Lewis base-catalyzed double nucleophilic substitution reaction of N-tosylaziridinofullerene with thioureas or guanidines

Article abstract of DOI:10.1016/j.tetlet.2017.05.048

Lewis base-catalyzed double nucleophilic substitution reaction of N-tosylaziridinofullerene with thioureas or guanidines affords the fullerothiazolidin-2-imine or fulleroimidazolidin-2-imine derivatives, respectively. In the case of unsymmetrical thiourea

Full text of DOI:10.1016/j.tetlet.2017.05.048

Accepted Manuscript
Lewis Base-Catalyzed Double Nucleophilic Substitution Reaction of N-Tosy-
laziridinofullerene with Thioureas or Guanidines
Qi Meng, Jun-Yu Cheng, Chun-Bao Miao, Xiao-Qiang Sun, Hai-Tao Yang
PII:
S0040-4039(17)30633-0
DOI:
http://dx.doi.org/10.1016/j.tetlet.2017.05.048
TETL 48941
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
30 March 2017
13 May 2017
15 May 2017
Please cite this article as: Meng, Q., Cheng, J-Y., Miao, C-B., Sun, X-Q., Yang, H-T., Lewis Base-Catalyzed Double
Nucleophilic Substitution Reaction of N-Tosylaziridinofullerene with Thioureas or Guanidines, Tetrahedron
Letters (2017), doi: http://dx.doi.org/10.1016/j.tetlet.2017.05.048
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2
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Lewis Base-Catalyzed Double Nucleophilic
Substitution Reaction of N-
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Tosylaziridinofullerene with Thioureas or
Guanidines
Qi Meng,* Jun-Yu Cheng, Chun-Bao Miao, Xiao-Qiang Sun and Hai-Tao Yang*
S
R'
R''
N
N
R'
N
S
H
H
N
Ts
DABCO (cat.)
or DMAP (cat.)
excellent chemoselectivity
N
R''
R
R', R'' = alkyl; R', R'' = aryl
R' = alky, R'' = aryl;
R' = Ts, R'' = alkyl
N
R
R
N
N
H
H
DABCO (cat.)
R
N
R
N
R
N
CS2
R = 4-MeO-C6H4
S
N
R
N
R

1
Tetrahedron Letters
Lewis Base-Catalyzed Double Nucleophilic Substitution Reaction of N-
Tosylaziridinofullerene with Thioureas or Guanidines
Qi Meng, Jun-Yu Cheng, Chun-Bao Miao, Xiao-Qiang Sun and Hai-Tao Yang,*
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Advanced Catalysis and Green Manufacturing Collaborative Innovation Center,
School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Lewis base-catalyzed double nucleophilic substitution reaction of N-tosylaziridinofullerene with
thioureas or guanidines affords the fullerothiazolidin-2-imine or fulleroimidazolidin-2-imine
derivatives, respectively. In the case of unsymmetrical thioureas connecting an alkyl and an aryl
group on each of the nitrogen atom, the transformation exhibits excellent chemoselectivity with
only the aryl substituted nitrogen atom bonding to C60. The generated tri-4-methoxyphenyl
substituted fulleroimidazolidin-2-imine reacts with CS2 smoothly to generate di-4-
methoxyphenyl fulleroimidazolidin-2-thione.
Available online
Keywords:
tosylaziridinofullerene
double nucleophilic substitution
thiourea
2009 Elsevier Ltd. All rights reserved.
guanidine
 Corresponding author.
E-mail address: estally@yahoo.com
http://dx.doi.org/10.1016/********
0040-4039/_ 2016 Elsevier Ltd. All rights reserved.

2
R3
Table 1 Screening of the Catalystsa
R1
O
S
N
R2
R1
R2
R1
R2
R1
R2
N
H
N
H
N
H
N
H
N
H
N
H
N
H
N
H
Bn
S
N
S
amidine
urea
thiourea
Ts
N
guanidine
Bn
Bn
Bn
N
N
N
Figure 1 Structures of the amidine, urea, thiourea, and guanidine
S
methylimidazole) as a catalyst in the double nucleophilic
substitution of N-tosylaziridinofullerene with amidines or ureas
for the easy preparation of cyclic 1,2-diaminated
[60]fullerenes.11a,b The easy operation process and the highly
synthetic efficiency encouraged us to develop more
conditions
PhCl
Bn
Bn
N
N
+
H
H
2a

