General One-step Synthesis of Symmetrical or Unsymmetrical 1,4-Di(organo)fullerenes from Organo(hydro)fullerenes through Direct Oxidative Arylation

Article abstract of DOI:10.1021/acs.joc.9b01272

A general one-step synthesis of symmetrical or unsymmetrical 1,4-di(organo)fullerenes from organo(hydro)fullerenes (RC₆₀H) is realized by direct oxidative arylation. The new combination of catalytic trifluoromethanesulfonic acid (TfOH) and stoichiometric o-chloranil is the first to be used to directly generate an R-C₆₀⁺ intermediate from common RC₆₀H. Unexpectedly, the in situ generated R-C₆₀⁺ intermediate is shown to be quite stable in whole ¹³C NMR spectroscopy characterization in the absence of cation quenching reagents. Because the direct oxidation of common RC₆₀H to form the corresponding R-C₆₀⁺ has never been realized, the present combination of TfOH and o-chloranil solves the challenges associated with the formation of stable RC₆₀⁺ cations from common RC₆₀H without any coordination of an R group.

Full text of DOI:10.1021/acs.joc.9b01272

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Article
A General One-step Synthesis of Symmetrical
or Unsymmetrical 1,4-Di(organo)fullerenes from
Organo(hydro)fullerenes through A Direct Oxidative Arylation
Yin-Fu Wu, Shan-Shan Wang, Chun-Rui Yao, Zuo-Chang Chen, Shu-Hui Li, Yang-Rong Yao, Xue-Peng
Zhang, Yin Su, Shun-Liu Deng, Qianyan Zhang, Fei Gao, Su-Yuan Xie, Rong-Bin Huang, and Lan-Sun Zheng
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01272 • Publication Date (Web): 17 Jul 2019
Downloaded from pubs.acs.org on July 19, 2019
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A General One-step Synthesis of Symmetrical or Unsymmetrical
1,4-Di(organo)fullerenes from Organo(hydro)fullerenes
through A Direct Oxidative Arylation
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Yin-Fu Wu1, Shan-Shan Wang2, Chun-Rui Yao1, Zuo-Chang Chen1, Shu-Hui Li1, Yang-Rong Yao1,
Xue-Peng Zhang1, Yin Su1, Shun-Liu Deng1, Qianyan Zhang1*, Fei Gao2*, Su-Yuan Xie1, Rong-Bin
Huang1 and Lan-Sun Zheng1
1State Key Lab for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Ma-
terials, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005
(China)
2College of Chemistry, Chemical Engineering and Environment, Fujian Province Key Laboratory of Modern Analytical
Science and Separation Technology, Minnan Normal University, Zhangzhou 363000 (China)
Supporting Information Placeholder
ABSTRACT: A general one-step synthesis of symmetrical or unsymmetrical 1,4-di(organo)fullerenes from organo(hydro)full-
erenes (RC60H) is realized by a direct oxidative arylation. The new combination of catalytic trifluoromethanesulfonic acid
+
(TfOH) and stoichiometric o-chloranil is the first to be used to directly generate R-C60 intermediate from common RC60H,
unexpectedly the in situ generated R-C60+ intermediate is shown to be quite stable in whole 13C NMR spectroscopy character-
ization in the absence of cations quenching reagents. Because a direct oxidation of common RC60H to form the corresponding
+
R-C60 has never been realized, the present combination of TfOH and o-chloranil solves the challenges associated with the
formation of stable RC60+ cations from common RC60H without any coordination of an R group.
1a).6 Unlike alkyl groups, the introduction of aromatic
groups bearing π electrons might give the aryl group-func-
tionalized fullerene derivatives unique electronic proper-
ties. However, the direct and effective arylation of the C–H
bond of RC60H remains challenging.7 Itami and coworkers
reported the first and only example of the C–H arylation of
common RC60H species using Pd complexes as the catalysts
via the key reaction intermediates of fullerenyl anions (Fig-
ure 1b).8 The isolated yields for the arylation of their two
different organo(hydro)fullerenes were reported to be 23%
and 6%, and the low yield is due to the formation of large
amounts of fullerene dimer or pristine fullerene byproducts
under Pd catalysis in an alkaline environment.
INTRODUCTION
The chemical modification of fullerenes through the instal-
lation of suitable organic functional groups onto the fuller-
ene core is a very successful approach for the preparation
of fullerene-based nanocarbon materials.1 Organo(hy-
dro)fullerenes (RC60H) bearing both organo and hydrogen
functional groups can easily be synthesized by various or-
ganic reactions starting from pristine fullerene.1b, To
2
achieve more stable fullerene materials for further applica-
tions, the C(sp3)–H bonds of RC60H are usually functional-
ized into C–C bonds.3 Owing to the acidity of the C(sp3)–H
bond,4 organo(hydro)fullerenes have been functionalized
with various alkyl groups5 in the presence of base (Figure
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To avoid the fullerenyl anion intermediates, we decide to
therefore, the R group is actually not a common organo
functional groups and which obviously limits the wide ap-
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develop an oxidative strategy through organofullerenyl cat-
ionic intermediates to realize the arylation of organo(hy-
dro)fullerene (Figure 1c). According to previous literatures,
organofullerenyl cationic intermediates were obtained
from an oxidation of organofullerenyl anions that produced
by deprotonation of organo(hydro)fullerene in an alkaline
environment.5,6 , or were produced from an oxidation of or-
ganofullerenyl dimers.2g, 9 In addition, aziridinofullerene is
also a useful precursor for the synthesis of 1,4-di(or-
gano)fullerenes via a fullerenyl cationic intermediate.10 No-
tably, Komatsu et al.11 successfully made a direct oxidation
of a special organofullerenyl dimer or a special organo(hy-
dro)fullerene to the corresponding organofullernenyl cati-
ons, however, the subsequent arylation reaction was only
suitable for the special organofullerenyl dimer, rather than
the special organo(hydro)fullerene. Herein, a direct oxida-
tive arylation of common RC60H has been realized by a novel
combination of o-chloranil and TfOH with arenes as orga-
nofullerenyl cationic intermediate trap reagents (Figure 1c).
plication of common organofullerenyl cations. To date, the
+
production of a stable organofullerenyl cations (R–C60
)
without any coordination from an R group has always been
a challenge for chemists (Figure 2c). In this work, R–C60+ as
stable species can be produced by a new combination of tri-
fluoromethanesulfonic acid (TfOH) and o-chloranil directly
from common organo(hydro)fullerene RC60H without any
coordination of an R group (Figure 2c). More importantly,
the stable organofullernenyl cations (R-C60+) were pro-
duced by the new combination are shown efficient in the
general one-step synthesis of 1,4-di(organo)fullerenes from
RC60H.
