Stereoselective synthesis of cis- and trans-2′,5′-disubstituted N-arylpyrrolo[3′,4′:1,9](C60-I h )[5,6]fullerenes by the 1,3-dipolar cycloaddition of azomethine ylides from dialkyl aziridinedicarboxylates to fullerene C60

Article abstract of DOI:10.1007/s11172-012-0121-7

A stereoselective method for the synthesis of 2′,5′- disubstituted N-arylpyrrolofullerenes from anilines, alkyl glyoxylates, alkyl diazoacetates, and fullerene C₆₀ was proposed. The key step of the synthesis is the 1,3-dipolar cycloaddition reaction of fullerene with azomethine ylides generated by heating of dialkyl aziridinedicarboxylates. The thermal opening of the aziridine ring to azomethine ylide and the cycloaddition of the latter to C₆₀ at 100 C are nearly completely stereoselective: only trans-adducts are formed from cis-aziridines, whereas trans-aziridines give exclusively cis-adducts.

Full text of DOI:10.1007/s11172-012-0121-7

Russian Chemical Bulletin, International Edition, Vol. 61, No. 4, pp. 863—870, April, 2012
863
Stereoselective synthesis of cisꢀ and transꢀ2´,5´ꢀdisubstituted
Nꢀarylpyrrolo[3´,4´:1,9](C60ꢀIh)[5,6]fullerenes
by the 1,3ꢀdipolar cycloaddition of azomethine ylides
from dialkyl aziridinedicarboxylates to fullerene C60
A. S. Konev,a A. A. Mitichkina,a A. F. Khlebnikov,a and H. Frauendorfb
aDepartment of Chemistry, Saint Petersburg State University,
26 Universitetsky prosp., 198504 Saint Petersburg, Russian Federation.
Fax: +7 (812) 428 6939. Eꢀmail: alexander.khlebnikov@pobox.spbu.ru
bInstitute of Organic and Biomolecular Chemistry of GeorgꢀAugustꢀUniversity,
2 Tammannstrasse, D37077 Göttingen, Germany
A stereoselective method for the synthesis of 2´,5´ꢀdisubstituted Nꢀarylpyrrolofullerenes
from anilines, alkyl glyoxylates, alkyl diazoacetates, and fullerene C60 was proposed. The key
step of the synthesis is the 1,3ꢀdipolar cycloaddition reaction of fullerene with azomethine
ylides generated by heating of dialkyl aziridinedicarboxylates. The thermal opening of the
aziridine ring to azomethine ylide and the cycloaddition of the latter to С60 at 100 С are nearly
completely stereoselective: only transꢀadducts are formed from cisꢀaziridines, whereas
transꢀaziridines give exclusively cisꢀadducts.
Key words: pyrrolofullerenes, aziridines, azomethine ylides.
For two recent decades compounds containing fulꢀ
lerene cage attract considerable attention of researchers in
the fields of medicine1—4 and solar energy storage.5—11
The data on the antioxidant,12 antibacterial,13,14 and antiꢀ
viral15 properties of these substances were published. In
particular, compound 1 (R = H, R´ = CH2COOH) deꢀ
scribed15 as a mixture of stereoisomers exhibits high activꢀ
ity against the human immunodeficiency virus (HIV) due
to the inhibition of a reverse transcriptase of this virus
(IC50 = 0.029 mol L–1).15 Since cisꢀ and transꢀisomers
can have different biological activity and toxicity, it beꢀ
comes urgent to develop a method of stereoselective synꢀ
thesis of compounds with general formula 1, which would
allow one to construct a diversified library for bioscreening
with the purpose of searching for an optimum structure of
a drug. The variation of substituents R in pyrrolidinoꢀ
fullerenes 1 makes it possible to modulate their lipophilic/
hydrophilic properties, whereas the change in substituent
R´ affects the basicity of the compound. In addition, the
introduction of an appropriate group into substituent R´
allows one to use compounds 1 as synthetic blocks with
specified stereochemistry for the subsequent modification
of the potential drug structure.
the fullerene core (Prato reaction).16 The most general
and studied method for azomethine ylide generation in
this reaction includes the condensation of carbonyl comꢀ
pounds with ꢀamino acids accompanied by decarbꢀ
oxylation and dehydration of the primary adducts16—28
(Scheme 1, route A) or the condensation of carbonyl comꢀ
pounds with amines followed by imine—ylide tautomerꢀ
ization or dehydration of the primary adduct29—35 (see
Scheme 1, route B). These two methods were widely studꢀ
ied during the recent decade. However, as a rule, reactions
of this type afford a mixture of stereoisomeric cycloadꢀ
ducts and the reactions with good stereoselectivity in the
synthesis of 2´,5´ꢀdisubstituted pyrrolidinofullerenes are
rather rare.29,34 In addition, it is difficult to predict the
stereochemical result of these reactions.
Several methods for the synthesis of pyrrolofullerenes
were described, and the most part of them are based on the
1,3ꢀdipolar cycloaddition of azomethine ylides to the С=С
bond, which is common for two sixꢀmembered rings of
Therefore, the generation of azomethine ylides by the
electrocyclic opening of the aziridine ring7,16,36—42 (see
Scheme 1, route С) in the case of stereoselective formaꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 0860—0867, April, 2012.
1066ꢀ5285/12/6104ꢀ0863 © 2012 Springer Science+Business Media, Inc.

864
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 4, April, 2012
Konev et al.
Scheme 1
tion of ylides and in the absence of their isomerization can
be a successful alternative.
based on two steps). Along with cisꢀaziridine 3a, isomeric
transꢀaziridine 4a was isolated from the reaction mixture
in a yield of 13%. An increase in the reaction time to 4 h
decreases the yields of both cisꢀ and transꢀaziridines (53 and
10%, respectively), which can be due to the lability of
aziridines in the presence of Lewis acids. The temperature
decrease to –20 C increased stereoselectivity but was
accompanied by a decrease in the total yield of aziridines
(68 and 3% for 3a and 4a, respectively). An increase in the
reaction temperature to 35 C decreased both the yield
and stereoselectivity (54 and 12% for 3a and 4a, respecꢀ
tively). An attempt to carry out the reaction in the oneꢀpot
regime was unsuccessful: the yield of aziridine 3a decreased
to 23%. Perhaps, this is due to the fact that diethyl ether is
the best solvent for the reaction of imine with EDA acꢀ
cording to the literature data.43
Thus, the optimum procedure for the synthesis of
target aziridines is the condensation of amine with alkyl
glyoxylate in benzene followed by the replacement of
the solvent by diethyl ether and stirring of the reacꢀ
tion mixture consisting of imine, diazo compound, and
BF3•OEt2 for 2 h at ambient temperature. These optiꢀ
mum conditions were used for the synthesis of a series of
cisꢀaziridines 3a—f and transꢀaziridines 4a—f (Scheme 2,
Table 1).
