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Organic Chemistry of C60 (Buckminsterfullerene): Chromatography and Osmylation

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Organic Chemistry of C60 (Buckminsterfullerene): Chromatography and Osmylation 6250 J. Org. Chem. 1990,55, 6250-6252 the above reaction. Interestingly, the reaction of 13 (1.0 Lab, University of Ottawa, for recording CI mass spectra; equiv) with TTMSS (1.2 equiv) in toluene, using AIBN Anne Webb, Elemental Analysis Lab (NRC, Ottawa) for as initiator gave the cyclic product 14 as nonseparable elemental analysis; and Dan Wayner for stimulating dis- mixture of 1:l cis and trans isomers. cussions. Further explorations of tris(trimethylsily1)silane in free-radical reactions are in progress. Supplementary Material Available: General procedures and experimental results for new compounds (5 pages). Ordering Acknowledgment. We thank the Mass Spectroscopy information is given on any current masthead page. Organic Chemistry of C6,, (Buckminsterfullerene): Chromatography and Osmylation Joel M. Hawkins,* Timothy A. Lewis, Stefan D. Loren, Axel Meyer, James R. Heath, Yoko Shibato, and Richard J. Saykally Department of Chemistry, University of California, Berkeley, California 94720 Received November 9, 1990 Summary: Treatment of CG0with osmium tetroxide and R pyridine gives the osmate ester (2:l adduct) establishing that oxygen functionality can be added to c60 without disrupting the carbon framework. The efficient macroscopic preparation of c60 by the contact-arc vaporization of graphite rods' has recently brought this enchanting molecule from the realm of mo- lecular beam experiments2 into that o€ synthetic organic chemistry. We are interested in selectively adding func- tional groups to c60 in a way that leaves the carbon Figure 1. HPLC separation of C, (12.2 min) and C70(23.5 min) on a Pirkle column7 (eluted with hexane at 5.0 mL/min, detected skeleton intact and allows for further tran~formation.~We at 280 nm). report here the chromatographic separation of CMand C70 on a Pirkle column and the osmylation of 0. purified c60 and C70 are shown in Figures 2 and 3. The We have found that the crude benzene-soluble material small mass 720 peak in the C70 spectrum is probably due from the carbon-arc apparatus' is a complex mixture. to fragmentati~n;~no Ce0 was visible by HPLC or I3C Flash chromatography by dry loading onto silica gel and NMR,I0 the former being quite sensitive." The 13C NMR elution with hexanes gives a 40% recovery of material that spectrum of purified C70 confirms'* that one of the C,o is almost exclusively C60 and C,. c60 and C70 are quite peaks is not under the Cm peak as suspected on the basis mobile on silica gel and separate only slightly on the flash of the examination of C,/C70 mixtures.13 The pronounced column. HPLC on silica gel gives partial but incomplete separation of c60 and C70 on the Pirkle column suggests separation. We reasoned that a stationary support con- that electron donor-acceptor complexes of these aromatic taining a-acids might increase the retention and promote carbon clusters can be prepared, and we are pursuing this the discrimination of these a-basic aromatic clusters. possibility. Pirkle's phenylglycine-based HPLC column was designed We chose the powerful but selective oxidant osmium for the separation of enantiomers by interactions that tetraoxide for the functionalization of C60. The pyri- include the attraction between a-basic aromatic groups on dine-accelerated osmylation of polycyclic aromatic hy- substrates and a-acidic dinitrobenzamide groups on the drocarbons is well Treatment of a homogeneous stationary ~upport.~We have found that this column can toluene solution of a ca. 4:l c6o/C,o mixture and 2 equiv separate c60 and C70 by a wide margin, CY = 2.25 (Figure of osmium tetraoxide at 0 "C with 5 equiv of pyridine gave 1).6 On the commercially available semipreparative col- a brown precipitate within 1 min. After 12 h at room umn,' ca. 0.5 mg of material can be separated per injection; temperature, the majority of the Cm and C70 had reacted large preparative columns are known.8 Mass spectra of according to TLC. Filtration and washing with toluene (1) (a) Kratschmer, W.; Lamb, L. D.; Fostiropoulos, K.; Huffman, D. R. Nature 1990,347,354. (b) Taylor, R.; Hare, J. P.; Abdul-Sada, A. K.; Kroto, H. W. J. Chem. SOC.,Chem. Commun. 