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Figure 2. (a, b) Previous work: two stable fullerenyl cati-
ons owing to the extra coordination stabilization. (c) This
work: stable fullerenyl cations R–C60+ without any coordina-
tion of an R group.
RESULTS AND DISCUSSION
C(sp3)–H bonds of organo(hydro)fullerene are a type of al-
lylic C(sp3)–H bond. Inspired by the similar successful oxi-
dation of a benzylic C(sp3)–H to form the corresponding cat-
ion intermediate from Shi and coworkers,15 we first chose
1,2-C60CH3H (1a) as a model substrate; benzene (2a) as the
simplest arene; 2,3-dichloro-5,6-dicyano-1,4-benzoqui-
none (DDQ), tetrachloro-para-benzoquinone (p-chloranil),
or tetrachloro-ortho-benzoquinone (o-chloranil) as the oxi-
dant; and transition-metal salts such as FeCl2, FeCl3,
Pd(OAc)2, Sc(OTf)3, Pd(OTf)2, or Cu(OTf)2 as the catalyst.
Under these conditions, the expected direct oxidative aryla-
tion reactions were inefficient and 1a was barely consumed
in the presence of quinone oxidants and transition-metal
catalysts, as shown in entries 1-8 of Table S1. However, ar-
ylation product 3a was obtained in 80% yield when the
transition-metal catalyst was replaced by a Bronsted acid,
TfOH, and o-chloranil was selected as the oxidant (Scheme
1 and Table S1, entry 10). The oxidative arylation reaction
with another slightly weaker Bronsted acid, methanesul-
fonic acid, as the catalyst also provided an acceptable yield
(Table S1, entry 9). Surprisingly, similar quinone oxidants
DDQ and p-chloranil with catalytic TfOH did not generate
the arylation products (Table S1, entries 11-12), indicating
that the adjacent carbonyl of o-chloranil is crucial for the ar-
ylation reaction. The combination of o-chloranil (2.5 equiv)
and TfOH (10 mol%) at 100 °C was found to be the optimal
reaction conditions for the one-step synthesis of 1,4-di(or-
gano)fullerenes with this new oxidative C(sp3)–H strategy.
Figure 1. Previous representative works and this work for
functionalization of the C(sp3)–H bond in organo(hy-
dro)fullerenes.
Fullerenyl cations are usually unstable because of their
electronegativity.12 To date, only three examples of the gen-
eration of fullerenyl cations as stable species have been re-
+
ported. In 2000, the long-sought-after H–C60 cation was
first prepared by Reed and coworkers13 through the direct
protonation of C60 with an extraordinarily strong superacid
involving an exceptionally inert carborane anion. Takeuchi
et al.15 reported the first example of organofullerenyl cation,
R–C60+(R=CHCl2 or CCl2CH2Cl), which was generated by ion-
ization of the corresponding fullerenol (Figure 2a). The sec-
ond example of R–C60+ was (EtO)2P(OH)CH2–C60+, which was
prepared by Komatsu et al.11 from (EtO)2P(O)CH2–C60H
+
(Figure 2b). However, the both R–C60 species are formed
mainly due to the extra coordination stabilization of the cat-
ionic center by the chlorine atom or the phosphoryl group,
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Although the RC60H starting materials are 1,2-ortho-di-
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substituted (Figures S9, S15), the oxidative arylation prod-
ucts (3a-3e and 4a-4e) are assumed to be regioselectively
formed as the 1,4-para-di(organo)fullerene derivatives ac-
cording to the UV-Vis data (Figures S10-14, S16-21).14, 16 Ad-
ditionally, single crystals of 3d and 4d were obtained by dif-
fusion methods, and the corresponding crystal structures
unambiguously show that both 3d and 4d were regioselec-
tively formed as the 1,4-para-substituted isomers (Figure 3,
Figures S27-28 and Table S3).
Scheme 1. TfOH-catalyzed oxidative arylation of or-
gano(hydro)fullerene 1a.
With the optimal conditions in hand, we first examined
the effect of substituents on the arene (Table 1, entries 1-5).
A variety of arenes with electron-donating or weak elec-
tron-withdrawing groups could provide the desired oxida-
tive arylation products, and the general trend was that in-
creased electron density on the aromatic ring improved the
yield. However, with strong electron-withdrawing substitu-
ents, such as carboxylic acid, methyl ester or trifluorome-
thyl groups, on the aromatic ring, no arylation products
were formed. Interestingly, the reaction of simple anisole
with a strong donating group gave a mixture of para- and
ortho-substituted (3b+3b’) regioisomers, while ortho-ester
substituted anisole 2c and other arenes provided 3c-3e
with high regioselectivity. Notably, substrates with elec-
tron-donating groups are much more reactive than those
with electron-withdrawing groups. Therefore, the experi-
mental results with various arenes show that the oxidative
arylation reaction follows a Friedel-Crafts-type reaction
mechanism.15
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Figure 3. X-ray crystallographic structures of 3d and 4d.
Hydrogen atoms and solvent molecules have been omitted
for clarity.
According to our hypothesis, the direct oxidative aryla-
tion of organo(hydro)fullerenes is proceeded by the in situ
generation of a fullerene cation and is followed by a Friedel-
Crafts-type reaction. To confirm the in situ generation of
fullerenyl cations, water was introduced as a trap reagent.14
As expected, the hydroxyl adducts were obtained as shown
in Figure S25 indicating that this arylation proceeds via a
carbocation intermediate. Furthermore, in the absence of
cation trap reagents, such as an arene, the in situ generated
fullerenyl cation was observed as a long-lived and stable
species by 13C NMR spectroscopy of a mixed sample (1b, o-
chloranil and TfOH).11, 13-14 The 13C NMR spectrum of the cat-
ion species generated from 1b shows fewer than 32 aro-
matic signals between 125 and 150 ppm and only one C(sp3)
signal at δ 53.25 ppm (Figure 4 and Figure S26), indicating
a change in the symmetry from C1 to Cs by a heterolytic
cleavage of the C(sp3)–H bond. The signal at 172.02 ppm is
assigned to the cationic carbon, which is close to the shifts
reported for analogous carbons (174.9 ppm for CH2ClCCl2–
Next, we investigated another organo(hydro)fullerene
substrate, 1,2-C60PhH (1b). The arylation efficiency for 1,2-
C60PhH (1b) is slightly higher than that for 1,2-C60CH3H (1a),
(Table1 entry 6-10) probably because the more electron-
donating phenyl group can further stabilize the in situ gen-
erated fullerenyl cation intermediate. With 1,2-C60PhH (1b)
as the starting material, the yields of the arylation products
(4a-4e) were also consistent with a Friedel-Crafts-type re-
action mechanism.