As has recently been shown theoretically (DFT calcuꢀ
lation using the B3LYP/6ꢀ31G(d):B3LYP/STOꢀ3G funcꢀ
tionals in the framework of the ONIOM approach),41 the
value of barriers of mutual transformations of isomeric
azomethine ylides generated from Nꢀphenylaziridinediꢀ
carboxylates by 7—9 kcal mol–1 exceeds their barrier for
cycloaddition to fullerene С60, which should provide
stereospecificity and a high stereoselectivity of the reacꢀ
tion of these aziridines with fullerene. The use of this apꢀ
proach for the stereoselective synthesis of 2´,5´ꢀdisubstiꢀ
tuted Nꢀarylpyrrolidinofullerenes is presented in this work.
It is known43 that cisꢀ2ꢀethoxycarbonylꢀsubstituted
aziridines can be obtained by the reaction of imines with
ethyl diazoacetate (EDA) catalyzed by Lewis acids. We
optimized this reaction for the synthesis of target cisꢀazirꢀ
idines. The treatment of imine 2a, which was synthesized
by the condensation of ethyl glyoxylate with 4ꢀmethoxyꢀ
aniline in benzene44 (89% yield), with EDA in the presꢀ
ence of the catalytic amount of BF3•OEt2 (ambient temꢀ
perature, 2 h) gave cisꢀaziridine 3a in a yield of 72% (64%
for two steps). It turned out that the reaction without
isolation of the imine in the pure form simplifies the proꢀ
cedure and also increases the yield of aziridine 3a (86%

Disubstituted Nꢀarylpyrrolofullerenes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 4, April, 2012
865
Scheme 2
Scheme 3
2—4
R
X
2—4
R
X
2—4
R
X
a
b
Et
MeO
c
d
Et BnO
Et Me
e
f
Et
Et CN
I
1ꢀoctyl MeO
3, 5
a
b
R
Et
X
MeO
3, 5
c
d
R
X
2—4
e
f
R
Et
Et CN
X
I
Table 1. Preparative yields of aziridines 3 and 4
Et BnO
Et Me
1ꢀoctyl MeO
Aziridines
Yield (%)
Aziridines
Yield (%)
3 and 4
3 and 4
3
4
3
4
Table 2. Preparative yields of adducts 5 and 6
a
b
c
86
80
50
13
13*
11
d
e
f
82
80
77
14*
15*
12*
Adducts
5 and 6
Yielda (%)
Adducts
5 and 6
Yielda (%)
5
6
5
6
* Purity 90% (see Experimental).
a
b
c
47/80
58/91b
41
—
31
—
d
e
f
41/97 26/76
24/99
30/90
—
—
As can be seen from the presented data (see Scheme 2
a Based on initial aziridine/reacted fullerene.
and Table 1), the character of the substituent in the benꢀ
zene ring exerts almost no effect on the occurrence of all
reaction steps. Therefore, this approach makes it possible
to synthesize aziridines with both donor and acceptor subꢀ
stituents in high yields.
b The reaction was carried out at 80 С.
the yield of polyaddition products of azomethine ylides to
a С60 molecule and to increase the yield of target monoꢀ
adduct, a solution of aziridine in oꢀDCB was slowly added
dropwise with a dosing syringe to a solution of fullerene in
the same solvent at 100 C. The reaction was stereoselecꢀ
tive and afforded only transꢀadducts. The yields are given
in Table 2. Microwave irradiation of the reaction mixture
did not increase the yields.
The reactions of transꢀaziridines 4b,d with fullerene
С60 (Scheme 4) was studied to check stereospecificity
of this reaction. The both reactions afforded only the
cisꢀadduct in each case. No transꢀadducts were detected
even in trace amounts.
It is known48 that aziridines can undergo isomerizaꢀ
tion through the following reaction sequence: ring openꢀ
ing—ylide isomerization—electrocyclization. Reflux of
a solution of cisꢀaziridine 3a in toluene (110 C) for 30 h
resulted in the formation of a complex mixture of products
with prevailing transꢀaziridine (the ratio of aziridines 3a : 4a
was 25 : 75). Thus, the absence of the cisꢀadduct in the
The configuration of aziridines was determined by an
analysis of satellite signals of the aziridine protons: these
signals for cisꢀaziridines are split into a doublet with
a constant of 6 Hz, whereas for transꢀaziridines they look
like singlets (the spinꢀspin coupling constants are close to
zero). According to the literature data,45—47 3JH,H = 6—7 Hz
3
and JH,H = 0—3 Hz for cisꢀ and transꢀaziridines, resꢀ
pectively.
Then cisꢀaziridines 3 were introduced into the reacꢀ
tion with fullerene C60 in oꢀdichlorobenzene (oꢀDCB)
(Scheme 3). The reaction of aziridine 3a with fullerene
nearly does not occur at 50 C, whereas at 80 C it ocꢀ
curred slowly: the initial aziridine is observed in the reacꢀ
tion mixture 24 h after the beginning of heating along with
fullerene С60 and the target monoadduct (the preparative
yield was 37%). The temperature increase to 100 C made
it possible to carry out the reaction within 10 h and to
enhance the yield of monoadduct 5a to 47%. To decrease

866
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 4, April, 2012
Konev et al.
Scheme 4
atoms of the fullerene and benzene ring, which exceeds the
maximum possible number of signals for the transꢀcomꢀ
pound of symmetry C2 (30 signals from the fullerene and
4 signals from the benzene ring) and thus indicates its
cisꢀstructure. The 13С NMR spectrum of compound 5b
contains 31 signals from the carbon atoms of the fullerene
and aromatic rings and does not contradict the assignꢀ
ment of its configuration as trans one. The 13С NMR
spectra of pyrrolidinofullerenes 5f,g useful for analysis of
this type were not obtained because of the low solubility of
these compounds in chloroform, benzene, and DMSO.
Nꢀ(4ꢀHydroxyphenyl)pyrrolidinofullerene is interestꢀ
ing for its subsequent modification due to the high reactivꢀ
ity of the hydroxyl group and possible solubility in alkaline
aqueous solutions. However, we failed to obtain this comꢀ
pound by the removal of the protective benzyl group in
adduct 5c by hydrogenation in the presence of Pd/C in
various solvents at both ambient and elevated temperaꢀ
tures. An alternative way, which is the preliminary elimiꢀ
nation of the benzyl protection from aziridine 3c followed
by the introduction of aziridine 3g into the reaction with
fullerene С60, turned out to be more successful. The reꢀ
moval of the benzyl protecting group by the hydrogenaꢀ
tion of aziridine 3c in THF using Pd/C as a catalyst gives
aziridine 3g in quantitative yield. However, its reaction
with fullerene afforded cycloadduct 5g in a yield of 12%
only. As in the above described reactions of cisꢀaziridines,
only one stereoisomer with the transꢀconfiguration was
formed in the reaction (Scheme 5).
