Aziridinofullerene: A Versatile platform for functionalized fullerenes

Article abstract of DOI:10.1021/ja111213k

An aziridine moiety on the fullerene core can serve as an acid-triggered reacting template for the controlled synthesis of a range of functionalized fullerenes that are otherwise difficult to synthesize in an efficient and selective manner. A copper-catal

Full text of DOI:10.1021/ja111213k

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
Supporting Information
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
Masakazu Nambo, Yasutomo Segawa, and Kenichiro Itami*
Department of Chemistry, Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
E-mail: itami@chem.nagoya-u.ac.jp
Table of Contents
1
2
3
4
.
.
.
.
General
S2
Substrate Synthesis
S3–S6
S6–S7
S8–S16
Cu-Catalyzed Aziridination of C Using TsN=IPh
6
0
Typical Procedure for TfOH-catalyzed Reaction of 1
with Aromatic Compounds
5
6
.
.
Typical Procedure for TfOH-catalyzed Reaction of 1
with Bifunctional Nucleophiles
S17–S23
S24–S29
Typical Procedure for TfOH-Catalyzed Reaction of 1
with 2,2’-Bithiophenes 6 and Arythiophenes 9
TfOH-Catalyzed Reaction of 1 with Alkyne 11
X-Ray Crystal Structure Analysis of 8c and 12
7
8
9
.
.
.
S29–S30
S30–S32
S33–S90
1
13
H and C NMR Spectra of Products
S1

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
1
. General
Unless otherwise noted, all materials including dry solvents were obtained from commercial
1
2
suppliers and used without further purification. TsN=IPh,
N-(1-hexyl)indole,
3
4
N-(1-butyl)carbazole, bis-(4-methoxyphenyl)-ethyne were prepared according to procedures
reported in the literature. Unless otherwise noted, all reactions were performed with dry solvents
under an atmosphere of argon in flame-dried glassware with standard vacuum-line techniques.
All work-up and purification procedures were carried out with reagent-grade solvents in air.
Analytical thin-layer chromatography (TLC) was performed using E. Merck silica gel 60 F254
precoated plates (0.25 mm). The developed chromatogram was analyzed by UV lamp (254 nm) and
ethanolic phosphomolybdic acid. Preparative recycling HPLC was performed with a JAI LC-9204
instrument equipped with a Buckyprep column (20 mm × 250 mm, Nacalai Tesque) using toluene
as an eluent and with JAIGEL-1H/JAIGEL-2H columns using chloroform as an eluent. HPLC
analysis was conducted on Shimadzu LC-20AB instrument equipped with a Buckyprep column
(
4.6 mm × 250 mm, Nacalai Tesque). High-resolution mass spectra (HRMS) were obtained from a
micrOTOF-QII (electrospray ionization time-of-flight mass spectrometry, ESI-TOFMS) and a
JMS-T100TD instrument (DART). Nuclear magnetic resonance (NMR) spectra were recorded on a
1
13
JEOL JMN-GSX-270 ( H 270 MHz, C 67.8 MHz) spectrometer and a JEOL A-400 and a JEOL
1
13
1
ECS-400 ( H 400 MHz, C 100 MHz) spectrometer. Chemical shifts for H NMR are expressed in
1
3
parts per million (ppm) relative to tetramethylsilane (δ 0.0 ppm). Chemical shifts for C NMR are
expressed in ppm relative to CDCl (δ 77.0 ppm). Data are reported as follows: chemical shift,
3
multiplicity (s = singlet, d = doublet, dd = doublet of doublets, t = triplet, q = quartet, quin =
quintet, sex = sextet, m = multiplet, br = broad signal), coupling constant (Hz), and integration.
1
Heuss, B. D.; Mayer, M. F.; Dennis, S.; Hossain, M. M. Inorg. Chim. Acta 2003, 342, 301.
Qi, T.; Qiu, W.; Liu, Y.; Zhang, H.; Gao, X.; Liu, Y.; Lu, K.; Du, C.; Yu, G.; Zhu, D. J. Org. Chem. 2008, 73,
2
4
638.
3
Zhao, T.; Liu, Z.; Song, Y.; Xu, W.; Zhang, D.; Zhu, D. J. Org. Chem. 2006, 71, 7422.
4
Rakshit, S.; Patureau, F. W.; Glorius, F. J. Am. Chem. Soc. 2010, 132, 9585.
S2

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
2
. Substrate Synthesis
5
Synthesis of 4,4’-Dinonyltriphenylamine (2c).
Nonyl
Pd(dba)2
P(tBu) ·HBF4
3
Nonyl
NaOtBu
PhNH2
PhN
toluene
reflux, 12 h
Br
Nonyl
2
c
A two-neck 50-mL glass round flask containing a magnetic stirring bar was flame-dried under
vacuum and filled with argon after cooling to room temperature. To this flask were added
Pd(dba) (69.0 mg, 0.12 mmol), P(tBu) ⋅HBF (52.2 mg, 0.18 mmol), NaOtBu (865 mg, 9 mmol), and
2
3
4
dry toluene (10 mL) under a stream of argon. After stirring the mixture at room temperature for 30
min, aniline (270 µL, 3 mmol) and 4-bromononylbenzene (2.55 g, 9 mmol) were added. The
reaction mixture was refluxed for 12 h. After cooling the reaction mixture to room temperature, the
mixture was passed through a short silica gel pad (EtOAc). The filtrate was evaporated and the
residue was purified by flash silica gel chromatography (hexane) to afford
1
4
,4’-dinonyltriphenylamine 2c (355 mg, 24%) as a colorless oil. Data of 2c: H NMR (400 MHz,
CDCl ) δ 0.88 (t, J = 6.8 Hz, 6H), 1.27–1.31 (m, 24H), 1.58–1.59 (m, 4H), 2.54 (t, J = 6.8 Hz, 4H), 6.92 (t,
3
1
3
J = 7.2 Hz, 1H), 6.97–7.04 (m, 10H), 7.19 (t, J = 7.2 Hz, 2H). C NMR (100 MHz, CDCl ) δ 14.1, 22.7,
3
2
9.3, 29.4, 29.5, 29.6, 31.5, 31.9, 35.4, 121.7, 123.1, 124.3, 129.0, 129.1, 137.4, 145.5, 148.3. HRMS
+
(
DART, positive) m/z calcd for C H N [M+H] : 498.4100, found 498.4100.
3
6
52
5
Synthesis of N-(p-Nonylphenyl)carbazole (2g).
Pd(dba)2
P(tBu) ·HBF4
3
Nonyl
NaOtBu
NH
N
Nonyl
toluene
reflux, 12 h
Br
2g
A two-neck 50-mL glass round flask containing a magnetic stirring bar was flame-dried under
vacuum and filled with argon after cooling to room temperature. To this flask were added
Pd(dba) (23.0 mg, 0.04 mmol), P(tBu) ⋅HBF (17.4 mg, 0.06 mmol), NaOtBu (144 mg, 1.5 mmol),
2
3
4
and dry toluene (5 mL) under a stream of argon. After stirring the mixture at room temperature for
5
Chen, C.-T.; Wei, Y.; Lin, J.-S.; Moturu, V. R. K.; Chao, W.-S.; Tao, Y.-T.; Chien, C.-H. J. Am. Chem. Soc. 2006,
1
28, 10992.
S3