Table 1. TfOH-catalyzed oxidative arylation of or-
gano(hydro)fullerenes 1a and 1b with various arenes.
+
C60 and 174.67 ppm for (EtO)2P(O)CH2–C60+).11,14 Bulk tri-
fluoromethanesulfonate anions generated from the combi-
nation of TfOH and o-chloranil might help stabilization of
the in situ-formed fullerenyl cation. It is worthy to note that
1b remains insoluble in Komatsu reported mixed acid sys-
tem (4:1 H2SO4 and CF3SO3H)11 after 24-hour magnetic stir-
ring at the room temperature, and no arylation product
were observed even upon addition of arenes, finally the re-
covered compound is intact 1b, revealing that common
RC60H can’t be transformed into the corresponding full-
erenyl cation according to the reported conditions11.
aIsolated yields
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one-step synthesis of 1,4-di(organo)fullerenes, a possible
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oxidative arylation mechanism via a fullerenyl cation as the
key reaction intermediate was proposed (Figure 5). In the
presence of catalytic TfOH, a small portion of the o-chloranil
is readily protonated to form highly oxidative intermediate
A. Then, induced by oxidation with intermediate A, RC60H
●
can lose one electron to generate RH–C60 + and intermediate
A itself is reduced to radical intermediate B. After losing an
●
electron, the C(sp3)–H bond of RH–C60 + is wakened, the hy-
●
+
drogen cation of RH–C60 can be abstracted by o-chloranil
to form intermediate A.19 Then the newly formed interme-
diate A can oxidize the formed fullerenyl radical to afford
the key fullerenyl cation intermediate and intermediate B.
Alternatively, the fullerenyl radical can dimerize, producing
fullerene dimer C,20 and C can be cleaved to generate the key
fullerenyl cation according to previous reports.11, 21 Finally,
the in situ formed R–C60+ and the arenes undergo a Friedel-
Crafts-type reaction to give the desired coupling products
and protons to turn over the TfOH catalytic cycle. Regiose-
lective attack of the fullerenyl cation by the arene at the 4-
position might be due to steric effects. Notably, the signal of
dimeric radical B is indeed observed in the HRMS spectrum
of the coupling product mixture, as shown in Figure S24.
The proposed mechanism reasonably explains the high cou-
pling efficiency and the need for more than two equivalents
of oxidants in the present oxidative coupling.
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Figure 4. 13C NMR spectrum of the cationic species in o-
chloranil-TfOH. (rt, 150MHz, C2D2Cl4) The signal of o-chlo-
ranil is marked with green dot; that of CF3SO3H is marked
with red triangle; that of the characteristic carbocation and
sp3 carbon on the C60 cage are marked with deep-blue dot
and green triangle respectively.
To determine whether the fullerenyl cation is generated
by a direct heterolytic cleavage of a C(sp3)–H bond in the
one-step synthesis of 1,4-di(organo)fullerenes, electron
paramagnetic resonance (EPR) spectroscopy17 and radical-
inhibition studies were conducted. The EPR spectrum of 1a,
o-chloranil and TfOH exhibited a distinct signal at g = 2.005
(Table S2 and Figure S22). This signal confirmed that full-
erenyl radicals or radical cations are generated in the pre-
sent coupling reaction. Additionally, when 3 equiv of bu-
tylated hydroxytoluene (BHT) was added as a radical scav-
enger,18 the coupling reaction was completely suppressed,
and the starting RC60H was completely recovered (Figure
S23), which also confirmed that a radical process is involved
in this reaction.
To better understand the single electron oxidation to
●
+
form RH–C60 and the subsequent hydrogen abstraction
process, DFT calculations were employed. The calculated
Mulliken charges suggest that electron transfer from RC60
H
●
to intermediate A to form RH–C60 + is favorable (Table S4).
Detailed analysis of the transition state of the subsequent
hydrogen abstraction step shows that the Mulliken charge
of the reactive hydrogen atom is 0.383, while its spin den-
sity is only 0.048, indicating that the reactive hydrogen
atom is abstracted as a positive ion (proton) rather than as
a free radical (Table S5).
Figure 6. The reaction energy barrier of two possible re-
action pathways calculated at the M06-2X/6-31G (d,p) level.
Additionally, a possible homolytic cleavage of the C(sp3)-
H bond of RC60H is revealed energetically unfavorable. The
estimated reaction energy barrier of the hydrogen cation
Figure 5. Proposed mechanism for the TfOH-catalyzed
oxidative arylation of organo(hydro)fullerenes.
●
●
+
abstraction step (RH–C60 + o-chloranil → R–C60 + A) is
around 27.4 kcal/mol as shown in Figure 6a, by comparison,
that of hydrogen radical abstraction step is up to 45.0
Based on the confirmed coexistence of radical and cation
as well as the features of Friedel-Crafts-type reactions in the
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(s, 1H). HRMS: (APCI-TOF, negative) m/z calcd for C61H4 [M]-:
kcal/mol (Figure 6b). Therefore, the DFT calculations sup-
●
+
1
736.0313, found 736.0324.
port the proposed SET transfer to form RH–C60 followed
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by a proton abstraction process.
1-phenyl-4-hydro [60] fullerene (1b) A two-neck 25-mL glass
round flask containing a magnetic stirring bar was flame-dried
under vacuum and filled with nitrogen after cooling to room
temperature. To this flask were added C60 (43.2 mg, 60 μmol),
potassium phenyltrifluoroborate (16.6 mg, 90 μmol),
[Rh(cod)(MeCN)2]BF4 (2.2 mg, 6 μmol), o-DCB (7.2 mL), H2O
In summary, the first direct oxidative arylation of C(sp3)
–H in common RC60H generating symmetrical or unsymmet-
rical 1,4-di(organo)fullerenes has been efficiently realized
by using a new combination of catalytic TfOH and stoichio-
metric o-chloranil as well as arenes. Unexpectedly, the in
situ formed fullerenyl cation intermediate has been con-
firmed by the 13C NMR spectroscopy of a mixture of RC60H,
o-chloranil and TfOH. In addition, the new strategy success-
fully solves the challenges associated with the production of
o
(1.8 mL). This mixture was stirred at 60 C for 12 h in the oil
bath, the mixture was cooled to room temperature. Then the
mixture was evaporated and the residue was dissolved by 50
mL toluene and subjected to preparative recycling HPLC
equipped with 5PPB column (eluent: toluene) to afford 1b (20.1
mg, 42 %) as dark brown solid. Data of compound 1b: 1H NMR
(500 MHz, CDCl3/CS2 = 1:2) δ 8.49-8.51 (d, J = 8, 2H), δ 7.80-
7.84 (d, J1 = 12 Hz, J2 = 8 Hz, 2H), δ 7.62-7.65 (m, 1H), δ 6.79
(s, 1H). HRMS: (APCI-TOF, negative) m/z calcd for C66H6 [M]-:
798.0469, found 798.0471.