4, 6: R = 1ꢀoctyl, X = MeO (b); R = Et, X = Me (d)
reaction products of fullerene С60 with aziridine 3a indiꢀ
cates a considerably higher rate of cycloaddition of azomeꢀ
thine ylide to the С=С bond of fullerene compared to the
rate of mutual transformation of ylides, which agrees with
the results of our calculations.41
The highꢀresolution mass spectra of synthesized pyrꢀ
rolofullerenes 5 and 6 confirm the elemental composition
of these compounds. Compound 5e forms no molecular
ion when the ESI method is used; however, molecular
ions are observed for ionization by field desorption.
1
The Н NMR spectra of transꢀadducts 5 contain the
Scheme 5
signals from the alkoxycarbonyl groups and aryl substituꢀ
ent along with the characteristic signals of the pyrrolidine
protons at  6.51—6.71. The signals of the same protons
for cisꢀadducts 6b,d lie in the range  5.72—5.86 (i.e., they
are shifted by ~0.7—0.8 ppm to a strongerꢀfield region of
the spectrum).
It is known28,29,33,41 that the signals of the pyrrolidine
protons of cisꢀ2´,5´ꢀdisubstituted pyrrolidinofullerenes
undergo the upfield shift relative to the signals from the
transꢀisomers, and independent and rather reliable criteria
were used for the assignment of the configuration. In parꢀ
ticular, the configuration of the cycloadducts was asꢀ
signed29 on the basis of the Xꢀray structure analysis of the
complex of one of the adducts with tetraphenylporphyriꢀ
natozinc. The NOESY spectra were used33 to prove the
proposed configuration of the cycloadducts. The cycloꢀ
adduct configuration was assigned28 on the basis of an
analysis of molecular symmetry: transꢀadducts of the C2
symmetry group have 30 signals of the fullerene cage in
the 13С NMR spectrum, whereas 32 signals of the fullerene
cage are characteristic of the cisꢀadducts of symmetry Cs.28
The application of this criterion to compounds 5b and 6b
indicates in favor of the assignment made: the 13С NMR
spectrum of compound 6b exhibits 35 signals of the carbon
Thus, it was found that the rate of cycloaddition of
azomethine ylides generated from aziridine dicarboxylates
to fullerene С60 considerably exceeds the rate of their muꢀ
tual transformation, providing stereospecificity and exꢀ

Disubstituted Nꢀarylpyrrolofullerenes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 4, April, 2012
867
Compound 4a. Yellow oil. IR (KBr), /cm–1: 1737 (C=O).
1Н NMR (СDCl3), : 1.23 (t, 6 H, CH3, J = 7.3 Hz); 3.44
(s, 2 H, С(2)H, C(3)Н); 3.76 (s, 3 H, OCH3); 4.17 (q, 4 H, CH2,
J = 7.3 Hz); 6.78 (pseudoꢀd, 2 H, Ar, J = 8.7 Hz); 6.95 (pseudoꢀd,
2 H, Ar, J = 8.7 Hz). 13С NMR (СDCl3), : 14.0 (СH3); 42.3
(CH); 55.4 (OCH3); 61.8 (CH2); 114.2 (CAr); 120.7 (CAr); 140.3
(CN); 155.8 (COMe); 167.0 (C=O). ESIꢀMS, found: m/z 294.1342
[МH]+. C15H20NO5+. Calculated: 294.1336.
Dioctyl cisꢀ1ꢀ(4ꢀmethoxyphenyl)aziridineꢀ2,3ꢀdicarboxylate
(3b) and dioctyl transꢀ1ꢀ(4ꢀmethoxyphenyl)aziridineꢀ2,3ꢀdicarbꢀ
oxylate (4b). Aziridine 3b (187 mg, 0.41 mmol, 81%) and aziriꢀ
dine 4b (30 mg, 0.06 mmol, 13%) as a mixture of 3b (33 mg,
10%) and 4b (90%) were obtained from 4ꢀmethoxyaniline (62 mg,
0.50 mmol), octyl glyoxylate (140 mg, 0.75 mmol), and octyl
diazoacetate (109 mg, 0.55 mmol) (reaction time 2 h).
clusive stereoselectivity of the reaction of aziridines with
fullerene С60: cisꢀaziridines form only transꢀadducts and
transꢀaziridines form only cisꢀadducts. This allows one to
use this reaction for the directed stereoselective synthesis
of cisꢀ and transꢀpyrrolofullerenes from cheap starting
material.
Experimental
IR spectra were recorded on a FTIRꢀ8400S Shimadzu
spectrometer (KBr) or on a Carl Zeiss URꢀ20 spectrometer
(CHCl3). 1H and 13C NMR spectra (300 and 75 NHz, respecꢀ
tively) were obtained on a Bruker Avance DPX 300 spectroꢀ
meter. 13C NMR spectra (125 MHz) were measured on a Varian
VXR Inova 500 S spectrometer. Chemical shifts () are presentꢀ
ed relative to Me4Si. Mass spectra were detected on 7TꢀFTICR
(ESI, 4.2 kV) and micrOTOF 10223 mass spectrometers. Mass
spectra under the conditions of ionization by field desorption
were detected on an AccuTOF GCv mass spectrometer using
a field desorption with a voltage of 10 kV. Flash chromatography
was carried out on silica gel (Мerck, diameter 0.040—0.063 mm).
TLC analysis was performed on aluminum plates Alugram®
SIL G/UV254 covered with a silica gel layer (0.2 mm) with the
UV indicator. Melting points were determined on the Boetius
heating stage (uncorrected values are presented). Elemental analꢀ
ysis was carried out on an HPꢀ185B CHN analyzer. Dichloꢀ
romethane was dried by distillation over P2O5; BF3•OEt2 was
distilled in vacuo prior to use. Alkoxyglyoxylates49 and diazo
compounds50 were synthesized according or similarly to pubꢀ
lished procedures.
Compound 3b. Colorless crystals, m.p. 24—27 С. IR (KBr),
1
/cm–1: 1748, 1724 (C=O). Н NMR (СDCl3), : 0.89 (t, 6 H,
СH3, J = 6.9 Hz); 1.20—1.50 (m, 20 H, СH2); 1.60—1.80 (m, 4 H,
СH2); 3.04 (s, 2 H, С(2)H, C(3)H); 3.77 (s, 3 H, СH3О); 4.21
(t, 4 H, СH2О, J = 6.9 Hz); 6.77—6.84 (m, 2 H, Ar); 6.94—7.01
(m, 2 H, Ar). 13С NMR (СDCl3), : 14.2 (CH3); 22.6; 25.8;
28.5; 29.1; 29.2; 31.8 (СH2С); 43.3 (CH); 55.5 (СH3О); 66.0
(CH2О); 114.3 (CAr); 120.9 (CAr); 144.2, 156.2 (CО, CN); 167.1
(C=O). ESIꢀMS, found: m/z 462.3226 [МH]+. C27H44NO5
.