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
3
0 min, carbazole (251 mg, 1.5 mmol) and 4-bromononylbenzene (283 mg, 1 mmol) were added.
The reaction mixture was refluxed for 12 h. After cooling the reaction mixture to room temperature,
the mixture was passed through a short silica gel pad (EtOAc). The filtrate was evaporated and the
residue was purified by flash silica gel chromatography (hexane) to afford
1
N-(p-nonylphenyl)carbazole 2g (237 mg, 64%) as a white solid. Data of 2g: H NMR (400 MHz,
CDCl ) δ 0.89 (t, J = 7.2 Hz, 3H), 1.29–1.35 (m, 12H), 1.63–1.71 (m, 2H), 2.67 (t, J = 8.0 Hz, 2H),
3
1
3
7
2
1
.21–7.27 (m, 2H), 7.31–7.41 (m, 8H), 8.10 (d, J = 8.0 Hz, 2H). C NMR (100 MHz, CDCl ) δ 14.1,
3
2.7, 29.36, 29.38, 29.5, 29.6, 31.5, 31.9, 35.7, 109.8, 119.7, 120.2, 123.2, 125.8, 126.9, 129.7, 135.1, 141.0,
+
42.3. HRMS (DART, positive) m/z calcd for C H N [M+H] : 370.2535, found 370.2536.
2
7
32
Synthesis of 4-tert-Butylthiobenzamide (4e).
O
S
Lawesson's reagent
NH2
NH2
THF
tBu
55 ºC, 4 h
tBu
4
e
A two-neck 50-mL glass round flask containing a magnetic stirring bar was flame-dried under
vacuum and filled with argon after cooling to room temperature. To this flask were added
-tert-butylbenzamide (354 mg, 2.0 mmol), Lawesson’s reagent (404 mg, 1.0 mmol), and dry THF
20 mL) under a stream of argon. After stirring the mixture at 55 °C for 4 h, solvent was
concentrated. The residue was purified by flash silica gel chromatography (CH Cl /hexane =
4
(
2
2
1
0
:1~1:0) to afford 4-tert-butylthiobenzamide 4e (123 mg, 32%) as a pale yellow solid. Data of 4e: H
NMR (400 MHz, CDCl ) δ 1.32 (s, 9H), 7.30 (brs, 1H), 7.41 (d, J = 8.4 Hz, 2H), 7.81 (d, J = 8.4 Hz, 2H),
3
1
3
7
.94 (brs, 1H). C NMR (100 MHz, CDCl ) δ 31.0, 34.9, 125.4, 126.8, 136.1, 155.8, 202.3. HRMS
3
+
(
DART, positive) m/z calcd for C H NS [M+H] : 194.1003, found 194.1002.
11
17
General Procedure for Synthesis of 5,5’-Dialkyl-2,2’-Bithiophenes.
Pd(OAc)2
bpy
Ag CO3
2
S
R
R
R
S
S
1,4-dioxane
120 ºC, 24 h
6
6
b (R = Hex)
c (R = Et)
R = Hex, Et
A 20-mL glass vessel equipped with J. Young® O-ring tap, containing a magnetic stirring bar
was flame-dried under vacuum and filled with argon after cooling to room temperature. To this
vessel were added Pd(OAc) (44.8 mg, 0.20 mmol), 2,2’-bipyridyl (31.2 mg, 0.20 mmol), Ag CO
2
2
3
S4

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
(
827 mg, 3.0 mmol), and dry 1,4-dioxane (4.0 mL) under a stream of argon. After stirring the
mixture at 60 °C for 30 min, 2-alkylthiophene (2.0 mmol) was added. The vessel was sealed with
O-ring tap, and then heated at 120 ºC for 24 h. After cooling the reaction mixture to room
temperature, the mixture was passed through a short silica gel pad (hexane). The filtrate was
evaporated and the residue was subjected to gel permeation chromatography (CHCl ) to afford
3
5
,5’-dialkyl-2,2’-bithiophene as a colorless oil.
5
6
1
2
,5’-Di-(1-hexyl)-2,2’-bithiophene (6b)
1
6% isolated yield. Data of 6b: H NMR (400 MHz, CDCl ) δ 0.89 (t, J = 7.2 Hz, 6H), 1.28–1.41 (m,
3
2H), 1.66 (quin, J = 8.0 Hz, 4H), 2.77 (t, J = 8.0 Hz, 4H), 6.64 (d, J = 3.6 Hz, 2H), 6.89 (d, J = 3.6 Hz,
1
3
H). C NMR (100 MHz, CDCl ) δ 14.0, 22.6, 28.7, 30.1, 31.6, 122.6, 124.5, 135.3, 144.7. HRMS
3
+
(
DART, positive) m/z calcd for C H S [M+H] : 335.1867, found 335.1870.
2
0
31 2
5
,5’-Diethyl-2,2’-bithiophene (6c)
1
5
3% isolated yield. Data of 6c: H NMR (400 MHz, CDCl ) δ 1.30 (t, J = 7.2 Hz, 6H), 2.81 (t, J = 7.2
3
1
3
Hz, 4H), 6.65 (d, J = 3.2 Hz, 2H), 6.89 (d, J = 3.2 Hz, 2H). C NMR (100 MHz, CDCl ) δ 15.8, 23.5,
3
+
1
2
22.6, 123.9, 135.21, 146.17. HRMS (DART, positive) m/z calcd for C H S [M+H] : 223.0615, found
1
2
15 2
23.0615.
6
Synthesis of 5-(1-Hexyl)-2-(p-methylphenyl)thiophene (9a).
PdCl (bpy)
2
Me
Ag CO
2
3
Hex
S
Hex
S
m-xylene
20 ºC, 12 h
Me
I
1
9a
A 20-mL glass vessel equipped with J. Young® O-ring tap, containing a magnetic stirring bar
was flame-dried under vacuum and filled with argon after cooling to room temperature. To this
vessel were added PdCl (bpy) (25 mg, 75 µmol), Ag CO (414 mg, 1.5 mmol), and dry m-xylene (7.5
2
2
3
mL) under a stream of argon. After stirring the mixture at room temperature for 30 min,
-iodotoluene (330 mg, 1.5 mmol) and 2-(1-hexyl)thiophene (410 µL, 2.3 mmol) were added. The
4
vessel was sealed with O-ring tap, and then heated at 120 ºC for 12 h. After cooling the reaction
mixture to room temperature, the mixture was passed through a short silica gel pad (EtOAc). The
filtrate was evaporated and the residue was subjected to gel permeation chromatography (CHCl3)
to afford 5-(1-hexyl)-2-(p-methylphenyl)thiophene 9a (146 mg, 29%) as an orange solid. Data of 9a:
1
H NMR (400 MHz, CDCl ) δ 0.89 (t, J = 6.8 Hz, 3H), 1.26–1.42 (m, 6H), 1.69 (quin, J = 7.6 Hz, 2H),
3
2
.34 (s, 3H), 2.80 (t, J = 7.6 Hz, 2H), 6.71 (d, J = 3.6 Hz, 1H), 7.06 (d, J = 3.6 Hz, 1H), 7.14 (d, J = 8.0
6
Yanagisawa, S.; Ueda, K.; Sekizawa, H.; Itami, K. J. Am. Chem. Soc. 2009, 131, 14622.
S5