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60
+
stable R–C60 cation species from common RC60H com-
pounds without any coordination of an R group. The pro-
posed mechanism assumes that protonated o-chloranil is
the crucial oxidant species for the indirect heterolytic cleav-
age of the C(sp3)–H bond of RC60H, forming the key full-
erenyl cation.
General Procedure for TfOH-Catalyzed Reaction of 1a and
1b with Aromatic Compounds. A two-neck 10-mL glass
round flask containing a magnetic stirring bar was flame-dried
under vacuum and filled with nitrogen after cooling to room
temperature. To this flask were added 1a or 1b (20 µmol), o-
chloranil (12.3 mg, 50 µmol), dry o-DCB (2.0 mL), and then
2a-2e (200 µmol) under a stream of nitrogen. To the reaction
mixture was added TfOH (0.1 M solution in o-DCB, 20 µL, 2
µmol) and then the mixture was stirred at 100 oC in the oil bath.
After cooling to room temperature, the mixture was evaporated
and the residue was dissolved by 15 mL toluene. The solution
was passed through a pad of silica gel with copious washings
with toluene (~20 mL). The filtrate was concentrated and sub-
jected to preparative recycling HPLC equipped with a 5PPB
column (eluent: toluene) to afford 3a-3e and 4a-4e.
EXPERIMENTAL SECTION
General conditions: Unless otherwise noted, all solvents in-
cluding o-dichlorobenzene(o-DCB) and reactants (Benzene,
Anisole, Toluene and Chlorobenzene, Benzoic acid, 2-meth-
oxy-, methyl ester) were dried with P2O5 (Phosphorus pentoxide)
over night, then distilled. Unless otherwise noted, all reactions
were performed with dry solvents under an atmosphere of ni-
trogen in flame-dried glassware with standard vacuum-line
techniques. All reactions that require heating were heated by oil
bath. All work-up and purification procedures were carried out
with reagent-grade solvents in air.
Preparative recycling HPLC was performed with a Shimadzu
LC-20AT instrument equipped with a 5PPB column (10 mm ×
250 mm, COSMOSIL). High-resolution mass spectra (HRMS)
were obtained from a microTOF-QII (Atmospheric Pressure
Chemical Ionization time-of-flight mass spectrometry, APCI-
TOF-MS) and a Bruker instrument. Nuclear magnetic reso-
nance (NMR) spectra were recorded on a Bruker AVANCE III
500 MHz (1H 500 MHz, 13C 125 MHz) spectrometer and a
Bruker AVANCE III 600 MHz (1H 600 MHz, 13C 150 MHz)
1-methyl-4-phenyl [60] fullerene (3a) Following the general
procedure, the reaction of 1a (14.7 mg, 20 µmol) with o-chlo-
ranil (12.3 mg, 50 µmol), 2a (200 µmol) and TfOH (0.1 M so-
o
lution in o-DCB, 20 µL, 2 µmol) at 100 C stirring for 10 h
1
afforded 3a (13.0 mg ,80%). H NMR (500 MHz, CDCl3/CS2
= 1:2) δ 2.8 (s, 3H), δ 7.55-7.58 (m, 1H), δ 7.68-7.71 (m, 2H),
δ 8.34-8.36 (m, 2H). 13C {1H} NMR (150 MHz, CDCl3/CS2 =
1:2) δ 37.4 (1C CH3), 54.5 (1C C60CH3), 61.7 (1C C60Ph), 119.2
(1C C60), 124.1 (1C C60)，127.37 (2C C6H5), 128.42 (1C
C6H5), 129.8 (2C C6H5), 129.96 (2C C60), 130.01 (2C C60),
137.5 (1C C60), 137.9 (1C C60), 138.9 (1C C60), 139.0 (1C C60),
140.2 (1C C6H5), 141.1 (1C C60), 141.2 (1C C60), 142.1 (1C C60),
142.3 (1C C60), 142.5 (1C C60), 142.66 (2C C60), 142.72 (1C
C60), 142.8 (1C C60), 142.9 (1C C60), 143.25 (1C C60), 143.28
(1C C60),143.29 (1C C60), 143.31 (1C C60), 143.37 (1C C60),
143.88 (1C C60), 144.06 (1C C60), 144.15 (1C C60), 144.26 (1C
C60), 144.34 (1C C60), 144.38 (1C C60), 144.44 (1C C60), 144.5
(2C C60), 144.8 (2C C60), 145.00 (1C C60), 145.04 (1C C60),
145.3 (2C C60), 145.6 (1C C60), 145.7 (1C C60), 147.01 (1C C60),
147.03 (1C C60), 147.06 (1C C60), 147.08 (1C C60), 147.13 (1C
C60), 147.14 (1C C60), 147.2 (1C C60), 147.3 (1C C60), 148.2 (1C
C60), 148.7 (1C C60), 148.77 (1C C60), 148.81 (1C C60), 150.7
7(1C C60), 152.9 (1C C60), 157.1 (1C C60), 158.4 (1C C60).
HRMS: (APCI-TOF, negative) m/z calcd for C67H8 [M]-:
812.0621, found 812.0637.
1
spectrometer. Chemical shifts for H NMR are expressed in
parts per million (ppm) relative to tetramethylsilane (δ 0.0 ppm).
Chemical shifts for 13C NMR are expressed in ppm relative to
CDCl3 (δ 77.0 ppm). Data are reported as follows: chemical
shift, multiplicity (s = singlet, d = doublet, dd = doublet of dou-
blets, t = triplet, q = quartet, quin = quintet, sex = sextet, m =
multiplet, br = broad signal), coupling constant (Hz), and inte-
gration.