+
Calculated: 462.3214.
Compound 4b. Yellowish oil. IR (KBr), /cm–1: 1743 (C=O).
1Н NMR (СDCl3), : 0.90 (t, 6 H, СH3, J = 6.5 Hz); 1.20—1.50
(m, 20 H, СH2); 1.50—1.70 (m, 4 H, СH2); 3.44 (s, 2 H, С(2)H,
C(3)H); 3.76 (s, 3 H, СH3О); 4.05—4.20 (m, 4 H, СH2О); 6.78
(pseudoꢀd, 2 H, Ar, J = 9.0 Hz); 6.85 (pseudoꢀd, 2 H, Ar,
J = 9.0 Hz). 13С NMR (СDCl3), : 14.1 (CH3); 22.6; 25.7; 28.4;
29.09; 29.11; 31.7 (СH2С); 42.3 (CH); 55.3 (СH3О); 66.0
Synthesis of aziridines 3 and 4 (general procedure). An aldeꢀ
hyde (0.75 mmol) solution in anhydrous С6Н6 (2 mL) and
Na2SO4 (~0.5 g) were added to a solution of amine (0.5 mmol)
in anhydrous С6Н6 (10 mL), and the mixture was stirred for
30—40 min at ambient temperature. The drying agent was filꢀ
tered off, and benzene was distilled off under reduced pressure.
The residue (the corresponding imine) was dissolved in anꢀ
hydrous Et2O (8 mL), one—two droplets of BF3•OEt2 were addꢀ
ed, and a solution of the diazo compound (0.55 mmol) in anꢀ
hydrous Et2O (2 mL) was introduced dropwise for 2—3 min. The
reaction mixture was stirred for 2 h at ambient temperature, after
which four droplets of Et3N and 1 mL of water were added. The
organic layer was separated and dried over Na2SO4. The crude
product was purified by column chromatography (silica gel, hexꢀ
ane—ethyl acetate). cisꢀAziridines 3 were isolated in the pure
form, whereas transꢀaziridines 4 contained ~10% admixtures.
Diethyl cisꢀ1ꢀ(4ꢀmethoxyphenyl)aziridineꢀ2,3ꢀdicarboxylate
(3a) and diethyl transꢀ1ꢀ(4ꢀmethoxyphenyl)aziridineꢀ2,3ꢀdicarꢀ
boxylate (4a). Aziridine 3a (126 mg, 0.43 mmol, 86%) and aziriꢀ
dine 4a (20 mg, 0.07 mmol, 13%) were obtained from 4ꢀmethꢀ
oxyaniline (62 mg, 0.5 mmol), ethyl glyoxylate (77 mg, 0.75 mmol),
and EDA (63 mg, 0.55 mmol).
(CH2О); 114.2 (CAr); 120.6 (CAr); 140.4, 155.8 (CО, CN); 167.2
(C=O). ESIꢀMS, found: m/z 462.3196 [МH]+. C27H44NO5
.
+
Calculated: 462.3214.
Diethyl cisꢀ1ꢀ(4ꢀbenzyloxyphenyl)aziridineꢀ2,3ꢀdicarboxylate
(3c) and diethyl transꢀ1ꢀ(4ꢀbenzyloxyphenyl)aziridineꢀ2,3ꢀdicarbꢀ
oxylate (4c). Aziridine 3c (93 mg, 0.25 mmol, 50%) and aziriꢀ
dine 4c (20 mg, 0.05 mmol, 11%) were obtained from 4ꢀbenzylꢀ
oxyaniline (100 mg, 0.50 mmol), ethyl glyoxylate (77 mg,
0.75 mmol), and EDA (63 mg, 0.55 mmol) (reaction time 2 h).
Compound 3c. Colorless crystals, m.p. 67—68 С. IR (KBr),
1
/cm–1: 1751 (C=O). Н NMR (СDCl3), : 1.34 (t, 6 H, СH3,
J = 7.1 Hz); 3.05 (s, 2 H, С(2)H, C(3)H); 4.30 (q, 4 H, СH2,
J = 7.1 Hz); 5.03 (s, 2 H, СH2Ph); 6.89 (pseudoꢀd, 2 H, Ar,
J = 8.9 Hz); 6.98 (pseudoꢀd, 2 H, Ar, J = 8.9 Hz); 7.30—7.50
(m, 5 H, Ar). 13С NMR (DMSOꢀd6), : 14.0 (CH3); 42.6 (CH);
60.8 (CH2); 69.5 (СH2Ph); 115.3 (CAr); 120.8 (CAr); 127.6 (CAr);
127.7 (CAr); 128.3 (CAr); 137.2 (CO); 144.3 (CO); 154.7 (CN);
166.8 (C=O). Found (%): C, 68.04; H, 6.19; N, 3.91. C21H23NO5.
Calculated (%): C, 68.28; H, 6.28; N, 3.79.
Compound 4c. IR (СHCl3), /cm–1: 1736 (C=O). 1Н NMR
(СDCl3), : 1.23 (t, 6 H, СH3, J = 7.1 Hz); 3.45 (s, 2 H, С(2)H,
C(3)H); 4.17 (q, 4 H, СH2, J = 7.1 Hz); 5.01 (s, 2 H, СH2Ph);
6.80—7.00 (m, 4 H, Ar); 7.30—7.50 (m, 5 H, Ar). 13С NMR
(СDCl3), : 14.0 (CH3); 42.3 (CH); 61.7 (CH2); 70.2 (СH2Ph);
115.2 (CAr); 120.7 (CAr); 127.5 (CAr); 127.9 (CAr); 128.5 (CAr); 137.0
(CO); 140.6 (CO); 155.0 (CN); 167.0 (C=O). ESIꢀMS, found:
m/z 392.1482 [МNa]+. C21H23NO5Na+. Calculated: 392.1468.
Diethyl cisꢀ1ꢀ(4ꢀmethylphenyl)aziridineꢀ2,3ꢀdicarboxylate
(3d) and diethyl transꢀ1ꢀ(4ꢀmethylphenyl)aziridineꢀ2,3ꢀdicarbꢀ
Compound 3a. Yellow oil. IR (СHCl3), /cm–1: 1736 (С=О).
