Preparation of [5,6]- and [6,6]-oxahomofullerene derivatives and their interconversion by Lewis acid assisted reactions of fullerene mixed peroxides.

[60]Fullerene mixed peroxides C60(O)(OOtBu)4 exhibit chemo- and regioselective reactions under mild conditions. The epoxy moiety is opened by ferric chloride to form vicinal hydroxy chloride C60Cl(OH)(OOtBu)4. BF3 is also effective in opening the epoxy moiety. The O-O bond of the fullerene mixed peroxide is cleaved by aluminum chloride to form both [5,6]- and [6,6]-fullerene hemiketals (oxohomo[60]fullerenes). A Hock-type rearrangement is proposed for the formation of the hemiketals, in which a fullerene C-C bond is cleaved. Lewis acids and/or visible light can initiate isomerization of the hemiketal isomers. Single-crystal X-ray analysis and theoretical calculations confirmed the results.

[1]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[2]  K. Kitazawa,et al.  Theoretical Studies of the Structures and Stabilities of Dumbell-like Fullerene Dimers: C121 , 2001 .

[3]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[4]  F. Diederich,et al.  Fullerene anions of different sizes and shapes: a 13C NMR and density-functional study. , 2003, The Journal of organic chemistry.

[5]  F. Diederich,et al.  ACHIRAL AND CHIRAL HIGHER ADDUCTS OF C70 BY BINGEL CYCLOPROPANATION , 1999 .

[6]  K. Kitazawa,et al.  First Unsymmetrical Bisfullerene, C121: Evidence for the Presence of Both Homofullerene and Methanofullerene Cages in One Molecule , 2001 .

[7]  M. Kertész,et al.  Identification for IPR Isomers of Fullerene C82 by Theoretical 13C NMR Spectra Calculated by Density Functional Theory , 2001 .

[8]  S. Bachilo,et al.  Synthesis and Characterization of the “Missing” Oxide of C60: [5,6]-Open C60O , 2001 .

[9]  M. Kertész,et al.  Isomer Identification for Fullerene C84by13C NMR Spectrum: A Density-Functional Theory Study , 2001 .

[10]  R. Taylor,et al.  Lecture Notes on Fullerene Chemistry , 1999 .

[11]  Xiaolu Chen,et al.  The first trisaza-bridged [60]fulleroid: drilling a hole on the fullerene. , 2004, Organic letters.

[12]  H. Kroto,et al.  Stable [60]fullerene carbocations , 1998 .

[13]  B. Patrick,et al.  7,8-(Dichloromethano)homo[70]fullerene, an Unusual, but Unexceptional, Methanoannulene , 2003 .

[14]  Geoffrey D. Brown,et al.  The mechanism of the spontaneous autoxidation of dihydroartemisinic acid , 2002 .

[15]  A. Hirsch,et al.  Highly diastereoselective formation of stable fulleroids , 1998 .

[16]  H. Kroto,et al.  13 C NMR spectroscopy of C76, C78, C84 and mixtures of C86–C102; anomalous chromatographic behaviour of C82, and evidence for C70H12 , 1993 .

[17]  Miklos Kertesz,et al.  Theoretical 13C NMR Spectra of IPR Isomers of Fullerenes C60, C70, C72, C74, C76, and C78 Studied by Density Functional Theory , 2000 .

[18]  C. Mioskowski,et al.  Lewis acid-catalyzed regiospecific opening of vinyl epoxides by alcohols , 2000 .

[19]  P. Fowler,et al.  Isolation and characterisation of two oxahomofullerene derivatives of C60F18 , 2000 .

[20]  T. Clark,et al.  Opening and Closure of the Fullerene Cage in cis‐Bisimino Adducts of C60: The Influence of the Addition Pattern and the Addend , 1996 .

[21]  F. Wudl.  The chemical properties of buckminsterfullerene (C60) and the birth and infancy of fulleroids , 1992 .

[22]  Roger Taylor,et al.  The chemistry of fullerenes , 1995, Nature.

[23]  Y. Rubin.  Ring Opening Reactions of Fullerenes: Designed Approaches to Endohedral Metal Complexes , 1999 .

[24]  Peter Pulay,et al.  Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations , 1990 .

[25]  Assigning the major isomers of fullerene C88 by theoretical 13C NMR spectra , 2003 .

[26]  F. Diederich,et al.  Syntheses, structures, and properties of methanofullerenes , 1994 .

[27]  Long Y. Chiang,et al.  Efficient synthesis of polyhydroxylated fullerene derivatives via hydrolysis of polycyclosulfated precursors , 1994 .

[28]  Harold W. Kroto,et al.  Isolation, separation and characterisation of the fullerenes C60 and C70 : the third form of carbon , 1990 .

[29]  B. Sitharaman,et al.  Fullerenols revisited as stable radical anions. , 2004, Journal of the American Chemical Society.

[30]  A. Hirsch,et al.  A Woodward-Hoffmann approach to the C60 cluster opening leading to homo[60]fullerenes , 2004 .

[31]  L. Chiang,et al.  Evidence of hemiketals incorporated in the structure of fullerols derived from aqueous acid chemistry , 1993 .

[32]  R. Haddon,et al.  Electronic structure of the fulleroids: Homoconjugation in bridged C60 derivatives , 1996 .

[33]  S. Murata,et al.  A novel photorearrangement of a cyclohexadiene derivative of C60. , 2002, Organic letters.

[34]  S. Bachilo,et al.  Ozonides, epoxides, and oxidoannulenes of C(70). , 2002, Journal of the American Chemical Society.

[35]  X. Zhang,et al.  Fullerenes as a tert-Butylperoxy Radical Trap, Metal Catalyzed Reaction of tert-Butyl Hydroperoxide with Fullerenes, and Formation of the First Fullerene Mixed Peroxides C60(O)(OOtBu)4 and C70(OOtBu)10 , 2002 .

[36]  X. Zhang,et al.  Selective preparation of oxygen-rich [60]fullerene derivatives by stepwise addition of tert-butylperoxy radical and further functionalization of the fullerene mixed peroxides. , 2004, The Journal of organic chemistry.

[37]  R. Taylor.  Why fluorinate fullerenes , 2004 .

[38]  R. Haddon,et al.  The First Structurally Characterized Homofullerene (Fulleroid) , 1999 .

[39]  R. Taylor,et al.  Isolation and characterisation of C60F4, C60F6, C60F8, C60F7CF3 and C60F2O, the smallest oxahomofullerene; the mechanism of fluorine addition to fullerenes , 2002 .

[40]  13C NMR spectra for IPR isomers of fullerene C86 , 2002 .

[41]  F. Diederich,et al.  Covalent Fullerene Chemistry , 1996, Science.

[42]  Y. Rubin,et al.  Solid-state NMR spectroscopy of molecular hydrogen trapped inside an open-cage fullerene. , 2004, Journal of the American Chemical Society.

[43]  Y. Murata,et al.  Synthesis, structure, and properties of novel open-cage fullerenes having heteroatom(s) on the rim of the orifice. , 2003, Chemistry.