Organo(hydro)fullerenes synthesis
1-methyl-4-hydro [60] fullerene (1a) A two-neck 500-mL
glass round flask containing a magnetic stirring bar was flame-
dried under vacuum and filled with nitrogen after cooling to
room temperature. To this flask were added C60 (720 mg, 1
mmol), CH3MgBr (2 M in THF) (1.5 mL, 3 mmol), DMF (2.3
mL, 30 mmol), o-DCB (180 mL). This mixture was mixed for
5 min. Then, the mixture was evaporated and the residue was
dissolved by100 mL toluene. The solution was subjected to pre-
parative recycling HPLC equipped with a Buckyprep column
(eluent: toluene/ isopropanol = 7/3) to afford 1a (390.1 mg,
53%). C60 was recovered in 40% (288.0 mg). Data of compound
1a: 1H NMR (500 MHz, CDCl3/CS2 = 1:2) δ 3.32 (s, 3H) δ 6.45
1-methyl-4-(4-methoxyphenyl) [60] fullerene (3b) and 1-me-
thyl-4-(2-methoxyphenyl) [60] fullerene (3b’) Following the
ACS Paragon Plus Environment

The Journal of Organic Chemistry
general procedure, the reaction of 1a (14.7 mg, 20 µmol) with
Page 6 of 9
54.5 (1C C60CH3), 56.2 (1C OMe), 60.5 (1C C60Ph), 113.1 (1C
C6H4), 121.3 (1C C6H4), 125.5 (1C C60), 128.4 (1C C60), 129.1
(1C C60), 129.99 (2C C60), 130.04 (2C C60), 130.7 (1C C6H4),
132.1 (1C C6H4), 133.0 (1C C60), 137.6 (1C C60), 137.9 (1C C60),
139.1 (1C C60), 141.2 (1C C60), 142.1 (1C C60), 142.3 (1C C60),
142.55 (1C C60), 142.67 (1C C60), 142.70 (1C C60), 142.75 (1C
C60), 142.83 (1C C60), 142.9 (1C C60), 143.28 (1C C60), 143.32
(1C C6H4), 143.34 (1C C60), 143.4 (2C C60), 143.8 (1C C60),
144.1 (1C C60), 144.2 (2C C60), 144.3 (1C C60), 144.37 (1C C60),
144.38 (2C C60), 144.5 (1C C60), 144.6 (2C C60), 144.7 (1C C60),
145.0 (1C C60), 145.26 (1C C60), 145.31 (1C C60), 145.66 (1C
C60), 145.72 (1C C60), 146.9 (1C C60), 147.0 (1C C60), 147.1 (1C
C60), 147.2 (1C C60), 147.3 (1C C60), 147.6 (1C C60), 148.2 (1C
C60), 148.6 (1C C60), 148.7 (1C C60), 148.8 (1C C60), 150.5 (1C
C60), 152.9 (1C C60), 156.5 (1C C60), 158.4 (1C C60), 159.1 (1C
C60), 166.8 (1C C6H4), 174.4 (1C COOMe). HRMS: (APCI-
TOF, negative) m/z calcd for C70O3H12 [M]-: 900.0783, found
900.0774.
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o-chloranil (12.3 mg, 50 µmol), 2b (200 µmol) and TfOH (0.1
M solution in o-DCB, 20 µL, 2 µmol) at 100 oC stirring for 5h
afforded 3b and 3b’ (14.1mg ,84%).1H NMR (500 MHz,
CDCl3/CS2 = 1:2) of 3b: δ 2.79 (s, 3H), δ 3.98 (s, 3H), δ 7.18-
7.21 (m, 2H), δ 8.22-8.25 (m, 2H). 13C {1H} NMR (150 MHz,
CDCl3/CS2 = 1:2) of 3b: δ 37.4 (1C CH3), 54.5 (1C OMe), 55.3
(2C C60), 115.2 (2C C6H4), 128.5 (2C C6H4), 129.97 (1C C60),
130.02 (1C C60), 133.2 (1C C60), 137.4 (1C C60), 137.9 (1C C60),
138.9 (1C C60), 140.0 (1C C60), 141.1 (1C C6H4), 142.1 (1C C60),
142.5 (2C C60), 142.66 (1C C60), 142.74 (1C C60), 142.83 (1C
C60), 142.84 (1C C60), 143.23 (1C C60), 143.28 (1C C60), 143.29
(2C C60), 143.31 (2C C60), 143.37 (1C C60), 143.9 (1C C60),
144.08 (2C C60), 144.10 (1C C60), 144.15 (1C C60), 144.30 (1C
C60), 144.35 (1C C60), 144.41 (1C C60), 144.48 (1C C60), 144.50
(2C C60), 144.52 (1C C60), 144.54 (1C C60), 144.55 (2C C60),
144.7 (1C C60), 145.0 (1C C60), 145.2 (1C C60), 145.3 (1C C60),
145.6 (1C C60), 145.68 (1C C60), 147.01 (2C C60), 147.02 (1C
C60), 147.06 (1C C60), 147.08 (1C C60), 147.14 (1C C60), 147.2
(1C C60), 147.3 (1C C60), 148.3 (1C C60), 148.6 (1C C60), 148.8
(2C C60), 151.0 (1C C60), 152.9 (1C C60), 157.3 (2C C60), 158.4
(1C C60), 159.7 (1C C6H4). HRMS of 3b: (APCI-TOF, negative)
m/z calcd for C68OH10 [M]-:842.0732, found 842.0725. HRMS
of 3b’: (APCI-TOF, negative) m/z calcd for C68OH10 [M]-:
842.0732, found 842.0714.
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1-methyl-4-(4-chloro-phenyl) [60] fullerene (3e) Following
the general procedure, the reaction of 1a (14.7 mg, 20 µmol)
with o-chloranil (12.3 mg, 50 µmol), 2e (200 µmol) and TfOH
(0.1 M solution in o-DCB, 20 µL, 2 µmol) at 100 oC stirring for
24 h afforded 3e (13.4 mg, 79%).1H NMR (500 MHz,
CDCl3/CS2 = 1:2) δ 2.8 (s, 3H), δ 7.65-7.68 (m, 2H), δ 8.32 -
8.31 (m, 2H). 13C {1H} NMR (150 MHz, CDCl3/CS2 = 1:2) δ
30.5(1C CH3), 51.8 (1C C60CH3), 52.6 (1C C60Ph), 125.7 (1C
C60), 126.8 (2C C6H4), 128.0 (2C C6H4), 128.7 (1C C60), 132.79
(1C C60), 135.60 (1C C60), 135.96 (1C C60), 136.76 (1C C60),
137.3 (1C C60), 137.7 (2C C60), 139.4 (1C C60), 140.2 (1C C60),
140.4 (1C C60), 140.6 (1C C60), 140.7 (1C C60), 140.8 (1C C60),
140.9 (1C C60), 141.0 (1C C60), 141.38 (2C C60), 141.40 (1C
C6H4), 141.44 (1C C60), 141.8 (1C C60), 142.17 (1C C60), 142.18
(1C C60), 142.20 (2C C60), 142.30 (1C C60), 142.35 (1C C60),
142.39 (1C C60), 142.42 (1C C60), 142.47 (1C C60), 142.51 (1C
C60), 142.59 (1C C60), 142.60 (1C C60), 142.7 (1C C60), 142.8
(1C C60), 143.02 (1C C60), 143.05 (1C C60), 143.3 (2C C60),
143.4 (2C C60), 143.7 (1C C60), 143.8 (1C C60), 144.9 (1C C60),
145.11 (1C C60), 145.13 (1C C6H4), 145.14 (1C C60), 145.2 (1C
C60), 145.3 (1C C60), 145.4 (1C C60), 145.6 (1C C60), 146.2 (1C
C60), 146.6 (1C C60), 146.85 (1C C60), 146.92 (1C C60), 148.2
(1C C60), 154.5 (1C C60), 156.3 (1C C60). HRMS: (APCI-TOF,
negative) m/z calcd for C67ClH7 [M]-: 846.0246, found
846.0233.