time
(h)
0.5
0.5
3
1
2
6
6
1
4
3
4
6
4
3a
1
molar
ratiob
1:1.5:5
1:1.5:2
1:1.5:0.2
1:1.5:1
1:1.5:1
yield
(%)c
0
transformation
through
the
easily
available
N-
entry conditions
T (ºC)
tosylaziridinofullerene. Thiourea and guanidine have structure
similarity with urea just with the variation of C=O double bonds
to C=S/N double bonds (Figure 1). We were inquisitive about
whether the thiourea and guanidine can react with N-
tosylaziridinofullerene to afford two new classes of
organofullerenes via a similar transformation.
1
2
3
4
5
6
7
8
9
10
11
12
13
80
80
80
80
80
80
80
80
80
120
120
120
120
BF3Et2O
CF3SO3H
DMAP
DMAP
NMI
0
51
67
71
40
35
91
77
0
Et3N
1:1.5:1
1:1.5:1
Results and discussion
pyridine
DABCO
DABCO
K2CO3
Sc(OTf)3
Zn(OT f)2
Cu(OTf)2
1:1.5:1
1:1.5:0.2
1:1.5:2
1:1.5:0.5
1:1.5:0.5
1:1.5:0.5
Our investigation began with the reaction of N-
tosylaziridinofullerene
Those reported effective catalyst in the transformations of
N-tosylaziridinofullerene such as CF3SO3H, BF3 Et2O,
DMAP, and NMI were tried firstly (Table 1, entries 1-
4).5b,10,11a,11b The CF3SO3H and BF3
Et2O showed no
catalytic activity and almost all of the was converted to C60
1 with 1,3-dibenzylthiourea 2a.
53
21
47


a
1
Unless notified, the reactions were carried out (1, 0.02
mmol) in 2.5 mL of dry chlorobenzene. 1:2a:catalyst.
b
c
(Table 1, entries 1 and 2). Using DMAP as the catalyst gave
a single product. However, the NMR analysis revealed that
it was not the anticipated diaminated product but the
fullerothiazolidin-2-imine 3a. The yield was not satisfactory
and only 51% yield of 3a was obtained after stirring for 3 h
at 80 ºC (Table 1, entry 3). Increasing the temperature to 120
ºC had no improvement on the yield because a large amount
of N-tosylaziridinofullerene was transformed to C60.
Although increasing the amount of DMAP to 1 equiv could
complete the conversion within 1 h and gave higher yield of
Isolated yield.
Introduction
There has been a good understanding of the chemical
reactivity of C60 and a large number of highly functionalized
fullerenes have been efficiently synthesized by various
techniques.1 Nevertheless, the diversity in the structures of
fullerene derivatives may lead to the creation of new application
in the fields of material and biomedicine science,2 further
exploration and development of new synthetic methods toward
organofullerenes with sophisticated and unprecedented
architectures is still required.3 At present, most of the fullerene
derivatives are prepared directly from pristine C60 through one-
step reaction. However, not all the fullerene derivatives can be
easily synthesized from C60. Thus, the development of new routes
to access functionalized fullerenes with novel structure from an
easily prepared fullerene derivative is in demand. For instance,
the fullerene epoxide,4 N-tosylaziridinofullerene,5 azafulleroids,6
3a, large decomposition of
entry 4). The NMI gave a decent yield of 3a, however, a
considerable decomposition of to C60 occurred also (Table
1 to C60 was inevitable (Table 1,
1
1, entry 5). Next, other Lewis base/acid catalysts such as
Sc(OTf)3, Zn(OTf)2, Cu(OTf)2, Et3N, pyridine, and DABCO
were examined (Table 1, entries 6-13). To our delight, the
DABCO could efficiently catalyze the reaction, affording
91% yield of the product within 1 h at 80 ºC (Table 1, entry
8). Reducing the amount of DABCO to 0.2 equiv led to
longer reaction time to complete the reaction, whereas, more
starting material was decomposed to C60 (Table 1, entry 9).
Replacing DABCO with Et3N, pyridine, or K2CO3 resulted
in dramatic decrease in the yield or no reaction (Table 1,
entries 6, 7, and 10). The commonly used Lewis acids such
as Sc(OTf)3, Zn(OTf)2, and Cu(OTf)2 also displayed certain
catalytic activity, albeit with a much lower yield (Table 1,
entries 11-13).
7
and NFSI adduct of C60 have been reported to undergo various
transformations to furnish a diversity of functionalized fullerenes.
Especially the N-tosylaziridinofullerene, which can be easily
synthesized from sulfonamides in good yield,8 not only takes
place a formal [3+2] reaction with isocyanates, CO2,9 or carbonyl
compounds10 with the reserve of “TsN” unit but also undergo an
unique double nucleophilic substitution reaction with
dinucleophiles accompanied by the loss of “TsN” unit.11 The
CF3SO3H and combination of HPCy3BF4-NaH have proved to be
the effective catalysts.5b,9 Recently, we applied commonly used
bases such as DMAP (4-dimethylaminopyridine) or NMI (N-