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
1
3
Hz, 2H), 7.44 (d, J = 8.0 Hz, 2H). C NMR (100 MHz, CDCl ) δ 14.1, 21.1, 22.6, 28.8, 30.2, 31.59,
3
3
1.62, 122.1, 124.8, 125.4, 129.4, 132.0, 136.7, 141.8, 145.1. HRMS (DART, positive) m/z calcd for
+
C H S [M+H] : 259.1521, found 259.1521.
1
7
23
7
Synthesis of 2-(1-Hexyl)-4-(p-methylphenyl)thiophene (9b)
Me
Pd(OAc)2
bpy
TEMPO
Me
Hex
Hex
S
CF C H
3 6 5
S
(
HO) B
2
80 ºC, 12 h
9b
A 10-mL glass vessel equipped with J. Young® O-ring tap, containing a magnetic stirring bar
was flame-dried under vacuum and filled with argon after cooling to room temperature. To this
vessel were added Pd(OAc) (11.2 mg, 50 µmol), 2,2’-bipyridyl (7.9 mg, 50 µmol), and dry
2
α,α,α-trifluorotoluene (100 µL) under a stream of argon. After stirring the mixture at 60 °C for 30
min, p-methylphenylboronic acid (272 mg, 2.0 mmol), TEMPO (312 mg, 2.0 mmol),
2
-(1-hexyl)thiophene (90 µL, 0.5 mmol), and then α,α,α-trifluorotoluene (100 µL) were added. The
vessel was sealed with O-ring tap, and then heated at 80 ºC for 12 h. After cooling the reaction
mixture to room temperature, the mixture was passed through a short silica gel pad (hexane). The
filtrate was evaporated and the residue was subjected to gel permeation chromatography (CHCl3)
1
to afford 2-(1-hexyl)-4-(p-methylphenyl)thiophene 9b (84.3 mg, 65%) as colorless oil. Data of 9b: H
NMR (400 MHz, CDCl ) δ 0.89 (t, J = 7.2 Hz, 3H), 1.26–1.40 (m, 6H), 1.70 (quin, J = 7.6 Hz, 2H), 2.35
3
1
3
(
s, 3H), 2.82 (t, J = 7.6 Hz, 2H), 7.04 (s, 1H). 7.16–7.18 (m, 3H), 7.45 (d, J = 7.6 Hz, 2H). C NMR (100
MHz, CDCl ) δ 14.1, 21.1, 22.6, 28.9, 30.2, 31.59, 31.61, 117.1, 123.4, 126.1, 129.4, 133.4, 136.6, 141.7,
3
+
1
46.5. HRMS (DART, positive) m/z calcd for C H S [M+H] : 259.1521, found 259.1523.
1
7
23
3
. Cu-Catalyzed Aziridination of C Using TsN=IPh (Table 1, entry 15).
60
Ts
N
CuCl
2,6-lutidine
TsN=IPh
1
,2-Cl C H
2 6 4
rt, 12 h
1
7
Kirchberg, S.; Tani, S.; Ueda, K.; Yamaguchi, J.; Studer, A.; Itami, K. Angew. Chem., Int. Ed. 2011, in press.
DOI: 10.1002/anie.201007060.
S6

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
A two-neck 200-mL glass round flask containing a magnetic stirring bar was flame-dried under
vacuum and filled with argon after cooling to room temperature. To this flask were added CuCl
(
1.2 mg, 12 µmol), o-dichlorobenzene (40 mL), and then 2,6-lutidine (2.0 µL, 24 µmol) under a
stream of argon. After stirring the mixture at room temperature for 30 min, C (432 mg, 600 µmol)
6
0
and TsN=IPh (224 mg, 600 µmol) were added. This mixture was stirred at room temperature for 12
h and purified by flash silica gel chromatography (toluene/hexane = 1:2~1:1) to afford
N-tosyl[1,2]aziridino[60]fullerene 1 (228 mg, 43%) as dark brown solid. C was recovered in 43%
6
0
8
1
yield (185 mg). Data of 1 : H NMR (400 MHz, CDCl /CS = 1:1) δ 2.56 (s, 3H), 7.50 (d, J = 8.3 Hz,
3
2
1
3
2
1
1
8
H), 8.19 (d, J = 8.3 Hz, 2H). C NMR (100 MHz, CDCl ) δ 21.75, 79.69, 128.44, 129.93, 135.63, 140.75,
3
41.20, 141.71, 142.02, 142.63, 142.94, 142.99, 143.12, 143.74, 143.81, 144.01, 144.36, 144.83, 144.89,
-
44.97, 145.14, 145.34. HRMS (ESI-TOF, negative) m/z calcd for C H NO S [M] : 889.0203, found
6
7
7
2
89.0205.
Figure S1. The HPLC chart of crude reaction mixture containing 1.
8
Minakata, S.; Tsuruoka, R.; Nagamachi, T.; Komatsu, M. Chem.Commun. 2008, 323.
S7

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
4
. Typical Procedure for TfOH-Catalyzed Reaction of 1 with Aromatic Compounds. (Table 2
entry 3)
A 10-mL glass Schlenk tube containing a magnetic stirring bar was flame-dried under vacuum
and filled with argon after cooling to room temperature. To this flask were added 1 (17.8 mg, 20
µmol), dry o-dichlorobenzene (2.0 mL), and then 4,4’-dinonyltriphenylamine 2c (100 mg, 200 µmol)
under a stream of argon. To the reaction mixture was added TfOH (0.2 M solution in
o-dichlorobenzene, 5 µL, 1 µmol) and then the mixture was stirred at 100 °C for 12 h. After cooling
to room temperature, the mixture was passed through a pad of silica gel with copious washings
with toluene (~20 mL). The filtrate was concentrated and subjected to preparative recycling HPLC
equipped with a Buckyprep column (eluent: toluene) to afford 1,4-bis[di(p-nonylphenyl)aminoph-
enyl]-1,4-dihydro[60]fullerene 3c (16.2 mg, 95%) as dark brown solid.
The Effect of Brønsted and Lewis Acids in the Reaction of 1 with Anisole (2a).
The effect of Brønsted acids employed in the nucleophilic substitution of 1 with 2a was
examined. Selected results are summarized in Table S1. Treatment of C (1 equiv) with anisole 2a
6
0
(
10 equiv) in the presence of TfOH (10 mol%) in o-dichlorobenzene at 100 ºC furnished
,4-bis(p-methoxyphenyl)-1,4-dihydro[60]fullerene (3a) in 81% yield (entry 1). When decreased the
1
amount of 2a, the reaction did not reach to full conversion (entry 2). TsOH also gave the product
but in a moderate yield (entry 3). When relatively weak Brønsted acids such as methanesulfonic
acid, trifluoroacetic acid, and acetic acid were employed, product was not observed (entries 4–6).
These results indicate that the acidity of Brønsted acid correlates with the reaction efficiency.
Lewis acid such as Sc(OTf) and Zn(OTf) were also examined, but the yield was not improved
3
2
(
entries 7 and 8).
Table S1. The effect of acids in the reaction of 1 with 2a.
MeO
OMe
Ts
N
1
0% Brønsted acid
or Lewis acid
H
1
,2-Cl C H
2 6 4
MeO
100 ºC, 12 h
2a
1
3a
entry
acid
CF SO H
yield (%)a
entry
acid
yield (%)a
1
2b
81
50c
69
<1
5
6
7
8
CF COOH
<1
<1
72
3
3
3
CF SO H
CH COOH
3
3
3
3
p-CH C H SO H
Sc(OTf)3
Zn(OTf)2
3
6
4
3
4
CH SO H
50c
3
3
a
Isolated yield. b 5 equiv of 2a was employed. c Converison of 1.
S8