1-methyl-4-(4-methyl-phenyl) [60] fullerene (3c) Following
the general procedure, the reaction of 1a (14.7 mg, 20 µmol)
with o-chloranil (12.3 mg, 50 µmol), 2c (200 µmol) and TfOH
(0.1 M solution in o-DCB, 20 µL, 2 µmol) at 100 oC stirring for
8 h afforded 3c (12.8 mg, 78%).1H NMR (500 MHz,
CDCl3/CS2 = 1:2) δ 2.57 (s, 3H), δ 2.79 (m, 1H), δ 7.49 (d, J =
10 Hz, 2H), δ 8.21 (d, J = 10 Hz, 2H). 13C {1H} NMR (150 MHz,
CDCl3/CS2 = 1:2) δ 21.6 (1C CH3), 28.2 (1C CH3), 54.5 (1C
C60CH3), 61.4 (1C C60Ph), 127.3 (2C C6H4), 130.5 (2C C6H4),
137.5 (1C C60), 137.9 (2C C60), 138.1 (1C C6H4), 138.2 (1C C60),
138.9 (1C C60), 139.0 (1C C60), 141.2 (1C C60), 142.1 (1C C60),
142.3 (1C C60), 142.5 (1C C60), 142.66 (1C C60), 142.73 (2C
C60), 142.8 (2C C60), 143.2 (1C C60), 143.26 (1C C60), 143.28
(2C C60), 143.3 (1C C60), 143.4 (1C C60), 143.92 (1C C60),
144.08 (1C C60), 144.09 (1C C60), 144.15 (1C C60), 144.26 (1C
C60), 144.30 (1C C60), 144.35 (1C C60), 144.39 (1C C60), 144.50
(2C C60), 144.52 (2C C60), 144.54 (1C C60), 144.8 (1C C60),
144.95 (1C C60), 145.00 (1C C60), 145.05 (1C C60), 145.22 (1C
C60), 145.25 (1C C60), 146.99 (1C C60), 147.08 (2C C60), 147.10
(1C C60), 147.13 (1C C60), 147.17 (1C C60), 147.22 (1C C60),
147.3 (1C C60), 148.3 (1C C60), 148.67 (1C C60), 148.75 (1C
C60), 148.78 (1C C60), 150.9 (1C C60), 152.9 (2C C60), 157.3 (2C
C60), 158.44 (1C C6H4). HRMS: (APCI-TOF, negative) m/z
calcd for C68H10 [M]-: 826.0782, found 826.0748.
1,4-bisphenyl [60] fullerene (4a) Following the general proce-
dure, the reaction of 1b (15.8 mg, 20 µmol) with o-chloranil
(12.3 mg, 50 µmol), 2a (200 µmol) and TfOH (0.1 M solution
in o-DCB, 20 µL, 2 µmol) at 100 oC stirring for 6 h afforded 4a
(15.0 mg, 86%).1H NMR (500 MHz, CDCl3/CS2 = 1:2) δ 7.48-
7.51 (m, 2H), δ 7.54-7.57 (m, 4H), δ 8.14-8.16 (m, 4H). 13C {1H}
NMR (150 MHz, CDCl3/CS2 = 1:2) δ 61.9 (2C C60C), 127.7
(4C C6H5), 128.4 (2C C6H5), 129.6 (4C C6H5), 137.6 (2C C60),
139.0 (2C C60), 140.5 (2C C60), 142.3 (2C C60), 142.4 (2C C60),
142.7 (2C C60), 142.8 (2C C60), 142.9 (2C C60), 143.34 (2C C60),
143.36 (2C C60), 143.4 (2C C60), 144.0 (2C C60), 144.1 (2C
C6H5), 144.4 (2C C60), 144.46 (2C C60), 144.52 (2C C60), 144.6
(2C C60), 144.9 (2C C60), 145.0 (2C C60), 145.3 (2C C60), 145.3
(2C C60), 145.8(2C C60), 147.0 (2C C60), 147.10 (2C C60), 147.2
(2C C60), 147.3 (2C C60), 148.6 (2C C60), 148.8 (2C C60), 151.1
(2C C60) 156.7 (2C C60). HRMS: (APCI-TOF, negative) m/z
calcd for C72H10 [M]-: 874.0783, found 874.0782.
1-methyl-4-(2-methoxybenzoate) [60] fullerene (3d) Follow-
ing the general procedure, the reaction of 1a (14.7 mg, 20 µmol)
with o-chloranil (12.3 mg, 50 µmol), 2d (200 µmol) and TfOH
(0.1 M solution in o-DCB, 20 µL, 2 µmol) at 100 oC stirring for
12 h. After cooling to room temperature, the mixture was evap-
orated and the residue was dissolved by 5 mL CS2. The solution
was passed through a silica gel (eluent: CS2: Dichloromethane
= 10:1) and afforded 3d (14.8 mg, 82%). 1H NMR (500 MHz,
CDCl3/CS2 = 1:2) δ 2.75 (s, 3H), 3.90 (s, 3H), 4.00 (s, 3H), δ
7.23-7.25 (d, J = 10 Hz, 1H), δ 8.36-8.48 (dd, J1 = 5 Hz J2 =10
Hz, 1H), δ 8.60-8.61 (d, J = 5 Hz, 1H). 13C {1H} NMR (150
MHz, CDCl3/CS2 = 1:2) δ 36.0 (1C CH3), 52.1 (1C COOMe),
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Page 7 of 9
The Journal of Organic Chemistry
1-phenyl-4-(4-methoxyphenyl) [60] fullerene (4b) and 1-
phenyl-4-(2-methoxyphenyl) [60] fullerene (4b’)Following
the general procedure, the reaction of 1b (15.8 mg, 20 µmol)
with o-chloranil (12.3 mg, 50 µmol), 2b (200 µmol) and TfOH
(0.1 M solution in o-DCB, 20 µL, 2 µmol) at 100 oC stirring for
6 h afforded 4b and 4b’ (17.4 mg, 96%). 1H NMR (500 MHz,
CDCl3/CS2 = 1:2) of 4b: δ 8.14 - 8.16 (d, J = 10 Hz, 2H), 8.01
- 8.03 (d, J = 10 Hz, 2H), 7.55 - 7.58 (m, 2H), 7.48 - 7.51 (m,
2H), 7.04 - 7.06 (d, J = 10 Hz, 2H), 3.93(S, 3H). 13C {1H} NMR
(150 MHz, CDCl3/CS2 = 1:2) of 4b: δ 55.26 (1C OMe), 61.3
(1C C60C), 61.8 (1C C60C), 114.9 (2C C6H4), 127.7 (2C C6H5),
128.4 (1C C6H5), 128.8 (2C C6H5), 129.6 (2C C6H4), 132.6 (1C
C60), 137.6 (1C C60), 138.96 (1C C60), 139.03 (1C C60),
137.5 (1C C60), 140.6 (1C C60), 141.2 (1C C60), 142.3 (1C