1Н NMR (СDCl3), : 1.34 (t, 6 H, CH3, J = 7.3 Hz); 3.04 (s, 2 H,
С(2)H, C(3)H); 3.78 (s, 3 H, OCH3); 4.29 (q, 4 H, CH2, J = 7.3 Hz);
6.81 (pseudoꢀd, 2 H, Ar, J = 8.7 Hz); 6.98 (pseudoꢀd, 2 H, Ar,
J = 8.7 Hz). 13С NMR (СDCl3), : 14.1 (СH3); 43.3 (CH); 55.5
(OCH3); 61.8 (CH2); 114.3 (CAr); 120.9 (CAr); 144.1 (CN); 156.2
(COMe); 167.1 (C=O). ESIꢀMS, found: m/z 294.1334 [MH]+.
C15H20NO5+. Calculated: 294.1336.

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Russ.Chem.Bull., Int.Ed., Vol. 61, No. 4, April, 2012
Konev et al.
oxylate (4d). Aziridine 3d (114 mg, 0.41 mmol, 82%) and aziriꢀ
dine 4d (20 mg, 0.07 mmol, 14%) were obtained from 4ꢀmethylꢀ
aniline (54 mg, 0.50 mmol), ethyl glyoxylate (77 mg, 0.75 mmol),
and EDA (63 mg, 0.55 mmol).
(CH2); 106.7 (CCN); 118.8 (CN); 120.4 (CAr); 133.2 (CAr); 151.5
(CN); 166.3 (C=O). ESIꢀMS, found: m/z 289.1193 [МH]+.
C15H17N2O4+. Calculated: 289.1183.
Diethyl cisꢀ1ꢀ(4ꢀhydroxyphenyl)aziridineꢀ2,3ꢀdicarboxylate
(3g). Method А. A mixture of aziridine 3c (10 mg, 0.027 mmol)
and 10% Pd/C (3 mg) in anhydrous THF (3 mL) was stirred for
6 days under dihydrogen. The catalyst was filtered off, and the
solvent was removed in vacuo. The yield of aziridine 3g was
quantitative. Yellowish oil. IR (СHCl3), /cm–1: 3604 (OH),
1734 (C=O). 1Н NMR (СDCl3), : 1.33 (t, 6 H, CH3, J = 7.1 Hz);
3.04 (s, 2 H, С(2)H, C(3)H); 4.29 (q, 4 H, CH2, J = 7.1 Hz);
6.75 (pseudoꢀd, 2 H, Ar, J = 8.8 Hz); 6.89 (pseudoꢀd, 2 H, Ar,
J = 8.8 Hz). 13С NMR (DMSOꢀd6), : 14.0 (CH3); 42.7 (CH);
60.8 (CH2); 115.5 (CAr); 120.8 (CAr); 142.7 (CO); 153.6 (CN);
166.9 (C=O). ESIꢀMS, found: m/z 278.1008 [М – H+]–.
C14H16NO5–. Calculated: 278.1034.
B. A mixture of aziridine 3c (52 mg, 0.14 mmol) and 10%
Pd/C (3 mg) in anhydrous methanol (5 mL) was stirred for 2 h
under dihydrogen. The catalyst was filtered off, the solvent was
removed in vacuo, and the residue was purified by column
chromatography (silica gel, petroleum ether—ethyl acetate).
Aziridine 3g was obtained in a yield of 23 mg (0.08 mmol, 58%).
Synthesis of compounds 5 and 6 (general procedure). A soluꢀ
tion of aziridine 3 or 4 (0.067 mmol) in oꢀDCB (2 mL) was
added dropwise with stirring for 5—7 h to a solution of fullerene
С60 (0.1 mmol) in oꢀDCB (3 mL) heated to 100 С. Then the
reaction mixture was stirred for 2 h more at the same temperaꢀ
ture. The product was isolated by column chromatography on
silica gel using benzene as an eluent.
Compound 3d. Colorless oil. IR (СHCl3), /cm–1: 1750
1
(С=О). Н NMR (СDCl3), : 1.35 (t, 6 H, СH3, J = 7.2 Hz);
2.30 (s, 3 H, СH3); 3.06 (s, 2 H, С(2)H, C(3)H); 4.30 (q, 4 H,
СH2, J = 7.2 Hz); 6.95 (pseudoꢀd, 2 H, Ar, J = 8.3 Hz); 7.09
(pseudoꢀd, 2 H, Ar, J = 8.3 Hz). 13С NMR (СDCl3), : 14.1
(CH3); 20.7 (СH3Ar); 43.0 (CH); 61.7 (CH2); 119.8 (CAr); 129.6
(CAr); 133.5 (CMe); 148.4 (CN); 167.0 (C=O). ESIꢀMS, found:
m/z 278.1376 [МH]+. C15H20NO4+. Calculated: 278.1387.
Compound 4d. Yellowish oil. IR (KBr), /cm–1: 1740 (C=O).
1H NMR (СDCl3), : 1.24 (t, 6 H, СH3, J = 7.2 Hz); 2.28 (s, 3 H,
СH3); 3.45 (s, 2 H, С(2)H, C(3)H); 4.10—4.30 (m, 4 H, СH2);
6.81 (pseudoꢀd, 2 H, Ar, J = 8.3 Hz); 7.05 (pseudoꢀd, 2 H, Ar,
J = 8.3 Hz). 13С NMR (СDCl3), : 14.0 (CH3); 20.7 (СH3Ar);
42.2 (CH); 61.8 (CH2); 119.6 (CAr); 129.5 (CAr); 132.8 (CMe);
144.6 (CN); 167.1 (C=O). ESIꢀMS, found: m/z 278.1386 [МH]+.
C15H20NO4+. Calculated: 278.1387.
Diethyl cisꢀ1ꢀ(4ꢀiodophenyl)aziridineꢀ2,3ꢀdicarboxylate (3e)
and diethyl transꢀ1ꢀ(4ꢀiodophenyl)aziridineꢀ2,3ꢀdicarboxylate
(4e). Aziridine 3e (157 mg, 0.4 mmol, 80%) and aziridine 4e
(30 mg, 0.08 mmol, 15%) were obtained from 4ꢀiodoaniline
(110 mg, 0.5 mmol), ethyl glyoxylate (77 mg, 0.75 mmol), and
EDA (63 mg, 0.55 mmol).
Compound 3e. Colorless oil rapidly turning yellow with time.
1
IR (СHCl3), /cm–1: 1757 (С=О). Н NMR (СDCl3), : 1.35
(t, 6 H, СH3, J = 7.3 Hz); 3.07 (s, 2 H, С(2)H, C(3)H); 4.30
(q, 4 H, СH2, J = 7.3 Hz); 6.83 (pseudoꢀd, 2 H, Ar, J = 8.3 Hz);
7.59 (pseudoꢀd, 2 H, Ar, J = 8.3 Hz). 13С NMR (СDCl3), : 14.1
(CH3); 42.9 (CH); 61.9 (CH2); 87.4 (CI); 122.2 (CAr); 138.0
(CAr); 150.6 (CN); 166.5 (C=O). ESIꢀMS, found: m/z 390.0172
[МH]+. C14H17NO4I+. Calculated: 390.0197.