3
Table 3 DABCO-Catalyzed Reaction of Aziridinofullerene 1
with Guanidines
Table 2 Substrate Scope
Ts
N
condition A:
DABCO (1 equiv), 80 o
Ts
N
C
condition B:
R2
N
R3
N
S
DMAP (0.2 euquiv), 120 o
PhCl
C
S
N
R3
R1
+
R2
N
R2
N
DABCO (0.2 equiv)
N
N
R1
R2
H
H
+
PhCl, 80 o
C
N
N
R1
N
R1
2
H
H
(1.5 equiv)
Ph
4
3
1
(1.5 equiv)
5
1
S
N
S
N
N
S
entry
1
2
substrate
product
5a (1 h, 85%)
5b (1 h, 67%)
N
N
4a (R1, R2, R3 = 4-MeC6H4)
N
4b (R1, R2, R3 = 4-MeOC6H4)
4c (R1, R2, R3 = 4-ClC6H4)
4d (R1, R2 = 4-MeC6H4, R3 = n-Bu)
4e (R1, R2, R3 = Bn)
Ph
3b
3a
, 1 h, 94%
, 1 h, 91%
3c, 1.5 h, 69%
Me
3
4
5
5b (2.5 h, 78%)
very low yield,
two isomers
S
N
S
N
S
N
N
N
N
5d (0.5 h, 0%)
Ph
With the optimal conditions in hand, the substrate scope
for the transformation was evaluated. As illustrated in Table
2, the preparative scope was rather general regardless of
whether alky or aryl groups were presented on the nitrogen
atoms, giving moderate to excellent yield of
3d
, 1.5 h, 88%
3e
, 1 h, 74%
3f
, 1 h, 84%
Me
OMe
CO2Et
Cl
S
N
S
N
S
N
N
N
N
fullerothiazolidin-2-imines
3. For dialkylated thioureas, a
3i
3h
, 0.5 h, 95%
3g, 1 h, 85%
, 0.5 h, 90%
OMe
CO2Et
Cl
noticeable steric effect was observed. Compared with the
high yield of 3a and 3b, only 69% yield of 3c was obtained
for the N,N'-diisopropylthiourea 2c and no desired product
was isolated for N,N'-di-tert-butylthiourea. When one of the
tert-butyl was replaced by benzyl, the reaction occurred to
selectively provide 3d in 88% yield with sterically less
hindered nitrogen atom bonding to C60. In terms of the
diarylated thioureas, using DABCO as the catalyst gave a
low conversion as detected by TLC. Replacing DABCO
CO2Et
OMe
Ph
S
N
S
N
S
N
N
N
N
3j
3k, 1 h, 79%
3j'
Me
OMe
3j 3j'
:
CO2Et
= 1.44 :1; 1 h, 69%
OH
OMe
OMe
Ts
S
S
N
S
N
N
N
N
N
Ph
3n
, 5 h, 51%
3l
, 1 h, 77%
3m, 1 h, 87%
Me
Me
a
The condition A was applied for 3a-d and 3k-n. The
condition B was applied for 3f-j.
on the reaction, the thioureas 2k-m having an alkyl and an
aryl group on each of the nitrogen atom were prepared and
introduced to the reaction. When one of the nitrogen atoms
linked with an alkyl group, DABCO could effectively
catalyze the transformation. It was noteworthy that the
reaction of
1 with 2k-m showed excellent chemoselectivity
and only single isomer was obtained with the arylated
nitrogen atom bonging to C60. In the case of the N-benzyl-
N'-tosylthiourea 2n, although it displayed lower reactivity,
Figure 2 HMBC Spectrum of 3a in CS2/CDCl3 (500 MHz)
its reaction with
1 showed high selectivity and furnished
single isomer 3n. The catalytic system showed a high degree
of functional group tolerance and the alkenyl, ester,
hydroxyl, and acetal groups were compatible with the
with DMAP and increasing the temperature to 120 ºC gave
good yield of 3f-i. It should be noted that only catalytic
amount of DMAP was required. For the unsymmetrical
diarylated thiourea 2j, which connected an electron-donating
and electron-withdrawing group on each of the nitrogen
conditions to afford good yields of 3e
Compared with our previous reported Lewis base-catalyzed
reaction of with amidines or ureas, in which the two
, 3i, 3j, 3l, and 3m.
1
atom, its reaction with
affording an inseparable mixture of the two isomers 3j and
3j' 3j 3j'=1.44:1) in overall 69% yield. In the major isomer,
1 showed low chemoselctivity,
substituents of amidines were restricted to both aryl groups
and one of the substituent of ureas was limited to electron
withdrawing group such as Ts and Bz group,11a,b the
thioureas displayed more extensive substrate scope in its
(
:
the nitrogen atom bearing an electron-rich aryl group
bonded to C60 probably due to its stronger nucleophilicity.
To investigate the influence of different types of substituents
reaction with 1.