C60), 142.43 (1C C60), 142.45 (1C C60), 142.7 (2C C60),
142.8 (2C C60), 143.0 (1C C60), 143.3 (1C C60), 143.3 (2C
C60), 143.36 (1C C60), 143.38 (2C C60), 144.0 (1C C60),
144.09 (1C C60), 144.12 (1C C60), 144.17 (2C C60), 144.18
(2C C60), 144.39 (1C C60), 144.43 (1C C60), 144.45 (1C C60),
144.49 (1C C60), 144.53 (2C C60), 144.6 (1C C60), 144.92 (2C
C60), 145.04 (1C C60), 145.1 (1C C60), 145.2 (1C C60), 145.3
(1C C60), 145.6 (1C C60), 145.7 (1C C6H5), 147.01 (1C C60),
147.02 (2C C60), 147.05 (1C C60), 147.1 (1C C60), 147.17 (2C
C60), 147.28 (1C C60), 147.30 (1C C6H4), 148.6 (1C C60),
148.7 (1C C60), 148.82 (1C C60), 148.84 (1C C60), 151.0 (1C
C60), 151.4 (1C C60), 156.7 (1C C60), 157.0 (1C C60), 159.6
(1C C6H4). HRMS for 4b: (APCI-TOF, negative) m/z calcd for
C73OH12 [M]-: 904.0888, found 904.0894. HRMS for 4b’:
(APCI-TOF, negative) m/z calcd for C73OH12 [M]-: 904.0888,
found 904.0895.
was passed through a silica gel (eluent: CS2:/CH2Cl2 = 10:1) and
afforded 4d (16.7 mg, 86%). H NMR (500 MHz, CDCl3/CS2
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= 1:2) δ 3.90 (s, 3H), δ 4.03 (s, 3H), δ 7.15 (d, J = 5 Hz, 1H), δ
7.49-7.52 (m, 1H), δ 7.57-7.60 (m, 2H), δ 8.16-8.18 (m, 2H), δ
8.22 (dd, J1 = 5 Hz, J2 =10 Hz, 1H), δ 8.46 (d, J = 2.5 Hz, 2H).
13C {1H} NMR (150 MHz, CDCl3/CS2 = 1:2) δ 52.1 (1C
COOOMe), 54.5 (1C C60C), 56.2 (1C OMe), 60.5 (1C C60C),
121.3 (1C C6H5), 125.5 (1C C6H3), 128.4 (1C C6H3), 129.1 (1C
C6H3), 129.99 (2C C60), 130.04 (2C C60), 130.6 (2C C6H5),
132.1 (2C C6H5), 133.0 (1C C6H3), 137.6 (1C C60), 137.9 (1C
C60), 138.7 (1C C60), 139.1 (1C C60), 141.2 (1C C60), 142.1
(1C C60), 142.3 (1C C60), 142.55 (1C C60), 142.67 (1C C60),
142.70 (1C C60), 142.75 (1C C60), 142.83 (1C C60), 142.86
(1C C60), 143.28 (1C C60), 143.32 (2C C600), 143.34 (1C C60),
143.4 (1C C60), 143.8 (1C C6H5), 144.1 (1C C60), 144.12 (1C
C60), 144.13 (1C C60), 144.2 (1C C60), 144.34 (1C C60),
144.37 (1C C60), 144.38 (1C C60), 144.39 (1C C6H3), 144.4
(1C C60), 144.5 (1C C60), 144.6 (2C C60), 144.7 (1C C60),
144.97 (1C C60), 145.00 (1C C60), 145.2 (1C C60), 145.3 (1C
C60), 145.66 (1C C60), 145.72 (1C C60), 146.9 (1C C60),
147.02 (1C C60), 147.04 (1C C60), 147.07 (1C C60), 147.09
(1C C60), 147.15 (1C C60), 147.25 (1C C60), 147.34 (1C C60),
147.5 (1C C60), 148.2 (1C C60), 148.5 (1C C60), 148.77 (1C
C60), 148.83 (1C C60), 150.5 (1C C60), 152.9 (1C C60), 156.5
(1C C60), 158.4 (1C C60), 159.1 (1C C60), 165.8 (1C C6H3),
174.4 (1C COOCH3). HRMS: (APCI-TOF, negative) m/z calcd
for C75O3H14 [M]-: 962.0943, found 962.0934.
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1-phenyl-4-(4-chloro-phenyl) [60] fullerene (4e) Following
the general procedure, the reaction of 1b (15.8 mg, 20 µmol)
with o-chloranil (12.3 mg, 50 µmol), 2e (200 µmol) and TfOH
(0.1 M solution in o-DCB, 20 µL, 2 µmol) at 100 oC stirring for
24 h afforded 4e (11.3 mg, 62%).1H NMR (500 MHz,
CDCl3/CS2 = 1:2) δ 7.50-7.54 (m, 3H), δ 7.57-7.61 (m, 2H), δ
8.05-8.09 (m, 2H), δ 8.13-8.13 (m, 2H). 13C {1H} NMR (150
MHz, CDCl3/CS2 = 1:2) δ 61.1 (1C C60C), 61.8 (1C C60C),
119.2 (1C C60), 124.0 (1C C6H5), 125.5 (1C C60), 127.6 (2C
C6H5), 128.4 (2C C6H4), 128.6 (1C C60), 129.0 (2C C6H5),
129.1 (1C C6H4), 129.7 (2C C6H4), 129.99 (1C C60), 130.04
(1C C60), 134.7 (1C C60), 137.5 (1C C60), 137.7 (1C C60),
138.87 (1C C60), 139.07 (1C C60), 139.2 (1C C60), 140.4 (1C
C60), 141.3 (1C C60), 142.2 (1C C60), 142.4 (1C C60), 142.5
(1C C60), 142.66 (1C C60), 142.70 (1C C60), 142.8 (1C C60),
143.0 (1C C60), 143.38 (1C C6H4), 143.40 (1C C6H5), 143.9
(1C C60), 144.07 (1C C60), 144.15 (2C C60), 144.21 (1C C60),
144.25 (1C C60), 144.29 (1C C60), 144.31 (1C C60), 144.36
(1C C60), 144.44 (1C C60), 144.49 (1C C60), 144.51 (1C C60),
144.57 (1C C60), 144.60 (1C C60), 144.7 (1C C60), 144.87 (1C
C60), 144.89 (1C C60), 144.98 (1C C60), 145.27 (1C C60),
145.35 (1C C60), 145.6 (1C C60), 145.8 (1C C60), 146.9 (1C
C60), 147.00 (1C C60), 147.06 (2C C60), 147.17 (1C C60),
147.20 (1C C60), 147.33 (1C C60), 147.35 (1C C60), 148.39
(1C C60), 148.6 (1C C60), 148.9 (1C C60), 149.0 (1C C60),
150.6 (1C C60), 151.0 (1C C60), 156.0 (1C C60), 156.7 (1C
C60). HRMS: (APCI-TOF, negative) m/z calcd for C72ClH9
[M]-: 908.0393, found 908.0407.
