Boomerang-type substitution reaction: reactivity of fullerene epoxides and a halofullerenol.

The C(s)-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)(OOtBu)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 epoxy 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 electron donor. A combination of an oxygen-atom shift and S(N)2'' 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.

[1]  S. Murata,et al.  Open-cage fullerenes : Synthesis, structure, and molecular encapsulation , 2005 .

[2]  R. Taylor,et al.  Evidence for the S(N)2' mechanism in hydrolysis of C60F48: origin of the stability of trannulenes. , 2003, Organic & biomolecular chemistry.

[3]  A. Hirsch.  Principles of Fullerene Reactivity , 1999 .

[4]  Shaohua Huang,et al.  Preparation of fullerendione through oxidation of vicinal fullerendiol and intramolecular coupling of the dione to form hemiketal/ketal moieties. , 2006, Organic letters.

[5]  Y. Rubin,et al.  Triple Scission of a Six-Membered Ring on the Surface of C60 via Consecutive Pericyclic Reactions and Oxidative Cobalt Insertion , 1996 .

[6]  R. Bensasson,et al.  Monomeric azaheterofullerene derivatives RC59N: influence of the R moiety on spectroscopic and photophysical properties. , 2006, Chemistry.

[7]  A. Hirsch,et al.  Reaction of [60]fullerene with morpholine and piperidine: preferred 1,4-additions and fullerene dimer formation , 1995 .

[8]  K. C. Kim,et al.  Taming superacids: stabilization of the fullerene cations HC60+ and C60.+. , 2000, Science.

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

[10]  Joseph F. Bunnett,et al.  Aromatic substitution by the SRN1 mechanism , 1978 .

[11]  O. Boltalina.  Fluorination of fullerenes and their derivatives , 2000 .

[12]  M. Saunders,et al.  The 3He NMR spectra of a [60]fullerene cation and some arylated [60]fullerenes , 1999 .

[13]  A. Hirsch,et al.  C59N+ and C69N+: Isoelectronic Heteroanalogues of C60 and C70 , 1995 .

[14]  A. Hirsch,et al.  C59N+ und C69N+: isoelektronische Hetero-Analoga von C60 und C70†‡ , 1995 .

[15]  T. Kitagawa,et al.  Electrophilic Addition of Polychloroalkanes to C60: Direct Observation of Alkylfullerenyl Cation Intermediates , 1999 .

[16]  E. Kemnitz,et al.  Synthesis and Structures of Fullerene Bromides and Chlorides , 2005 .

[17]  Daoben Zhu,et al.  Amination of [60]fullerene by ammonia and by primary and secondary aliphatic amines--preparation of amino[60]fullerene peroxides. , 2007, Chemistry.

[18]  F. Diederich,et al.  The Higher Fullerenes: Covalent Chemistry and Chirality , 1999 .

[19]  Takatsugu Tanaka,et al.  Regioselective oxygenative tetraamination of [60]fullerene. Fullerene-mediated reduction of molecular oxygen by amine via ground state single electron transfer in dimethyl sulfoxide. , 2005, The Journal of organic chemistry.

[20]  G. Miller.  Reactions between aliphatic amines and [60]fullerene: a review , 2006 .

[21]  Fred Wudl,et al.  Isolation of the Heterofullerene C59N as Its Dimer (C59N)2 , 1995, Science.

[22]  K. Takeuchi,et al.  Lewis acid-assisted nucleophilic substitution of fullerene epoxide. , 2006, Organic letters.

[23]  Shaohua Huang,et al.  Lewis acid promoted preparation of isomerically pure fullerenols from fullerene peroxides C60(OOt-Bu)6 and C60(O)(OOt-Bu)6. , 2006, The Journal of organic chemistry.

[24]  C. Galli,et al.  Unequivocal S(RN)1 route of vinyl halides with a multitude of competing pathways: reactivity and structure of the vinyl radical intermediate. , 2003, Accounts of chemical research.

[25]  R. Rossi,et al.  Nucleophilic substitution reactions by electron transfer. , 2003, Chemical reviews.

[26]  X. Zhang,et al.  Preparation of [5,6]- and [6,6]-oxahomofullerene derivatives and their interconversion by Lewis acid assisted reactions of fullerene mixed peroxides. , 2005, Chemistry.

[27]  N. Martín.  New challenges in fullerene chemistry. , 2006, Chemical communications.

[28]  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 .

[29]  Wallace W. H. Wong,et al.  Regio- and diastereoselective synthesis of bis- and tetrakisadducts of C70 by directed remote functionalization using Tröger base tethers. , 2006, Chemistry.

[30]  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.

[31]  Charles L. Wilkins,et al.  C62, a Non-Classical Fullerene Incorporating a Four-Membered Ring , 2000 .

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

[33]  Y. Murata,et al.  Synthesis and properties of endohedral C60 encapsulating molecular hydrogen. , 2006, Journal of the American Chemical Society.

[34]  M. Saunders,et al.  Carbon monoxide inside an open-cage fullerene. , 2006, Angewandte Chemie.

[35]  Y. Murata,et al.  Encapsulation of Molecular Hydrogen in Fullerene C60 by Organic Synthesis , 2005, Science.

[36]  R. Taylor,et al.  In the first proven SN2' fullerene reaction, both C3 and C1 C60F36 hydrolyse to C1 isomers of C60F35OH that eliminate HF to give epoxides C60F34O; C60F36O oxides are shown to be ethers, and a fourth isomer of C60F36 exists. , 2003, Organic & biomolecular chemistry.

[37]  P. Troshin,et al.  Bromination of [60]Fullerene. II. Crystal and Molecular Structure of [60]Fullerene Bromides, C60Br6, C60Br8, and C60Br24 , 2003 .

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

[39]  Guan-Wu Wang,et al.  Unexpected reactions of [60]fullerene involving tertiary amines and insight into the reaction mechanisms. , 2006, Chemistry.

[40]  T. Kitagawa,et al.  Electron-transfer-induced substitution of alkylated C60 chlorides with proton sponge. , 2004, The Journal of organic chemistry.

[41]  T. Kitagawa,et al.  Nucleophilic substitution of alkylchlorodihydro[60]fullerenes: thermodynamic stabilities of alkylated C60 cation intermediates. , 2002, Chemical communications.