Compound 4e. Yellowish oil. IR (KBr), /cm–1: 1737 (С=О).
1Н NMR (СDCl3), : 1.25 (t, 6 H, СH3, J = 7.2 Hz); 3.45 (s, 2 H,
С(2)H, C(3)H); 4.20 (q, 4 H, СH2, J = 7.1 Hz); 6.01 (pseudoꢀd,
2 H, Ar, J = 8.6 Hz); 7.55 (pseudoꢀd, 2 H, Ar, J = 8.6 Hz).
13С NMR (СDCl3), : 14.0 (CH3); 42.0 (CH); 62.0 (CH2);
86.6 (CI); 122.0 (CAr); 137.8 (CAr); 147.1 (CN); 166.6 (C=O).
ESIꢀMS, found: m/z 390.0167 [МH]+. C14H17NO4I+. Calculatꢀ
ed: 390.0197.
Diethyl cisꢀ1ꢀ(4ꢀcyanophenyl)aziridineꢀ2,3ꢀdicarboxylate (3f)
and diethyl transꢀ1ꢀ(4ꢀcyanophenyl)aziridineꢀ2,3ꢀdicarboxylate
(4f). Aziridine 3f (111 mg, 0.39 mmol, 77%) and aziridine 4f
(18 mg, 0.06 mmol, 12%) were obtained from 4ꢀaminobenzoꢀ
nitrile (59 mg, 0.5 mmol), ethyl glyoxylate (77 mg, 0.75 mmol),
and EDA (63 mg, 0.55 mmol).
Compound 3f. Colorless oil. IR (KBr), /cm–1: 1747 (СО),
2226 (CN). 1Н NMR (СDCl3), : 1.35 (t, 6 H, СH3, J = 7.1 Hz);
3.16 (s, 2 H, С(2)H, C(3)H); 4.32 (q, 4 H, СH2, J = 7.1 Hz);
7.28 (pseudoꢀd, 2 H, Ar, J = 8.5 Hz); 7.60 (pseudoꢀd, 2 H, Ar,
J = 8.5 Hz). 13С NMR (СDCl3), : 14.1 (CH3); 42.8 (CH); 62.2
(CH2); 107.6 (CCN); 118.6 (CN); 120.8 (CAr); 133.5 (CAr); 154.6
(CN); 166.1 (C=O). ESIꢀMS, found: m/z 289.1183 [МH]+.
C15H17N2O4+. Calculated: 289.1183.
Diethyl transꢀ1´ꢀ(4ꢀmethoxyphenyl)ꢀ2´,5´ꢀdihydropyrroloꢀ
[3´,4´:1,9](C60ꢀIh)[5,6]fullereneꢀ2´,5´ꢀdicarboxylate (5a). Adꢀ
duct 5a (31.6 mg, 47%) was obtained from aziridine 3a (19.5 mg,
0.067 mmol) and C60 (72 mg, 0.1 mmol). The reaction mixture
also gave unreacted С60 (44 mg). The yield of 5a based on reactꢀ
ed С60 was 80%. Brown powder. IR (СHCl3), /cm–1: 1734
1
(С=О). Н NMR (СDCl3), : 1.18 (t, 6 H, CH3, J = 7.3 Hz);
3.88 (s, 3 H, OCH3); 4.26 (m, 4 H, CH2, J = 7.0 Hz); 6.51 (s, 2 H,
CH); 7.03 (pseudoꢀd, 2 H, Ar, J = 8.7 Hz); 7.36 (pseudoꢀd, 2 H,
Ar, J = 8.7 Hz). 13С NMR (СDCl3), : 14.2 (СH3); 55.5 (CH);
61.8 (OCH3); 71.2 (CH2); 74.7 (Csp3 of fullerene); 114.8; 120.9;
130.5; 139.7; 140.2; 141.8; 142.0; 142.2; 145.6; 145.8; 146.1;
146.4 (CAr); 170.3 (C=O) (the rest signals of fullerene were
not unambiguously differentiated from the noise). 13С NMR
(125 МHz, С6D6), : 14.3 (CH3); 55.1 (CH3O); 61.6 (CH2);
72.1 (C of pyrrole); 75.4 (CH); 115.1 (CArH); 122.0 (CArH);
136.8; 137.5; 139.1; 140.0; 140.5; 140.8; 142.08; 142.14; 142.2;
142.3; 142.4; 142.5; 142.9; 143.0; 143.2; 143.4; 144.77; 144.85;
145.5; 145.6; 145.89; 146.0; 146.28 (4 C); 146.33; 146.6; 146.7;
147.7; 151.5; 154.1 (CAr); 156.2; 170.0 (C=O). ESIꢀMS, found:
m/z 1014.1335 [МH]+. C75H20NO5+. Calculated: 1014.1336.
Dioctyl transꢀ1´ꢀ(4ꢀmethoxyphenyl)ꢀ2´,5´ꢀdihydropyrroloꢀ
[3´,4´:1,9](C60ꢀIh)[5,6]fullereneꢀ2´,5´ꢀdicarboxylate (5b).
A solution of aziridine 3b (31 mg, 0.06 mmol) in oꢀDCB (2 mL)
was slowly added dropwise with a dosing syringe to a solution of
fullerene C60 (72 mg, 1 mmol) in oꢀDCB (3 mL) for 4.5 h at
80 C. The reaction mixture was stirred for 41 h at 80 C. The
purification by column chromatography (silica gel, benzene) gave
compound 5b as a brown powder (46 mg, 58%) and 41 mg of
unreacted C60. The yield of 5b based on reacted C60 was 91%. IR
Compound 4f. Yellowish oil. IR (KBr), /cm–1: 1734 (СО),
2225 (CN). 1Н NMR (СDCl3), : 1.27 (t, 6 H, СH3, J = 7.1 Hz);
3.50 (s, 2 H, С(2)H, C(3)H); 4.22 (pseudoꢀq, 4 H, СH2, J = 6.8 Hz);
6.97 (pseudoꢀd, 2 H, Ar, J = 8.6 Hz); 7.57 (pseudoꢀd, 2 H, Ar,
J = 8.6 Hz). 13С NMR (СDCl3), : 14.0 (CH3); 42.0 (CH); 62.2
1
(KBr), /cm–1: 1755, 1730 (С=О). H NMR (CDCl3), : 0.87
(t, 6 H, 2 CH3, J = 6.8 Hz); 1.15—1.40 (m, 20 H, 10 CH2);

Disubstituted Nꢀarylpyrrolofullerenes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 4, April, 2012
869
1.50—1.65 (m, 4 H, 2 CH2); 3.87 (s, 3 H, CH3O); 4.10—4.25
(m, 4 H, 2 CH2O); 6.52 (s, 2 H, CH); 6.95—7.10 (m, 2 H,
H arom.); 7.30—7.45 (m, 2 H, H arom.). 13C NMR (CDCl3),
: 14.1 (CH3); 22.6 (CH2); 25.9 (CH2); 28.5 (CH2); 29.1 (CH2);
31.7 (CH2); 55.4 (CH3O); 65.9 (CH2O); 71.2 (Csp3); 74.8 (CH);
114.7; 120.9; 136.3; 136.9; 138.4; 139.7; 140.1; 141.75; 141.81;
141.9; 142.1; 142.2; 142.65; 142.7; 143.1; 144.48; 144.54; 145.27;
145.33; 145.57; 145.59; 145.70; 145.78; 146.1; 146.36; 146.41;
147.5; 150.7; 153.3; 155.3 (Csp2); 170.4 (C=O). ESIꢀMS, found:
m/z 1182.3213 [МH]+. C87H44NO5+. Calculated: 1182.3214.