1-phenyl-4-(4-methyl-phenyl) [60] fullerene (4c) Following
the general procedure, the reaction of 1b (15.8 mg, 20 µmol)
with o-chloranil (12.3 mg, 50 µmol), 2c (200 µmol) and TfOH
(0.1 M solution in o-DCB, 20 µL, 2 µmol) at 100 oC stirring for
12 h afforded 4c (15.2 mg, 86%).1H NMR (500 MHz,
CDCl3/CS2 = 1:2) δ 2.52 (S, 3H), δ 7.345 (d, J = 5Hz, 2H), δ
7.48-7.51 (m, 1H), δ 7.55-7.58 (m, 2H), δ 7.99-8.01 (m, 2H), δ
8.14-8.16 (m, 2H).13C {1H} NMR (150 MHz, CDCl3/CS2 = 1:2)
δ 21.6 (1C CH3). 61.6 (1C C60C), 61.8 (1C C60C), 127.6 (2C
C6H3), 127.7 (2C C6H3), 128.4 (1C C6H5), 129.6 (2C C6H4),
130.2 (2C C6H4), 137.5 (1C C60), 137.60 (1C C60), 137.64 (1C
C60), 138.0 (1C C6H4), 138.97 (1C C60), 139.06 (1C C60),
140.6 (2C C60), 141.2 (2C C60), 142.3 (1C C60), 142.4 (2C
C60), 142.7 (2C C60), 142.8 (2C C60), 142.9 (1C C60), 143.31
(1C C60), 143.34 (2C C60), 143.35 (1C C60), 143.38 (1C C6H4),
144.02 (1C C60), 144.07 (1C C60), 144.1 (1C C60), 144.2 (1C
C6H5), 144.39 (1C C60), 144.42 (1C C60), 144.47 (1C C60),
144.49 (1C C60), 144.53 (2C C60), 144.55 (1C C60), 144.56
(1C C60), 144.9 (2C C60), 145.0 (1C C60), 145.1 (1C C60),
145.2 (1C C60), 145.3 (1C C60), 145.5 (1C C60), 145.7 (2C
C60), 147.0 (2C C60)1, 147.10 (1C C60), 147.11 (2C C60),
147.2 (1C C60), 147.3 (2C C60), 148.6 (1C C60), 148.7 (1C
C60), 148.8 (1C C60), 151.0 (1C C60), 151.3 (1C C60), 156.8
(1C C60),157.0 (2C C60). HRMS: (APCI-TOF, negative) m/z
calcd for C73H12 [M]-: 888.0939, found 888.0960.
1-phenyl-4-(2-methoxybenzoate) [60] fullerene (4d) Follow-
ing the general procedure, the reaction of 1b (15.8 mg, 20 µmol)
with o-chloranil (12.3 mg, 50 µmol), 2d (200 µmol) and TfOH
(0.1 M solution in o-DCB, 20 µL, 2 µmol) at 100 oC stirring for
12 h. After cooling to room temperature, the mixture was evap-
orated and the residue was dissolved by 5 mL CS2. The solution
ASSOCIATED CONTENT
Supporting Information
Experimental section including 1H and 13C NMR spectra and X-
ray crystallography data, CIF files and computation data.
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(7) Si, W.; Lu, S.; Bao, M.; Asao, N.; Yamamoto, Y.; Jin, T., Cu-Cata-
lyzed C–H Amination of Hydrofullerenes Leading to 1,4-Difunction-
alized Fullerenes. Org. Lett. 2014, 16, 620-623.
AUTHOR INFORMATION
Corresponding Author
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(8) Nambo, M.; Itami, K., Palladium-Catalyzed Carbon–Carbon
Bond Formation and Cleavage of Organo(hydro)fullerenes. Chem.
Eu. J. 2009, 15, 4760-4764.
*xmuzhangqy@xmu.edu.cn, *fgao@mnnu.edu.cn,
Notes
The authors declare no competing financial interest.
(9) (a) Zhang, Y.; Matsuo, Y.; Nakamura, E., Regiocontrolled Syn-
thesis of 1,2-di(organo)fullerenes Via Copper-assisted 1,4-aryl Mi-
gration from Silicon to Carbon. Org. Lett. 2011, 13, 6058-6061; (b)
Yang, X. Y.; Lin, H. S.; Jeon, I.; Matsuo, Y., Fullerene-Cation-Mediated
Noble-Metal-Free Direct Introduction of Functionalized Aryl
Groups onto [60]Fullerene. Org. Lett. 2018, 20, 3372-3376.
(10) Nambo, M.; Segawa, Y.; Itami, K., Aziridinofullerene: a Ver-
satile Platform for Functionalized Fullerenes. J. Am. Chem. Soc.
2011, 133, 2402-2405.
(11) Murata, Y.; Cheng, F.; Kitagawa, T.; Komatsu, K., Generation
of Fullerenyl Cation (EtO)2P+(OH)CH2−C60+ from RC60−H and from
RC60−C60R (R = CH2P(O)(OEt)2). J. Am. Chem. Soc. 2004, 126, 8874-
8875.
(12) (a) Hirsch, A., The Chemistry of the Fullerenes: An Overview.
Angew. Chem. Int. Ed. 1993, 32, 1138-1141; (b) Taylor, R.; Walton,
D. R. M., The Chemistry of Fullerenes. Nature. 1993, 363, 685-693;
(c) Diederich, F.; Thilgen, C., Covalent Fullerene Chemistry. Science.
1996, 271, 317-323; (d) Olah, G. A.; Bucsi, I.; Ha, D. S.; Aniszfeld, R.;
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ACKNOWLEDGMENT
This research was supported by the National Natural Science
Foundation of China (21771152, 2172100121, 21390390,
51572231, 21701134, 2170010228), the 973 Program of China
(2015CB932301) and the Fundamental Research Funds for the
Central Universities (20720170028, 20720160084).
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