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
Compound Data for 1,4-Disubstituted Fullerenes 3
Unless otherwise noted, 1,4-disubstituted fullerenes 3 described in this section were prepared
following the typical procedure. All products were purified by preparative recycling HPLC
equipped with a Buckyprep column (eluent: toluene).
9
1
,4-Bis(p-methoxyphenyl)-1,4-dihydro[60]fullerene (3a)
MeO
OMe
Ts
N
H
MeO
2
a
1
3a
Table 2, entry 1: 10% of catalyst was employed. 81% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 3.88 (s, 6H), 7.01 (d, J = 8.8 Hz, 4H), 7.98 (d, J = 8.8 Hz, 4H).
3
2
1
3
C NMR (100 MHz, CDCl /CS = 1:1) δ 55.02, 60.92, 114.57, 128.53, 132.48, 137.19, 138.68, 140.86,
3
2
1
1
1
41.94, 142.16, 142.49, 142.51, 142.63, 143.02, 143.05, 143.08, 143.79, 143.84, 143.88, 144.12, 144.20,
44.26, 144.64, 144.73, 144.92, 145.10, 145.44, 146.72, 146.78, 146.88, 146.99, 148.33, 148.53, 151.05,
-
56.69, 159.33. HRMS (ESI-TOF, negative) m/z calcd for C H O [M] : 934.0999, found 934.1000.
7
4
14
2
Figure S2. The HPLC chart of crude reaction mixture containing 3a.
9
Tajima, Y.; Hara, T.; Honma, T.; Matsumoto, S.; Takeuchi, K. Org. Lett. 2006, 8, 3203.
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Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
1
,4-Bis(2,5-dimethoxyphenyl)-1,4-dihydro[60]fullerene (3b)
OMe
MeO
Ts
N
MeO
OMe
OMe
H
MeO
2b
1
3b
Table 2, entry 2: 30% of catalyst was employed. 90% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 3.80 (d, J = 0.7 Hz, 6H), 3.94 (s, 6H), 6.89 (ddd, J = 8.8, 2.9,
3
2
1
3
0
5
1
1
.7 Hz, 2H), 6.97 (d, J = 8.8 Hz, 2H), 7.63 (d, J = 2.9 Hz, 2H). C NMR (100 MHz, CDCl /CS = 1:1) δ
3 2
5.40, 55.63, 59.74, 112.39, 113.89, 115.96, 130.32, 138.49, 139.16, 140.38, 141.67, 142.17, 142.18, 142.49,
42.69, 142.77, 142.94, 143.11, 143.46, 143.62, 143.91, 144.15, 144.18, 144.46, 144.51, 144.83, 144.95,
45.05, 145.36, 146.36, 146.65, 146.91, 146.94, 147.49, 147.99, 148.45, 150.58, 153.63, 153.87. HRMS
-
(
ESI-TOF, negative) m/z calcd for C H O [M] : 994.1211, found 994.1221.
7
6
18
4
Figure S3. The HPLC chart of crude reaction mixture containing 3b.
S10

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
1
,4-Bis[di(p-nonylphenyl)aminophenyl]-1,4-dihydro[60]fullerene (3c)
R N
2
NR2
Ts
N
H
R N
2
(
R = p-nonylphenyl)
2c
1
3c
Table 2, entry 3: Typical procedure. 95% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 0.88 (t, J = 6.4 Hz, 12H), 1.26–1.32 (m, 48H), 1.59 (quin, J =
3
2
8
.0 Hz, 8H), 2.54 (t, J = 8.0 Hz, 8H), 7.01 (brs, 16H), 7.13 (d, J = 8.4 Hz, 4H), 7.88 (d, J = 8.4 Hz, 4H).
C NMR (100 MHz, CDCl /CS = 1:1) δ 14.23, 22.89, 29.48, 29.59, 29.69, 29.72, 31.64, 32.00, 35.51,
1
3
3
2
6
1
1
1.13, 122.77, 124.53, 128.22, 129.14, 133.18, 137.33, 137.58, 138.69, 140.82, 141.94, 142.17, 142.49,
42.52, 142.69, 142.99, 143.02, 143.09, 143.81, 143.88, 144.12, 144.27, 144.64, 144.75, 144.89, 144.92,
45.08, 145.42, 146.70, 146.88, 146.93, 146.97, 147.97, 148.40, 148.51, 151.11, 156.56. HRMS (ESI-TOF,
-
negative) m/z calcd for C H N O [M+OAc] : 1743.8076, found 1743.8082.
1
33 103
2
Figure S4. The HPLC chart of crude reaction mixture containing 3c.
S11

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
1
,4-Bis(5-ethylthien-2-yl)-1,4-dihydro[60]fullerene (3d)
Et
Et
Ts
N
S
S
Et
H
S
2d
1
3d
Table 2, entry 4: Typical procedure. 94% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 1.40 (t, J = 7.6 Hz, 6H), 2.95 (dq, J = 7.6, 1.0 Hz, 4H),
3
2
1
3
6
6
1
1
9
.82–6.83 (m, 2H), 7.38 (d, J = 3.6 Hz, 2H). C NMR (100 MHz, CDCl /CS = 1:1) δ 16.05, 23.92,
3 2
9.51, 123.54, 125.81, 137.13, 138.60, 140.99, 142.21, 142.49, 142.63, 143.10, 143.14, 143.72, 143.81,
44.02, 144.16, 144.25, 144.31, 144.48, 144.51, 144.61, 145.05, 145.48, 146.50, 146.52, 146.75, 146.93,
-
47.04, 147.92, 147.96, 148.61, 150.47, 155.73. HRMS (ESI-TOF, negative) m/z calcd for C H S [M] :
7
2
14 2
42.0542, found 942.0537.
Figure S5. The HPLC chart of crude reaction mixture containing 3d.
S12