4
Encouraged by the promising results achieved above, we
next turned our attention to investigate the preparation of
fulleroimidazolidin-2-imines through a similar method. We
were pleased to find that the DABCO-catalyzed reaction of
NMR, and UV−vis spectra (Supporting Information). In
the H NMR and 13C NMR spectra of 3a, a noticeable
difference between the two CH2 groups was observed. The
two peaks at 84.60 and 68.03 ppm was attributed to the two
sp3-carbons of C60 linking to nitrogen and sulfur atom,
respectively. The higher electronegativity of nitrogen atom
than sulfur atom resulted in the downfield shift. To
accurately assign the two CH2 groups, 3a was further taken
the H-H COSY and HMBC spectroscopic analysis (Figure 2
and Supporting Information), which would be helpful to
confirm the structure of 3d, 3j, 3k, 3l, 3m, and 3n generated
from the unsymmetrical thioureas. The observed J Cb-Hd
and J Ca-Ha correlation precisely discriminated the two CH2
groups (Figure 2). The CH2 group (b) attached on the
1
N-tosylaziridinofullerene
1 with 1,2,3-tri-p-tolylguanidine
4a afforded the desired fulleroimidazolidin-2-imine 5a in
85% yield. Either electron-donating or electron-withdrawing
group on the phenyl had no influence on the reaction. When
one of the aryl groups was replaced by an alkyl group, the
reaction proceeded miserably and afforded very low yield of
product as inseparable mixture of two isomers. Meanwhile,
3
large amount of N-tosylaziridinofullerene
C60. Trialkylguanidine was not suitable for this
transformation yet and all of the staring material
1
decomposed to
1
1
1
decomposed. A possible explanation might be due to the
strong basicity of alklylated guanidines because in our
previous work we found that the strong organic base such as
saturated nitrogen atom showed downfield H NMR shift
(5.74 vs 4.82 ppm) and upfield 13C NMR shift (49.74 vs
H: 4.82 ppm
C: 59.09 ppm
a
H: 4.76 ppm
C: 59.57 ppm
DBU could not catalyze the reaction of
1 with amidines and
c
Ph
Ts
Ph
S
S
N
S
N
S
N
all of the
1 was transformed to C60 and unidentified product
N
N
N
N
e
b
with very high polarity.11b
d
N
7.56
Ph
During the course of NMR analysis of product 5b with
CS2-CDCl3 as the solvent, the compound 5b was found
reacting with CS2 slowly to furnish a single product with
lower polarity. Stirring a solution of 5b in CS2-CHCl3 at
Ph
Ph
3n
3k
3d
3a
H: 5.74 ppm
C: 49.74 ppm
5.75 ppm
51.06 ppm
5.63 ppm
49.83 ppm
7.26
Me
Me
N
Me
7.02
7.10
S
OH
room
temperature
for
5
days
afforded
the
6.63
6.61
Me
N
N
S
N
fulleroimidazolidinthione
6
in 78% yield. In comparison, the
N
N
N
5a and 5c was much more stable in carbon disulfide.
7.61
7.49
7.53
5a
The structures of fullerothiazolidin-2-imines
3 and
3l
3f
7.28
7.06
7.24
Me
Me
Me
fulleroimidazolidin-2-imines
5
were unambiguously
Figure 3 Comparison of the NMR Chemical Shifts of
Compounds 3a, 3d, 3n, 3k, 3l, 3f, and 5a
1
characterized by their MALDI-TOF HRMS, H NMR, 13C
R1
N
R1
N
R1
N
R1
HN
Ts
Ts
Ts
H
H
H
N
NH
N
N
N
N
N
S
R2
R2
R2
R2
R1
R2
S
S
S
S
N
H
N
H
LB
stronger nucleophicity
TsNH
-TsNH
11
Ts
N
S
7
9
13
3
alkyl
N
N
H
R2
S
R2
S
R1
HN
R1
N
N
R2
HN
I
LB
HN
S
R2
HN
S
Ts
R1
N
R1
Ts
Ts
N
N
N
NH
S
LB
S
R1
R2
1
alkyl
N
H
N
H
HN
N
TsNH
-TsNH
II
14
3
8
12
10
stronger nucleophicity
N
R
N
R
N
S
N
R
N
R
N
S
S
S
C S
-
RN C
S
N R
S
S
N
H
III
R
N
R
N
R
N
R
N
R
N
R
6
15
16
5b
R = 4-MeOC6H4
Scheme 2 Proposed Mechanism
59.09 ppm) compared with the CH2 group (a) attaching on
OMe
3
3
OMe
S
the imine nitrogen atom. From the J Cb-H4 and J Ca-H1
correlation and the H-H COSY spectrum the signals for the
two phenyl ring could be assigned accurately. By
N
N
CHCl3
rt.
1
comparison of the H NMR and 13C NMR chemical shifts of
N
OMe
+
CS2
N
N
the methylene group in compounds 3d (5.63 and 49.83
ppm), 3n (5.75 and 51.06 ppm), and 3k (4.76, 59.57 ppm)
with that of 3a we could precisely infer their structure
(Figure 3). In the 1H NMR spectrum of 5a, the 4-
5b
6 (5 days, 78%)
OMe
OMe
Scheme 1 The reaction of 5b with CS2