1990, 1423. (c) Haufler, 5 Cs!isN R. E.; Conceicao, J.; Chibante, L. P. F.; Chai, Y.; Byrne, N. E.; Flanagan, ceo + 2010, S.; Haley, M. M.; O'Brien, S. C.; Pan, C.; Xiao, Z.; Billups, W. E.; Ciu- folini, M. A.; Hauge, R. H.; Margrave, J. L.; Wilson, L. J.; Curl, R. F.; Smalley, R. E. J. Phys. Chem. In press. (2) (a) Kroto, H. W.; Heath, J. R.; OBrien, S. C.; Curl, R. F.; Smalley, R. E. Nature 1985,318, 162. (b) Weltner, W., Jr.; Van Zee, R. J. Chem. vacuum Reu. 1989, 89, 1713. (c) Kroto, H. Pure Appl. Chem. 1990, 62, 407. (3) The conversion of Cm to CmHs (structure undetermined) by Birch reduction is described in ref IC. (9) O'Brien, S. C.; Heath, J. R.; Curl, R. F.; Smalley, R. E. J. Chem. (4) Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923. Phys. 1988,88, 220. (5) Pirkle, W. H.; Finn, J. M.; Hamper, B. C.; Schreiner, J.; Pribish, (10) Cjo NMR (C&): 6 150.7, 148.1, 147.4, 145.4, 130.9. J. R. In Asymmetric Reactions and Processes in Chemistry; Eliel, E. L., (11) The relative molar absorptivities of C70and Cm, ~(C,~)/e(C60),is Otsuka, S., Eds.; ACS Symposium Series 185; American Chemical Society: 1.2 at 280 mn. Washington, DC, 1982; pp 245-260. (12) Taylor et al. just reported a similar but 0.6 ppm upfield shifted (6) Taylor et al. just reported the separation of CBoand Cio on alu- spectrum of CT0run in the presence of Cr(a~ac)~.'~ mina.Ib (13) Meijer, G.; Bethune, D. S.; Wilson, R. J.; Johnson, R. D. Sub- (7) Pirkle type 1-A ionically bound phenylglycine column, 25 cm x 10 mitted for publication. mm i.d., Regis Chemical Company, Morton Grove, IL. (14) (a) Schroder, M. Chem. Reu. 1980, 80, 187. (b) Wallis, J. M.; (8) Pirkle, W. H.; Finn, J. M. J. Org. Chem. 1982, 47, 4037. Kochi, J. K. J. Am. Chem. SOC.1988, 220, 8207. 0022-3263/90/1955-6250$02.50/0 0 1990 American Chemical Society Communications J. Org. Chem., Vol. 55, No. 26, 1990 6251 mal 1me. 72WBASE =e. i7sa 56.8 i r 188.8- - 18848. 9.8- - 188.8 - - 18848. 58.8- - "'7 58.8- - 428 1w.a - - i624. 58.8- - 720 1624. Figure 3. Electron impact mass spectrum of chromatographed C70. gave an 819'0 yield of osmate ester corresponding to the resonances were visible in the 'H NMR (DMSO-&); low addition of two osmium(V1) units per carbon cluster. Use solubility precluded 13C NMR. The 2:l stoichiometry is of 1 equiv of osmium tetraoxide and 2.5 equiv of pyridine consistent with the elemental analy~is.'~The presence gave the same material in 41% yield with respect to c60. of the intact ($0 skeleton was established by thermal re- The Dresence of the diolatodioxobis(amine)osmium(VI) ester moiety in the product was established'by the char- (16) Collin, R. J.; Jones, J.; Griffith, W. P. J. Chem. SOC.,Dalton acteristic IR band at 836 cm-' (U~~(OSO~)).~~-'~Pyridine Trans. 1974. 1094. (17) Elemental analysis of dried precipitate. Calcd for C&ImN,080s2: (15) IR (KBr): 1607,1482,1450,1215,1069,972,954,876,836(a), 763, C, 62.17;H, 1.30; N, 3.63; Os, 24.61. Found: C, 61.11;H, 1.42; N, 3.67; 692, 627, 618, 526 cm-'. Os, 24.49. 6252 J. Org. Chem. 1990, 55, 6252-6259 version to c60 under vacuum.18 This was first observed been reformed upon heating. in the electron impact mass chromatogram. Heating the These experiments establish that heteroatom function- sample in the mass spectrometer probe under vacuum at ality can be added to c60 without disrupting the carbon ca. 290 "C and recording E1 spectra at 0.45-min intervals framework. We are currently exploring the regiochemistry gave spectra of Os04 and pyridine (maximum at 1.8 min) of the osmylation and converting the glycolates to other followed by the spectrum of c60 (maximum at 5.85 min). organic functional groups in order to manipulate the c60 Prolonged heating is required to detect the CG0due to its framework. low volatility; this was also observed for the spectrum of Acknowledgment. J.M.H. is grateful to the National the pure cluster. A preparative version of this experiment Science Foundation (Presidential Young Investigator whereby the osmate ester was heated under vacuum for Award, CHE-8857453), the Camille and Henry Dreyfus 2 min (heat gun, 0.05 mmHg) gave a 47% combined yield Foundation (New Faculty Grant), the Shell Oil Company of c60 and CT0(enriched in c60 relative to the starting Foundation (Shell Faculty Fellowship), Xerox Corporation, material) as determined by HPLC with respect to a Monsanto Company, and the Merck Sharp & Dohme naphthalene standard. The osmate ester was free of un- Research Laboratories for financial support. J.R.H. thanks reacted Cm according to IR and TLC, so the Cm must have the NASA SET1 foundation and R.J.S. thanks the Na- tional Science Foundation for support. We thank Joseph (18) ReOC1(OCHzCHzO)(phen)similarly gives ethylene and Re03C1- (phen) when heated under vacuum: Pearlstein, R. M.; Davison, A. Lyssikatos for assistance with the 13C NMR spectrum of Polyhedron 1988, 7, 1981. GO. Articles Lipase-Catalyzed Asymmetric Hydrolysis of Esters Having Remote Chiral/Proc hiral Centers D. L.
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