ORGANIC
LETTERS
2006
Vol. 8, No. 7
1355-1358
[60]Fullerene-Fused Lactones:
Manganese(III) Acetate-Mediated
Synthesis and Novel Reductive Ring
Opening
Guan-Wu Wang,* Fa-Bao Li, and Ting-Hu Zhang
Hefei National Laboratory for Physical Sciences at Microscale and Department of
Chemistry, UniVersity of Science and Technology of China, Hefei, Anhui 230026, PRC
Received January 12, 2006
ABSTRACT
[60]Fullerene-fused lactones were prepared by the manganese(III) acetate-mediated reactions of [60]fullerene with carboxylic acids, carboxylic
anhydrides, or malonic acids. Novel reductive ring opening of the lactones with Grignard reagents was observed.
Free-radical reactions1 were one of the first investigated
reactions of fullerenes and continue to be of interest as
important methodologies to functionalize fullerenes.2 Over
the past decades, manganese(III)-mediated free-radical reac-
tions have been explored extensively, have found widespread
applications in organic synthesis, and have demonstrated
remarkable advantages over traditional peroxide- or light-
initiated processes.3 We were the first to report the free-
radical reactions of [60]fullerene (C60) promoted by man-
ganese(III) acetate dihydrate (Mn(OAc)3‚2H2O).4 The
Mn(OAc)3‚2H2O-mediated reactions of C60 with various
active methylene compounds and aromatic methyl ketones
afforded 1,4-adducts and 1,16-adducts of C60,4a,b singly
bonded fullerene dimers,4a dihydrofuran-fused C60 derivatives,4c
and methanofullerenes.4a,c In our recent work, we found that
the in situ generated ArC60-H could be transformed to
ArC60-OAc by Mn(OAc)3‚2H2O in a one-pot procedure.4d
(1) (a) Krusic, P. J.; Wasserman, E.; Keizer, P. N.; Morton, J. R.; Preston,
K. F. Science 1991, 254, 1183. (b) Krusic, P. J.; Wasserman, E.; Parkinson,
B. A.; Malone, B.; Holler, E. R., Jr.; Keizer, P. N.; Morton, J. R.; Preston,
K. F. J. Am. Chem. Soc. 1991, 113, 6274.
(2) For recent examples, see: (a) Gan, L.; Huang, S.; Zhang, X.; Zhang,
A.; Cheng, B.; Cheng, H.; Li, X.; Shang, G. J. Am. Chem. Soc. 2002, 124,
13384. (b) Darwish, A. D.; Avent, A. G.; Abdul-Sada, A. K.; Taylor, R.
Chem. Commun. 2003, 1374. (c) Maeda, Y.; Rahman, G. M. A.; Wakahara,
T.; Kako, M.; Okamura, M.; Sato, S.; Akasaka, T.; Kobayashi, K.; Nagase,
S. J. Org. Chem. 2003, 68, 6791. (d) Huang, S.; Xiao, Z.; Wang, F.; Gan,
L.; Zhang, X.; Hu, X.; Zhang, S.; Lu, M.; Pan, Q.; Xu, L. J. Org. Chem.
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Biomol. Chem. 2004, 2, 3464. (f) Vougioukalakis, G. C.; Orfanopoulos,
M. J. Am. Chem. Soc. 2004, 126, 15956. (g) Xiao, Z.; Wang, F.; Huang,
S.; Gan, L.; Zhou, J.; Yuan, G.; Lu, M.; Pan, J. J. Org. Chem. 2005, 70,
2060. (h) Isobe, H.; Tanaka, T.; Nakanishi, W.; Lemie`gre, L.; Nakamura,
E. J. Org. Chem. 2005, 70, 4826. (i) Kareev, I. E.; Kuvychko, I. V.;
Lebedkin, S. F.; Miller, S. M.; Anderson, O. P.; Seppelt, K.; Strauss, S.
H.; Boltalina, O. V. J. Am. Chem. Soc. 2005, 127, 8362. (j) Nakamura, Y.;
Suzuki, M.; O-kawa, K.; Konno, T.; Nishimura, J. J. Org. Chem. 2005, 70,
8472.
(3) For reviews, see: (a) Melikyan, G. G. Synthesis 1993, 833. (b) Iqbal,
J.; Bhatia, B.; Nayyar, N. K. Chem. ReV. 1994, 94, 519. (c) Snider, B. B.
Chem. ReV. 1996, 96, 339. For recent examples of manganese(III)-based
radical reactions, see: (d) Zhang, Z.; Wang, G.-W.; Miao, C.-B.; Dong,
Y.-W.; Shen, Y.-B. Chem. Commun. 2004, 1832. (e) Zhou, H.; Huang, X.;
Chen, W. J. Org. Chem. 2004, 69, 5471. (f) Huang, J.-W.; Shi, M. J. Org.
Chem. 2005, 70, 3859.
(4) (a) Zhang, T.-H.; Lu, P.; Wang, F.; Wang, G.-W. Org. Biomol. Chem.
2003, 1, 4403. (b) Wang, G.-W.; Zhang, T.-H.; Cheng, X.; Wang, F. Org.
Biomol. Chem. 2004, 2, 1160. (c) Wang, G.-W.; Li, F.-B. Org. Biomol.
Chem. 2005, 3, 794. (d) Chen, Z.-X.; Wang, G.-W. J. Org. Chem. 2005,
70, 2380.
10.1021/ol060090y CCC: $33.50
© 2006 American Chemical Society
Published on Web 03/04/2006