5
methylphenyl group attached on the saturated nitrogen atom
clearly showed more downfield shift than that of attached on
the imine nitrogen atom. According to this, in the H NMR
spectrum of 3f, the two doublets with downfield shift (7.28
and 7.61 ppm) was assigned to the aryl ring attached on the
saturated nitrogen atom, whereas the two doublets with
upfield shift (7.02 and 7.10 ppm) was attributed to the aryl
ring attached on the imine nitrogen atom (Figure 3). The
observed difference of the two aryl ring further supported
bearing an alkyl and an aryl group on each of the nitrogen
atom shows excellent chemoselectivity. The tri-4-
methoxyphenyl substituted fulleroimidazolidin-2-imine
reacts with CS2 smoothly to generate fulleroimidazolidin-2-
thione.
1
Acknowledgments
We are grateful for financial support from the Natural Science
Foundation of Jiangsu Province (BK20141171), the Jiangsu
Province Science and Technology Support Program, China
(BY2106029-18), the Jiangsu Key Laboratory of Advanced
Catalytic Materials and Technology (BM2012110), and
Advanced Catalysis and Green Manufacturing Collaborative
Innovation Center.
the structure assignment of 3k, 3l, and 3m, in which the
chemical shift of 7.49-7.56 and 7.22-7.26 ppm for the 4-
methyphenyl ring implied it attached on the saturated
nitrogen atom (Figure 2).
A plausible mechanism for the formation of
was depicted in Scheme 2. Nucleophilic attack of the Lewis
base on the fullerene cage of along with the ring-opening
of azirdine ring would generate the zwitterion
or 8,9 which
undergoes further SN2' reaction with thiourea to give or 10
3, 5, and 6
1
Supplementary Material
7
General synthetic procedures, characteristic data, and NMR
spectra of the products can be found, in the online version, at
http://dx.doi.org/10.1016/j.tetlet.
9
.
After intramolecular proton exchange, further SN2' reaction
affords 13 or 14 and the subsequent deprotonation furnishs
the fullerothiazolidin-2-imine 3. No diaminated product is
References and notes
generated probably due to the stronger nucleophilicity of
sulfur atom than that of nitrogen atom. For the
unsymmetrical thiourea bearing an alkyl and an aryl group
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Reactions, Wiley-VCH Verlag GmbH
& Co. KGaA: Weinheim,
Germany, 2005. (b) Langa, F.; Nierengarten, J.-F. Fullerenes: Principles
and Applications, RSC Publishing: Cambridge, UK, 2007. For recent
reviews, see: (c) Tzirakis, M. D.; Orfanopoulos, M. Chem. Rev. 2013,
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Zhu, S.-E.; Li, F.; Wang, G.-W. Chem. Soc. Rev. 2013, 42, 7535.
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Adv. 2014, 4, 46383. (g) Yan, W.; Seifermann, S. M.; Pierrat, P.; Bräse,
S. Org. Biomol. Chem. 2015, 13, 25.
on each of the nitrogen atom, the intermediate 11
(12)
preferred the structure of but not II because in the reported
I
S-alky isothioureas the aryl group connected on the imine
nitrogen atom.12 Like the imidazole (III), the imine nitrogen
should show stronger nucleophilicity than the saturated
nitrogen atom linking with alky group, which results in the
excellent chemoselectivity. At present, we have no a definite
answer to the relationship between the base choice and the
substituent on the nitrogen atom. The reaction of
guanidine takes the same process to afford
fulleroimidazolidin-2-imine . When the nitrogen atom
1 with
5
3. For recent papers, see: (a) Liu, T.-X.; Ma, J.; Di, C.; Zhang, P.; Ma, N.;
Liu, Q.; Shi, L.; Zhang, Z.; Zhang, G. Org. Lett. 2016, 18, 4044. (b) Wu,
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linked with a 4-methoxyphenyl group, the strong electron
donating character of the methoxyl group increases the
nucleophilicity of the nitrogen atom dramatically.
Nucleophilic addition of 5b with CS2 followed by an
intramolecular nucleophilic cyclization generates an
intermediate 16, which dissociates to give product
6 and 4-
methoxyphenylisothiocyanate. The less electron-donating
character of chloro and methyl group than methoxyl group
results in the low nucleophilicity of imine-nitrogen atom in
5a and 5c, which explains the stability of 5a and 5c in CS2
compared with 5b. The compounds 3g and 3j' are very
stable in CS2. It can be explained that the imine nitrogen
atom of S-substituted isothiourea has weaker basicity and
nucleophilicity than that of guanidine because the
electron-donating conjugation effect of nitrogen atom is
stronger than sulfur atom.
6. (a) Ikuma, N.; Dio, Y.; Fujioka, K.; Mikie, T.; Kokubo, K.; Oshima, T.
Chem. Asian J. 2014, 9, 3084. (b) Hummelen, J. C.; Prato, M.; Wudl, F.
J. Am. Chem. Soc. 1995, 117, 7003. (c) Ikuma, N.; Nakagawa, K.;
Kokubo, K.; Oshima, T. Org. Biomol. Chem. 2016, 14, 7103. (d)
Hummelen, J. C.; Knight, B.; Pavlovich, J.; González, R.; Wudl, F.
Scienec 1995, 269, 1554.
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X.-Q.; Yang, H.-T. J. Org. Chem. 2013, 78, 12257.
Conclusions
In summary, an easy preparation of two new classes of
fullerothiazolidin-2-imine or fulleroimidazolidin-2-imine
derivatives via Lewis base-catalyzed double nucleophilic
reaction of N-tosylaziridinofullerene with thioureas or
guanidines has been developed. The reaction of N-
tosylaziridinofullerene with unsymmetrical thioureas
9. Takeda, Y.; Kawai, H.; Minakata, S. Chem.–Eur. J. 2013, 19, 13479.