Diethyl transꢀ1´ꢀ(4ꢀbenzyloxyphenyl)ꢀ2´,5´ꢀdihydropyrroloꢀ
[3´,4´:1,9](C60ꢀIh)[5,6]fullereneꢀ2´,5´ꢀdicarboxylate (5c). Adꢀ
duct 5c (27.0 mg, 41%) was obtained from aziridine 3c (22.1 mg,
0.059 mmol) and С60 (72 mg, 0.1 mmol). Brown powder. IR
146.9; 147.9; 151.2; 153.9 (CAr); 169.8 (C=O). ESIꢀMS, found:
m/z 1110.0196 [МH]+. C74H17INO4+. Calculated: 1110.0197.
Diethyl transꢀ1´ꢀ(4ꢀcyanophenyl)ꢀ2´,5´ꢀdihydropyrroloꢀ
[3´,4´:1,9](C60ꢀIh)[5,6]fullereneꢀ2´,5´ꢀdicarboxylate (5f). Adꢀ
duct 5f (16.6 mg, 25%) was obtained from aziridine 3f (19.2 mg,
0.067 mmol) and C60 (72 mg, 0.1 mmol). Unreacted С60 (54 mg)
was isolated from the reaction mixture. The yield of 5f based on
reacted С60 was 65%. Brown powder. IR (KBr), /cm–1: 2222
(CN), 1751, 1734 (C=O). 1Н NMR (СDCl3), : 1.20 (t, 6 H,
CH3, J = 7.3 Hz); 4.30 (m, 4 H, CH2, J = 7.3 Hz); 6.56 (s, 2 H,
CH); 7.31 (pseudoꢀd, 2 H, Ar, J = 8.7 Hz); 7.78 (pseudoꢀd, 2 H,
Ar, J = 8.7 Hz). MS (field desorption), found: m/z 1008.1 [M+].
C75H16N2O4. Calculated: 1008.1110.
Diethyl transꢀ1´ꢀ(4ꢀhydroxyphenyl)ꢀ2´,5´ꢀdihydropyrroloꢀ
[3´,4´:1,9](C60ꢀIh)[5,6]fullereneꢀ2´,5´ꢀdicarboxylate (5g). Adꢀ
duct 5g (8.0 mg, 13%) was obtained from aziridine 3g (16.7 mg,
0.060 mmol) and C60 (72 mg, 0.1 mmol). Unreacted С60 (65 mg)
was isolated from the reaction mixture. The yield of 5g based on
С60 was 82%. Brown powder. IR (KBr), /cm–1: 1739 (C=O).
1Н NMR (СDCl3), : 0.78 (t, 6 H, CH3, J = 7.3 Hz); 2.41 (s, 1 H,
OH); 3.87—3.99 (m, 4 H, CH2); 6.62 (pseudoꢀd, 2 H, Ar,
1
(KBr), /cm–1: 1755, 1745 (С=О). Н NMR (СDCl3), : 1.17
(t, 6 H, CH3, J = 7.1 Hz); 4.26 (q, 2 H, CH2, J = 7.1 Hz); 4.27
(q, 2 H, CH2, J = 7.1 Hz); 5.13 (s, 2 H, CH2Ph); 6.51 (s, 2 H,
CH); 7.11 (pseudoꢀd, 2 H, Ar, J = 9.0 Hz); 7.36 (pseudoꢀd, 2 H,
Ar, J = 9.0 Hz); 7.35—7.55 (m, 5 H, Ph). 13С NMR (125 МHz,
С6D6), : 14.3 (СH3); 61.6 (H2СО); 70.5 (СH2Ar); 72.1 (C of pyrꢀ
role); 75.4 (С of pyrrole); 116.3 (СArH); 122.2 (СArH); 128.9
(СArH); 136.9; 137.7; 137.9; 139.5; 140.2; 140.7; 142.27; 142.33;
142.4; 142.5; 142.6; 142.7; 143.1; 143.2; 143.6; 144.97; 145.04;
145.7; 145.8; 146.07; 146.09; 146.2; 146.46; 146.47; 146.52 (4 C);
146.8; 146.9; 147.9; 151.7; 154.3; 155.6 (CAr); 170.0 (C=O) (two
signals from the C atoms of the benzyl ring are overlapped with
the signal from benzene). ESIꢀMS, found: m/z 1090.1657 [МH]+.
C81H24NO5+. Calculated: 1090.1649.
J = 8.8 Hz); 6.71 (s, 2 H, CH); 7.35 (pseudoꢀd, 2 H, Ar,
+
J = 8.8 Hz). ESIꢀMS, found: m/z 1000.1173 [MH]+. C74H18NO5
.
Calculated: 1000.1180.
Dioctyl cisꢀ1´ꢀ(4ꢀmethoxyphenyl)ꢀ2´,5´ꢀdihydropyrroloꢀ
[3´,4´:1,9](C60ꢀIh)[5,6]fullereneꢀ2´,5´ꢀdicarboxylate (6b).
