376
S. Chopin et al. / Tetrahedron Letters 46 (2005) 373–376
References and notes
warmed to 40–50 °C. When the reaction time is over, the
solid reaction products are filtered off, and isolated
through column chromatography.
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1
1
3
4; (b) Meskens, F. A. Synthesis 1981, 501–522.
7. (a) Fukuzumi, S.; Suenobu, T.; Hirasaka, T.; Arakawa,
R.; Kadish, K. M. J. Am. Chem. Soc. 1998, 120, 9220–
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Nierengarten, J.-F.; Felder, D.; Nicoud, J.-F. Tetrahedron
Lett. 2000, 41, 41–44.
1
1
2
8. Hann, R. M.; Richtmyer, N. K.; Diehl, H. W.; Hudson,
C. S. J. Am. Chem. Soc. 1950, 72, 561–566.
9. Huet, F.; Lechevallier, A.; Pellet, M.; Conia, J. M.
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0. (a) Maggini, M.; De Faveri, C.; Scorrano, G.; Prato, M.;
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Bolognesi, M. L.; Marucci, G.; Angeli, P.; Buccioni, M.;
Minarini, A.; Rosini, M.; Tumiatti, V.; Melchiorre, C. J.
Med. Chem. 2001, 44, 362–371.
8
2
2
1. Meier, M. S.; Bergosh, R. G.; Gallagher, M. E.; Spiel-
mann, H. P.; Wang, Z. J. Org. Chem. 2002, 67, 5946–5952.
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. Allard, E.; Delaunay, J.; Cheng, F.; Cousseau, J.; Ord u´ na,
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1
2. Selected analytical data. Compound 1. NMR: H (CS
/
1
0. (a) Meier, M. S.; Poplawska, M. Tetrahedron 1996, 52,
043–5052; (b) An, Y.-Z.; Anderson, J. L.; Rubin, Y. J.
2
acetone-d ): 3.82 (s, 4H, CH
6
2
–C60), 4.27 (t, 2H, OH,
5
3
3
J = 5.1 Hz), 4.46 (d, 4H, CH –OH, J = 5.1 Hz);
13
C
Org. Chem. 1993, 58, 4799–4801; (c) Ikeda, A.; Nobukuni,
S.; Udzu, H.; Zhong, Z.; Shinkai, S. Eur. J. Org. Chem.
2
(
been assigned: 70.76 (CH
DMSO-d
6
/chlorobenzene) only some carbon atoms have
–OH), 63.78 (CH –OH), 50.89
2
000, 3287–3293.
1. Allard, E.; Delaunay, J.; Cousseau, J. Org. Lett. 2003, 5,
239–2242.
2
2
ꢀ
1
(
3
CH –C60), 46.70 (CH –C60). IR (KBr) (cm ): 525 (C60),
402 (OH). UV (CH Cl ), k (nm): 431, 326, 304, 255. MS
2
2
1
1
1
2
2
2
Åꢀ
2. Allard, E.; Rivi e` re, L.; Delaunay, J.; Dubois, D.; Cous-
seau, J. Tetrahedron Lett. 1999, 40, 7223–7226.
(
try (o-DCB/acetonitrile (95:5), n-Bu
ESI): Mtheo = 822.07, M obs = 822.07. Cyclic voltamme-
NPF
ꢀ
1
, 100 mV s ):
4
6
+
E1/2 (vs Fc/Fc ) = ꢀ1.150, ꢀ1.525, ꢀ2.070 V. Compound
3. (a) Prato, M.; Suzuki, T.; Foroudian, H.; Li, Q.; Khemani,
K.; Wuld, F.; Leonetti, J.; Little, R. D.; White, T.;
Rickborn, B.; Yamago, S.; Nakamura, E. J. Am. Chem.
Soc. 1993, 115, 1594–1595; (b) Yamago, S.; Tokuyama,
H.; Nakamura, E. J. Org. Chem. 1993, 58, 4796–4798; (c)
Nakamura, E.; Isobe, H. Acc. Chem. Res. 2003, 36, 807–
1
0. H NMR (CS /CDCl ): 3.54 (s, 2H, CH –C ), 4.17 (s,
1
2
2
2 3 2 60
2
–O, J = 11.3 Hz), 5.17 (d,
H, CH
H, CH
2
–C60), 4.48 (d, 2H, CH
2
2
2
–O, J = 11.3 Hz), 5.81 (s, 1H, CH–O), 7.39–7.45
ꢀ
m, 3H, H ), 7.63–7.65 (m, 2H, H ). IR (KBr) (cm ):
ar ar
1
(
5
2 2
26 (C60), 1119 (CO ketal), 1638 (C@C). UV (CH Cl ), k
ꢀ
1
ꢀ1
(
nm) (e, L mol cm ): 431 (3470), 325 (32,400), 308
815.
(
33,400), 256 (113,000), 246 (104,000). MS (MALDI-
= 910. Cyclic voltammetry (o-
1
4. We have also observed that the reaction between 1,3-
Å+
2
ꢀ
TOF): Mtheo = 910, M
diiodo-2-propanol ICH
tonitrile gives rise to the alcohol C60(CH )
2
–CHOH–CH
2
I and C60 in ace-
CHOH 2 only
obs
ꢀ1
DCB/acetonitrile (95:5), n-Bu
4
NPF
Fc/Fc ) = ꢀ1.145, ꢀ1.520, ꢀ2.045 V. Compound 12. H
NMR (CDCl ): 4.00 (s, 4H, CH –C60), 5.37 (s, 4H, CH
O), 8.01 (d, 4H, H , J = 8.2 Hz), 8.33 (d, 4H, H ,
6
, 100 mV s ): E1/2 (vs
2 2
+
1
2ꢀ
as traces. Besides, a test experiment has shown that C60
anion remains stable in the presence of propan-2-ol.
5. Typical procedure: In a glove box, sodium methanethiolate
3
2
2
–
1
ar
ar
ꢀ
+
J = 8.2 Hz), 10.14 (s, 2H, CHO). MS (MALDI-TOF):
M
CH
C60 in 80 mL acetonitrile, and this mixture is stirred for
4 h at room temperature. Then the unreacted sodium
methanethiolate is filtered off, and the halo derivative (20–
3
S Na in excess is added to a suspension of 100 mg
+
th e´ o = 1086, M obs = 1086. Cyclic voltammetry (o-DCB,
ꢀ1
n-Bu NPF , 100 mV s ): E1/2 = ꢀ1.17, ꢀ1.55 V.
2
4
6
1
Compound 14. H NMR (CS /acetone-d ): 3.25 (s,
2
6
2ꢀ
+
6
H, SO
CH –OSO
2
–CH ), 3.96 (s, 4H, CH
3
2
–C60), 5.10 (s, 4H,
30 equiv) is added to the resulting C60 , 2Na red
ꢀ
1
). IR (KBr) (cm ): 526 (C60), 1176, 1358
solution. After, this resulting reaction mixture is taken
out off the glove box and is stirred at room temperature or
2
2
(
SO2).