6
10. Yang, H.-T.; Xing, M.-L.; Zhu, Y.-F.; Sun, X.-Q.; Cheng, J.; Miao, C.-
B.; Li, F.-B. J. Org. Chem. 2014, 79, 1487.
11. (a) Xing, M.-L.; Lu, X.-W.; Miao, C.-B.; Li, J.-X.; Sun, X.-Q.; Yang, H.-
T. J. Org. Chem. 2014, 79, 11774. (b) Yang, H.-T.; Xing, M.-L.; Lu, X.-
W.; Li, J.-X.; Cheng, J.; Sun, X.-Q.; Miao, C.-B. J. Org. Chem. 2014,
79, 11744. (c) Wu, J.; Li, F.-B.; Zhang, X.-F.; Shi, J.-L.; Liu, L. RSC
Adv. 2015, 5, 30549.
12. It could be clearly seen from the 1H NMR sepectrum the hydrogen
on nitrogen atom was split by the adjacent alkyl group. For example, see:
Mampuys, P.; Zhu, Y.; Vlaar, T.; Ruijter, E.; Orru, R. V. A.; Maes, B.

7
Highlight
1. Base catalyzed reaction of N-tosylaziridinofullerene with thioureas or guanidines is developed.
2. The reaction exhibits excellent chemoselectivity for the unsymmetrical thioureas.
3. An unusual reaction of cyclic guanidine fused C60 with CS2 is observed.