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
1
,4-Bis[N-(1-hexyl)indol-3-yl]-1,4-dihydro[60]fullerene (3e)
Hex
N
Hex
Ts
N
N
H
N
Hex
2e
1
3e
Table 2, entry 5: Typical procedure. 88% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 0.89 (t, J = 6.8 Hz, 6H), 1.24–1.29 (m, 12H), 1.70–1.78 (m,
3
2
4
H), 4.03 (t, J = 7.6 Hz, 4H), 7.06 (t, J = 8.0 Hz, 2H), 7.22 (t, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H),
1
3
7
.40 (s, 2H), 8.30 (d, J = 8.0 Hz, 2H). C NMR (100 MHz, CDCl /CS = 1:1) δ 14.14, 22.73, 26.77,
3 2
3
0.27, 31.48, 46.41, 56.21, 109.47, 109.52, 114.69, 119.80, 120.99, 121.05, 122.11, 126.31, 126.68, 126.79,
36.77, 137.50, 138.53, 140.76, 141.90, 142.13, 142.55, 142.61, 142.97, 143.00, 143.16, 143.83, 143.88,
43.99, 144.20, 144.32, 144.55, 144.64, 144.67, 144.99, 145.03, 145.38, 146.64, 146.89, 146.96, 147.19,
1
1
-
1
48.38, 148.44, 151.24, 156.66. HRMS (ESI-TOF, negative) m/z calcd for C H N [M] : 1120.2884,
8
8
36
2
found 1120.2886.
Figure S6. The HPLC chart of crude reaction mixture containing 3e.
S13

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
1
,4-Bis[N-(1-butyl)carbazol-3-yl]-1,4-dihydro[60]fullerene (3f)
Bu
N
Bu
Ts
N
N
H
N
Bu
2f
1
3f
Table 2, entry 6: Typical procedure. 86% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 0.94 (t, J = 7.3 Hz, 6H), 1.39 (sex, J = 7.3 Hz, 4H), 1.86 (quin,
3
2
J = 7.3 Hz, 4H), 4.31 (t, J = 7.3 Hz, 4H), 6.88–6.92 (m, 2H), 7.32–7.38 (m, 4H), 7.44 (d, J = 8.6 Hz, 2H),
1
3
7
.64 (d, J = 7.8 Hz, 2H), 8.23 (dd, J = 8.3, 2.0 Hz, 2H), 8.74 (d, J = 2.0 Hz, 2H). C NMR (100 MHz,
CDCl /CS = 1:1) δ 13.98, 20.76, 31.26, 42.87, 61.82, 108.32, 108.47, 109.14, 119.00, 119.85, 120.55,
3
2
1
1
1
22.52, 123.56, 125.05, 125.89, 131.48, 137.44, 138.74, 139.89, 140.68, 140.80, 141.98, 142.23, 142.49,
42.58, 142.96, 143.02, 143.09, 143.86, 143.89, 143.91, 144.13, 144.26, 144.29, 144.45, 144.68, 144.82,
44.95, 145.39, 145.57, 146.66, 146.86, 146.95, 147.05, 148.49, 148.57, 151.65, 156.98. HRMS (ESI-TOF,
-
negative) m/z calcd for C H N [M] : 1164.2571, found 1164.2559.
9
2
32
2
Figure S7. The HPLC chart of crude reaction mixture containing 3f.
S14

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
1
,4-Bis[N-(1-nonylphenyl)carbazol-3-yl]-1,4-dihydro[60]fullerene (3g)
R
N
R
Ts
N
N
H
N
R
(
R = p-nonylphenyl)
1
2g
3g
Table 2, entry 7: Typical procedure. 85% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 0.89 (t, J = 7.2 Hz, 6H), 1.24–1.39 (m, 24H), 1.70 (quin, J =
3
2
7
7
.6 Hz, 4H), 2.70 (t, J = 7.6 Hz, 4H), 6.96 (t, J = 7.6 Hz, 2H), 7.28–7.35 (m, 8H), 7.42 (d, J = 8.8 Hz, 4H),
.46 (d, J = 8.4 Hz, 2H), 7.67 (d, J = 7.6 Hz, 2H), 8.18 (dd, J = 8.4, 1.6 Hz, 2H), 8.77 (d, J = 1.6 Hz, 2H).
C NMR (100 MHz, CDCl /CS = 1:1) δ 14.25, 22.91, 29.49, 29.58, 29.69, 29.72, 31.54, 32.01, 35.80,
1
3
3
2
6
1
1
1
1.80, 109.66, 110.44, 119.83, 120.00, 120.46, 122.91, 124.10, 125.23, 126.19, 126.60, 129.67, 132.58,
34.76, 137.46, 138.72, 140.39, 140.72, 141.27, 141.93, 142.13, 142.18, 142.41, 142.51, 142.90, 142.98,
43.04, 143.83, 143.85, 144.07, 144.22, 144.39, 144.62, 144.76, 144.91, 145.34, 145.55, 146.62, 146.81,
46.90, 147.00, 148.45, 148.53, 151.54, 156.81. HRMS (ESI-TOF, negative) m/z calcd for C H N
114 60
2
-
[
M] : 1456.4762, found 1456.4769.
Figure S8. The HPLC chart of crude reaction mixture containing 3g.
S15

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
1
,4-Bis(1-pyrenyl)-1,4-dihydro[60]fullerene (3h)
Ts
N
H
2
h
1
3h
Table 2, entry 8: Typical procedure. 94% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 7.91 (d, J = 9.2 Hz, 2H), 7.93 (t, J = 7.6 Hz, 2H), 7.97 (d, J =
3
2
1
3
9
.2 Hz, 2H), 8.05–8.12 (m, 8H), 8.99 (d, J = 8.0 Hz, 2H), 10.07 (d, J = 9.6 Hz, 2H). C NMR (100 MHz,
CDCl /CS = 1:1) δ 63.07, 124.59, 125.10, 125.33, 125.56, 125.61, 126.00, 127.01, 127.93, 128.01, 128.05,
3
2
1
1
1
1
30.11, 130.16, 131.11, 131.18, 134.02, 138.16, 140.66, 142.19, 142.56, 142.99, 143.11, 143.34, 143.52,
44.01, 144.22, 144.42, 144.67, 145.12, 145.31, 145.66, 146.67, 146.70, 146.84, 146.92, 147.15, 147.32,
-
47.41, 148.47, 150.70. HRMS (ESI-TOF, negative) m/z calcd for C H [M] : 1081.1547, found
9
2
18
081.1550.
Figure S9. The HPLC chart of crude reaction mixture containing 3h.
S16

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
5
3
. Typical Procedure for TfOH-Catalyzed Reaction of 1 with Bifunctional Nucleophlies. (Table
, entry 1)
A 10-mL glass Schlenk tube containing a magnetic stirring bar was flame-dried under vacuum
and filled with argon after cooling to room temperature. To this flask were added 1 (8.9 mg, 10
µmol), dry o-dichlorobenzene (1.0 mL), and 4-tert-butylphenol 4a (2.3 mg, 15 µmol) under a stream
of argon. To the reaction mixture was added TfOH (0.2 M solution in o-dichlorobenzene, 5 µL, 1
µmol) and then the mixture was stirred at 100 °C for 12 h. After cooling to room temperature, the
mixture was passed through a pad of silica gel with copious washings with toluene (~15 mL). The
filtrate was concentrated and subjected to preparative recycling HPLC equipped with a Buckyprep
column (eluent: toluene) to afford 5’-tert-butyl[60]fullereno[1,9-b]benzofuran 5a (8.3 mg, 96%) as
dark brown solid.
Compound Data for 1,2-Fused Fullerenes 5
Unless otherwise noted, 1,2-fused fullerenes 5 described in this section were prepared
following the typical procedure. All products were purified by preparative recycling HPLC
equipped with a Buckyprep column (eluent: toluene).
S17

