.  1985,  26:  2011 
• 10 Cotton FA. Kibala PA. J. Am. Chem. Soc.  1987,  109:  3308 
• 11 Godfrey SM. Kelly DG. McAuliffe CA. Mackie AG. Pritchard RG. Watson SM. J. Chem. Soc., Chem. Commun.  1991,  17:  1163 

8

Single crystals suitable for X-ray diffraction analysis were obtained for 2b by slow evaporation of a toluene solution at 5 °C. Crystal data for 2b C_86.5H₄₉ClO₉, M = 1267.71, monoclinic, P2 (1)/c, a = 12.749 (3), b = 13.984 (3), c = 33.372 (7) Å, α = 90°, β = 97.35 (3)°, γ = 90°, V = 5901 (2) ų, T = 293 (2) K, Z = 4, ρ _calcd = 1.4427 mg/m³, graphite monochromatized MoK_α-radiation, λ = 0.71073 Å, crystal size 0.50 ¥ 0.20 ¥ 0.15 mm³. Data collected on a Rigaku RAXIS RAPID IP diffractometer, 9979 unique reflections (R _int = 0.0529). Refinement on F ², final residuals R1 = 0.0723 for 4561 reflections with I>2sI), wR2 = 0.2122 for all data. CCDC-287295 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/consts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB12 1EZ, UK; fax: [phone]; or e-mail: [e-mail]].