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
5
’-tert-Butyl[60]fullereno[1,9-b]benzofuran (5a)
tBu
Ts
N
O
HO
H
tBu
4a
1
5a
Table 3, entry 1: Typical procedure. 96% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 1.44 (s, 9H), 7.30 (d, J = 8.5 Hz, 1H), 7.54 (dd, J = 8.5, 2.2 Hz,
3
2
1
3
1
1
1
1
H), 7.84 (d, J = 2.2 Hz, 1H). C NMR (100 MHz, CDCl /CS = 1:1) δ 31.68, 34.47, 71.32, 102.87,
3 2
11.27, 121.99, 125.79, 127.79, 135.67, 137.37, 139.65, 140.67, 141.64, 142.01, 142.15, 142.19, 142.55,
42.59, 142.78, 144.25, 144.31, 144.89, 144.91, 145.05, 145.13, 145.41, 145.48, 145.57, 145.80, 145.91,
46.02, 146.07, 146.16, 147.26, 147.99, 150.17, 155.11. HRMS (ESI-TOF, negative) m/z calcd for
-
C H O [M] : 868.0894, found 868.0889.
7
0
12
Figure S10. The HPLC chart of crude reaction mixture containing 5a.
S18

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
1
0
5
’-Butyl-1H-[60]fullereno[1,9:2’,3’]indole (5b)
Bu
Ts
N
HN
H N
2
H
Bu
4b
1
5b
Table 3, entry 2: The reaction time was 48 h. 62% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 0.97 (t, J = 7.3 Hz, 3H), 1.28–1.47 (m, 2H), 1.63–1.71 (m, 2H),
3
2
2
.67 (t, J = 7.8 Hz, 2H), 5.59 (brs, 1H), 7.03 (d, J = 8.1 Hz, 1H), 7.19 (dd, J = 8.1, 1.3 Hz, 1H), 7.60 (d, J
1
3
=
1.3 Hz, 1H). C NMR (100 MHz, CDCl /CS = 1:1) δ 14.17, 22.74, 34.30, 35.48, 73.87, 84.10, 111.64,
3 2
1
1
1
25.47, 126.32, 130.03, 135.47, 135.49, 136.17, 139.71, 140.61, 141.60, 141.93, 141.95, 141.99, 142.22,
42.33, 142.43, 142.50, 142.86, 144.17, 144.31, 144.51, 144.87, 144.89, 145.20, 145.33, 145.47, 145.64,
45.74, 145.80, 145.92, 145.94, 146.03, 147.17, 147.72, 148.35, 150.97. HRMS (ESI-TOF, negative) m/z
-
calcd for C H N [M] : 867.1053, found 867.1062.
7
0
13
Figure S11. The HPLC chart of crude reaction mixture containing 5b.
1
0
Numata, Y.; Kawashima, J.; Hara, T.; Tajima, Y. Chem. Lett. 2008, 37, 1018.
S19

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
1
1
5
’-Phenyl[60]fullereno[1,9-b]furan-4’-carboxylic acid ethyl ester (5c)
Ph
Ts
N
CO Et
2
O
O
CO Et
2
Ph
H H
4c
1
5c
Table 3, entry 3: Typical procedure. 86% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 1.17 (t, J = 7.3 Hz, 3H), 4.25 (q, J = 7.3 Hz, 2H), 7.56–7.60 (m,
3
2
1
3
3
1
1
1
H), 8.09–8.11 (m, 2H). C NMR (100 MHz, CDCl /CS = 1:1) δ 13.89, 60.59, 64.63, 104.56, 127.79,
3 2
29.34, 129.88, 130.41, 131.01, 135.39, 137.42, 139.30, 139.80, 141.37, 141.47, 142.17, 142.21, 142.34,
42.40, 142.57, 142.64, 144.11, 144.25, 144.39, 144.68, 144.90, 145.05, 145.32, 145.53, 145.83, 145.89,
46.05, 146.11, 146.32, 147.20, 147.24, 147.90, 148.17, 163.63, 166.44. HRMS (ESI-TOF, negative) m/z
–
calcd for C H O [M] : 910.0635, found 910.0636.
7
1
10
3
Figure S12. The HPLC chart of crude reaction mixture containing 5c.
11
Li, C.; Zhang, D.; Zhang, X.; Wu, S.; Gao, X. Org. Biomol. Chem. 2004, 2, 3464.
S20

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
4
’-(4-Methylbenzoyl)-5’-(4-methylphenyl)[60]fullereno[1,9-b]furan (5d)
p-Tol
O
Ts
N
O
p-Tol
O
O
p-Tol
p-Tol
H H
4
d
1
5d
Table 3, entry 4: Typical procedure. 87% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 2.33 (s, 3H), 2.36 (s, 3H), 7.04 (d, J = 7.6 Hz, 2H), 7.08 (d, J =
3
2
1
3
7
1
1
1
1
.6 Hz, 2H), 7.60 (dm, J = 8.0 Hz, 2H), 7.81 (dm, J = 8.0 Hz, 2H). C NMR (100 MHz, CDCl /CS =
3 2
:1) δ 21.36, 21.57, 74.83, 101.72, 110.73, 125.98, 128.81, 129.08, 129.40, 129.79, 130.30, 130.56, 134.99,
35.38, 137.48, 139.69, 139.81, 140.92, 141.44, 141.54, 142.06, 142.13, 142.24, 142.41, 142.46, 142.55,
42.61, 143.01, 143.98, 144.17, 144.36, 144.76, 144.82, 144.97, 145.19, 145.49, 145.77, 145.81, 145.90,
46.06, 146.21, 146.55, 147.08, 147.87, 148.90, 162.14, 191.27. HRMS (ESI-TOF, negative) m/z calcd for
–
C H O [M] : 970.0999, found 970.1001.
7
7
14
2
Figure S13. The HPLC chart of crude reaction mixture containing 5d.
S21

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
2
’-(4-tert-Butylphenyl)[60]fullereno[1,9-d]thiazole (5e)
p-tBuC H
6
4
Ts
N
S
N
S
H N
2
tBu
4
e
1
5e
Table 3, entry 5: The reaction time was 48 h. 67% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 1.44 (s, 9H), 7.59 (d, J = 8.0 Hz, 2H), 8.09 (d, J = 8.0 Hz, 2H).
3
2
1
3
C NMR (100 MHz, CDCl /CS = 1:1) δ 31.03, 34.76, 74.33, 104.46, 125.72, 128.78, 129.38, 134.76,
3
2
1
1
1
9
35.20, 139.51, 140.13, 141.51, 141.60, 141.70, 141.92, 142.17, 142.41, 142.49, 142.52, 142.81, 143.50,
44.11, 144.24, 145.04, 145.07, 145.22, 145.42, 145.57, 145.77, 145.86, 145.90, 145.95, 146.18, 146.41,
–
47.59, 147.65, 149.36, 155.52, 167.58. HRMS (ESI-TOF, negative) m/z calcd for C H NS [M] :
7
1
13
11.0774, found 911.0765.
Figure S14. The HPLC chart of crude reaction mixture containing 5e.
S22

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
4
-([60]Fullereno[1,9-d][1,3,2]-dioxaborolan-2-yl)toluene (5f)
p-Tol
Ts
N
B
O
O
(
HO) B
2
4f
1
5f
Table 3, entry 6: 3 equiv of 4f was employed. 57% isolated yield.
1
H NMR (400 MHz, CDCl /CS = 1:1) δ 2.51 (s, 3H), 7.38 (d, J = 8.4 Hz, 2H), 8.17 (d, J = 8.4 Hz, 2H).
3
2
1
3
C NMR (100 MHz, CDCl /CS = 1:1) δ 31.03, 34.76, 74.33, 104.46, 125.72, 128.78, 129.38, 134.76,
3
2
1
1
1
9
35.20, 139.51, 140.13, 141.51, 141.60, 141.70, 141.92, 142.17, 142.41, 142.49, 142.52, 142.81, 143.50,
44.11, 144.24, 145.04, 145.07, 145.22, 145.42, 145.57, 145.77, 145.86, 145.90, 145.95, 146.18, 146.41,
–
47.59, 147.65, 149.36, 155.52, 167.58. HRMS (ESI-TOF, negative) m/z calcd for C H BO [M+OAc] :
6
9
10
4
13.0689, found 913.0688.
Figure S15. The HPLC chart of crude reaction mixture containing 5f.
S23

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
6
. Typical Procedure for TfOH-Catalyzed Reaction of 1 with 2,2’-Bithiophenes 6 and
Arythiophenes 9. (Schemes 2 and 3)
Hex
S
Hex
S
S
S
Hex
S
S
S
1
Hex
S
6a
7a
8a
A 10-mL glass Schlenk tube containing a magnetic stirring bar was flame-dried under vacuum
and filled with argon after cooling to room temperature. To this flask were added 1 (17.6 mg, 20
µmol), dry o-dichlorobenzene (2.0 mL), and then 5-(1-hexyl)-2,2’-bithiophene 6a (47 µL, 200 µmol)
under a stream of argon. To the reaction mixture was added TfOH (0.2 M solution in
o-dichlorobenzene, 10 µL, 2 µmol) and then the mixture was stirred at 100 °C for 12 h. After cooling
to room temperature, the mixture was passed through a pad of silica gel with copious washings
with toluene (~20 mL). The filtrate was concentrated and subjected to preparative recycling HPLC
equipped with a Buckyprep column (eluent: toluene) to afford 1,4-bis(bithienyl)fullerene 7a (9.6
mg, 39%) and fused fullerene 8a (7.3 mg, 38%) as dark brown solid.
1
7
1
2
2
1
1
1
8
6
=
a: 39% isolated yield. H NMR (400 MHz, CDCl /CS = 1:1) δ 0.91 (t, J = 6.8 Hz, 6H), 1.33–1.40 (m,
3
2
2H), 1.69 (quin, J = 8.0 Hz, 4H), 2.79 (t, J = 8.0 Hz, 4H), 6.63 (d, J = 3.6 Hz, 2H), 6.93 (d, J = 3.6 Hz,
1
3
H), 7.07 (d, J = 3.6 Hz, 2H), 7.44 (d, J = 3.6 Hz, 2H). C NMR (100 MHz, CDCl /CS = 1:1) δ 14.26,
3
2
2.90, 28.95, 30.28, 31.69, 31.72, 57.05, 122.78, 123.72, 124.73, 126.66, 134.21, 137.15, 138.47, 138.54,
40.99, 141.76, 141.79, 142.11, 142.34, 142.52, 142.97, 142.99, 143.05, 143.42, 143.63, 143.65, 144.00,
44.09, 144.13, 144.22, 144.34, 144.44, 145.00, 145.37, 146.29, 146.63, 146.77, 146.93, 147.69, 148.48,
-
49.98, 154.99. HRMS (ESI-TOF, negative) m/z calcd for C H S [M] : 1218.1549, found 1218.1541.
8
8
34 4
1
a: 38% isolated yield. H NMR (400 MHz, CDCl /CS = 1:1) δ 0.90 (t, J = 6.4 Hz, 3H), 1.33–1.47 (m,
3
2
H), 1.77 (quin, J = 8.0 Hz, 2H), 2.89 (t, J = 8.0 Hz, 2H), 7.28 (d, J = 5.6 Hz, 1H), 7.44 (s, 1H), 7.76 (d, J
1
3
5.6 Hz, 1H). C NMR (100 MHz, CDCl /CS = 1:1) δ 14.19, 22.80, 29.05, 30.61, 31.68, 31.70, 64.57,
3
2
6
1
1
4.74, 122.53, 126.77, 127.90, 128.56, 128.73, 129.72, 130.74, 134.18, 140.08, 141.24, 141.26, 142.00,
42.10, 142.56, 143.22, 144.46, 144.57, 144.94, 145.20, 145.50, 145.57, 146.06, 146.10, 146.24, 147.69,
-
52.68, 153.09. HRMS (ESI-TOF, negative) m/z calcd for C H S [M] : 968.0699, found 968.0692.
7
4
16 2
S24

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
Figure S16. The HPLC chart of crude reaction mixture containing 7a and 8a.
Compound Data for 8 and 10
Unless otherwise noted, fused fullerenes 8 and 10 described in this section were prepared
following the typical procedure. All products were purified by preparative recycling HPLC
equipped with a Buckyprep column (eluent: toluene).
Fused Fullerene 8b
Hex
Hex
S
S
Ts
N
Hex
S
Hex
S
6b
1
8b
1
8
b: 1.5 equiv of 6b was employed. 92% isolated yield. H NMR (400 MHz, CDCl /CS = 1:1) δ 0.90
3 2
(
t, J = 7.0 Hz, 6H), 1.31–1.48 (m, 12H), 1.75 (quin, J = 7.8 Hz, 4H), 2.87 (t, J = 7.8 Hz, 4H), 7.41 (s, 2H).
1
3
C NMR (100 MHz, CDCl /CS = 1:1) δ 14.19, 22.78, 29.05, 30.59, 31.68, 31.74, 64.67, 126.66, 127.61,
3
2
1
1
1
28.25, 134.18, 140.04, 141.26, 142.04, 142.11, 142.56, 143.23, 143.76, 144.48, 144.93, 145.20, 145.64,
-
46.07, 146.15, 146.25, 147.70, 153.02. HRMS (ESI-TOF, negative) m/z calcd for C H S [M] :
8
0
28 2
052.1638, found 1052.1638.
S25

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
Figure S17. The HPLC chart of crude reaction mixture containing 8b.
Fused Fullerene 8c
Et
Et
S
S
Ts
N
Et
S
Et
S
6c
1
8c
1
8
c: 1.5 equiv of 6c was employed. 84% isolated yield. H NMR (400 MHz, CDCl /CS = 1:1) δ 1.40 (t,
3 2
1
3
J = 7.2 Hz, 6H), 2.93 (q, J = 7.2 Hz, 4H), 7.43 (s, 2H). C NMR analysis was not conducted due to
-
the low solubility of 8c. HRMS (ESI-TOF, negative) m/z calcd for C H S [M] : 940.0386, found
7
2
12 2
9
40.0390.
S26

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
Figure S18. The HPLC chart of crude reaction mixture containing 8c.
Fused Fullerene 10a
Hex
S
Me
Ts
N
Hex
S
Me
9a
1
10a
1
1
0
7
0a: 1.5 equiv of 9a was employed. 94% isolated yield. H NMR (400 MHz, CDCl /CS = 1:1) δ
3 2
.88–0.92 (m, 3H), 1.33–1.46 (m, 6H), 1.78 (quin, J = 7.6 Hz, 2H), 2.44 (s, 3H), 2.89 (t, J = 7.6 Hz, 2H),
1
3
.22 (d, J = 7.6 Hz, 1H), 7.46 (s, 1H), 7.60 (d, J = 7.6 Hz, 1H), 8.45 (s, 1H). C NMR (100 MHz,
CDCl /CS = 1:1) δ 14.19, 21.84, 22.80, 29.09, 30.74, 31.66, 31.69, 64.35, 64.96, 124.00, 126.59, 127.56,
3
2
1
1
1
27.61, 127.67, 127.71, 128.98, 129.17, 132.25, 133.40, 134.00, 134.16, 137.68, 139.20, 140.00, 141.14,
41.25, 141.88, 141.99, 142.21, 142.28, 142.64, 142.65, 143.23, 144.51, 144.61, 144.88, 145.19, 145.54,
46.05, 146.12 146.25 146.29, 146.37, 146.51, 147.65, 147.76, 154.15, 155.49. HRMS (ESI-TOF,
-
negative) m/z calcd for C H S [M] : 976.1291, found 976.1290.
7
7
20
S27

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
Figure S19. The HPLC chart of crude reaction mixture containing 10a.
Fused Fullerene 10b
Hex
Me
Ts
N
S
Hex
Me
S
9b
1
10b
1
1
0b: 1.5 equiv of 9b was employed. 93% isolated yield. H NMR (400 MHz, CDCl /CS = 1:1) δ 0.92
3 2
(
t, J = 6.8 Hz, 3H), 1.35–1.48 (m, 6H), 1.79 (quin, J = 8.0 Hz, 2H), 2.45 (s, 3H), 2.93 (t, J = 8.0 Hz, 2H),
1
3
7
1
1
1
1
9
.22–7.28 (m, 2H), 7.77 (d, J = 7.6 Hz, 1H), 8.51 (s, 1H). C NMR (100 MHz, CDCl /CS = 1:1) δ
3 2
4.25, 21.77, 22.84, 29.07, 30.63, 31.62, 31.74, 63.40, 65.15, 119.95, 124.56, 127.12, 128.57, 128.88, 132.38,
32.55, 132.76, 133.41, 134.24, 137.43, 139.17, 140.12, 141.16, 141.33, 141.81, 141.92, 142.17, 142.60,
43.09, 144.43, 144.61, 144.78, 144.89, 144.91, 145.13, 146.00, 146.07, 146.19, 146.31, 146.46, 147.65,
-
47.75, 147.91, 154.65, 155.92. HRMS (ESI-TOF, negative) m/z calcd for C H S [M] : 976.1291, found
7
7
20
76.1291.
S28

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
Figure S20. The HPLC chart of crude reaction mixture containing 10b.
7
. TfOH-Catalyzed Reaction of 1 with Alkyne 11. (Scheme 4)
Ar
TsN
Ar
1
0% TfOH
,2-Cl C H
6 4
1
+
Ar
Ar
1
1
2
00 ºC, 12 h
11 (10 equiv)
(
Ar = 4-MeOC H )
6 4
12 (81%)
A 10-mL glass Schlenk tube containing a magnetic stirring bar was flame-dried under vacuum
and filled with argon after cooling to room temperature. To this flask were added 1 (17.6 mg, 20
µmol), bis-(4-methoxyphenyl)-ethyne 11 (47.7 mg, 200 µmol), and dry o-dichlorobenzene (2.0 mL)
under a stream of argon. To the reaction mixture was added TfOH (0.2 M solutiuon in
o-dichlorobenzene, 10 µL, 2 µmol) and then the mixture was stirred at 100 °C for 12 h. After cooling
to room temperature, the mixture was passed through a pad of silica gel with copious washings
with toluene (~20 mL). The filtrate was evaporated and the residue was purified by flash silica gel
chromatography (toluene/hexane = 1:2~1:1) to afford 12 (18.3 mg, 81%) as a dark brown solid.
1
Data of 12: H NMR (400 MHz, CDCl /CS = 10:1) δ 2.45 (s, 3H), 3.88 (s, 3H), 3.90 (s, 3H), 6.87 (dm,
3
2
S29

Supporting Information (Nambo, Segawa, Itami)
Aziridinofullerene: A Versatile Platform for Functionalized Fullerenes
J = 8.8 Hz, 2H), 7.02 (dm, J = 9.2 Hz, 2H), 7.19 (d, J = 8.4 Hz, 2H), 7.72 (d, J = 8.4 Hz, 2H), 7.94 (dm, J
1
3
=
8.8 Hz, 2H), 8.07 (dm, J = 9.2 Hz, 2H). C NMR (100 MHz, CDCl /CS = 10:1) δ 21.65, 55.26, 55.32,
3 2
6
1
1
1
1
1
6.28, 70.90, 74.08, 74.43, 114.10, 114.39, 125.39, 126.39, 127.85, 128.39, 128.85, 129.45, 136.79, 138.22,
38.65, 139.53, 139.98, 140.54, 141.14, 141.73, 141.79, 141.84, 141.92, 142.20, 142.31, 142.46, 142.72,
42.75, 142.88, 143.07, 143.11, 143.30, 143.55, 143.74, 143.76, 143.94, 144.02, 144.12, 144.27, 144.30,
44.35, 144.39, 144.48, 144.50, 144.64, 145.25, 145.41, 145.43, 145.64, 145.94, 146.05, 146.08, 146.17,
46.24, 146.63, 146.66, 146.93, 147.61, 147.96, 148.07, 148.12, 148.25, 148.46, 149.39, 150.13, 150.34,
-
58.13, 160.06, 160.19. HRMS (ESI-TOF, negative) m/z calcd for C H NO S [M] : 1127.1197, found
8
3
21
4
1127.1203.
Figure S21. The HPLC chart of crude reaction mixture containing 12.
8
. X-Ray Crystal Structure Analysis of 8c and 12
Single crystal of 8c and 12 were obtained by slow mixing of CS solution of 8c with Et O and
2
2
toluene solution of 12 with hexane at room temperature, respectively. A suitable crystal was
mounted with mineral oil on a glass fiber and transferred to the goniometer of a Rigaku Saturn
CCD diffractometer. Graphite-monochromated Mo Kα radiation (λ = 0.7107 Å) was used. The
1
2
structures were solved by direct methods with (SIR-97) and refined by full-matrix least-squares
2
13
techniques against F (SHELXL-97). The intensities were corrected for Lorentz and polarization
effects. The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were placed using
AFIX instructions. Details of the crystal data and a summary of the intensity data collection
1
2
Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G. L.; Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G.
G.; Polidori, G.; Spagna, R. J. Appl. Crystallogr. 1999, 32, 115–119.
13
Sheldrick, G. M.; University of Göttingen: Göttingen, Germany, 1997.
S30