A solution of aziridine 4b (29 mg, 0.06 mmol) in oꢀDCB (2 mL)
was slowly added dropwise with a dosing syringe to a solution of
fullerene C60 (68 mg, 0.09 mmol) in oꢀDCB (3 mL) for 7 h at
80 C. The reaction mixture was stirred for 24 h at 80 C. The
purification by column chromatography (silica gel, benzene) gave
compound 6b as a brown powder (17 mg, 31%). IR (KBr),
Diethyl transꢀ1´ꢀ(4ꢀmethylphenyl)ꢀ2´,5´ꢀdihydropyrroloꢀ
[3´,4´:1,9](C60ꢀIh)[5,6]fullereneꢀ2´,5´ꢀdicarboxylate (5d). Adꢀ
duct 5d (27.4 mg, 41%) was obtained from aziridine 3d (18.5 mg,
0.067 mmol) and C60 (72 mg, 0.1 mmol). Unreacted C60 (51 mg)
was isolated from the reaction mixture. The yield of 5d based on
reacted С60 was 94%. Brown powder. IR (СHCl3), /cm–1: 1726
1
/cm–1: 1757, 1730 (С=О). H NMR (CDCl3), : 0.86 (t, 6 H,
2 CH3, J = 6.9 Hz); 1.10—1.40 (m, 20 H, 10 CH2); 1.45—1.55
(m, 4 H, 2 CH2); 3.90 (s, 3 H, CH3O); 4.05—4.25 (m, 4 H, 2 CH2O);
5.72 (s, 2 H, CH); 7.00—7.10 (m, 2 H, H arom.); 7.75—7.85 (m, 2 H,
H arom.). 13C NMR (CDCl3), : 14.1 (CH3); 22.6 (CH2); 25.9
(CH2); 28.5 (CH2); 29.1 (CH2); 31.8 (CH2); 55.4 (CH3O); 66.0
(CH2O); 71.4 (Csp3); 78.1 (CH); 114.9; 127.0; 136.0; 138.15;
138.18; 140.1; 140.3; 142.2; 142.3; 142.40; 142.43; 142.6; 142.7;
143.13; 143.14; 143.5; 143.6; 144.8; 145.1; 145.72; 145.74;
145.84; 145.89; 146.1; 146.16; 146.51; 146.54; 146.7; 146.8; 146.9
(Csp2); 147.9; 151.4; 152.8; 158.4; 168.9 (C=O). ESIꢀMS, found:
m/z 1182.3209 [МH]+. C87H44NO5+. Calculated: 1182.3214.
Diethyl cisꢀ1´ꢀ(4ꢀmethylphenyl)ꢀ2´,5´ꢀdihydropyrroloꢀ
[3´,4´:1,9](C60ꢀIh)[5,6]fullereneꢀ2´,5´ꢀdicarboxylate (6d). Adꢀ
duct 6d (17.2 mg, 26%) was obtained from aziridine 4d (18.5 mg,
0.067 mmol) and C60 (72 mg, 0.1 mmol). Unreacted С60 (55 mg)
was isolated from the reaction mixture. The yield of 6d based on
reacted С60 was 76%. Brown powder. IR (KBr), /cm–1: 1757,
1734 (C=O). 1H NMR (СDCl3), : 1.19 (t, 6 H, CH3, J = 7.2 Hz);
2.44 (s, 3 H, CH3); 4.27 (q, 4 H, CH2, J = 7.3 Hz); 5.86 (s, 2 H,
СH); 6.82 (pseudoꢀd, 2 H, Ar, J = 8.7 Hz); 7.58 (pseudoꢀd, 2 H,
Ar, J = 8.6 Hz). 13С NMR (125 МHz, С6D6), : 14.5 (CH3);
30.5 (CH3); 61.9 (CH2); 72.3 (C of pyrrole); 77.8 (C of pyrrole);
123.9 (CArH); 130.5 (CArH); 135.2; 135.9; 138.5; 140.2; 140.4;
142.2; 142.42; 142.44; 142.47; 142.65; 142.67; 143.2 (4 С);
143.55; 143.57; 143.6; 144.9; 145.1; 145.70; 145.73; 146.0; 146.1;
146.20; 146.22; 146.3; 146.46; 146.52; 146.7; 146.8; 146.9; 147.8;
151.8; 153.5; 168.6 (C=O). ESIꢀMS, found: m/z 998.1381
[МH]+. C75H20NO4+. Calculated: 998.1387.
1
(С=О). Н NMR (СDCl3), : 1.18 (t, 6 H, CH3, J = 7.0 Hz);
2.40 (s, 3 H, CH3); 4.18—4.36 (m, 4 H, CH2); 6.54 (s, 2 H, СH);
7.25—7.29 (m, 4 H, Ar). 1H NMR (С6D6), : 1.18 (t, 6 H, CH3,
J = 7.0 Hz); 2.40 (s, 3 H, CH3); 4.30 (q, 4 H, CH2, J = 7.3 Hz);
6.54 (s, 2 H, СH); 6.82 (pseudoꢀd, 2 H, Ar, J = 8.7 Hz); 7.58
(pseudoꢀd, 2 H, Ar, J = 8.6 Hz). 13С NMR (125 МHz, С6D6),
: 14.2 (CH3); 30.3 (CH3); 61.6 (CH2); 71.9 (C of pyrrole); 75.1
(CH); 120.1 (CArH); 130.3 (CArH); 132.1; 136.7; 137.4; 139.9;
140.5; 142.07; 142.1; 142.2; 142.3; 142.4; 142.5; 142.9; 143.0;
143.4; 143.7; 144.76; 144.84; 145.5; 145.6; 145.87; 145.89; 146.0;
146.2; 146.26 (4 С); 146.32; 146.6; 146.67; 147.7; 151.4; 154.1
(CAr); 170.0 (C=O). ESIꢀMS, found: m/z 998.1386 [МH]+.
C75H20NO4+. Calculated: 998.1387.
Diethyl transꢀ1´ꢀ(4ꢀiodophenyl)ꢀ2´,5´ꢀdihydropyrroloꢀ
[3´,4´:1,9](C60ꢀIh)[5,6]fullereneꢀ2´,5´ꢀdicarboxylate (5e). Adꢀ
duct 5e (18.0 mg, 24%) was obtained from aziridine 3e (26.0 mg,
0.067 mmol) and C60 (72 mg, 0.1 mmol). Unreacted С60 (59 mg)
was isolated from the reaction mixture. The yield of 5e based on
reacted С60 was 90%. Brown powder. IR (KBr), /cm–1: 1725
1
(С=О). Н NMR (СDCl3), : 1.22 (t, 6 H, CH3, J = 7.3 Hz);
4.28 (m, 4 H, CH2, J = 7.3 Hz); 6.51 (s, 2 H, СH); 7.11 (pseudoꢀd,
2 H, Ar, J = 8.7 Hz); 7.77 (pseudoꢀd, 2 H, Ar, J = 8.7 Hz). 13С NMR
(125 МHz, С6D6), : 14.4 (СH3); 62.0 (CH2); 71.9 (C of pyrꢀ
role); 75.0 (C of pyrrole); 122.0 (CArH); 136.7 (CAr); 137.5 (CAr);
138.7 (CArH); 140.1; 140.7; 142.2; 142.3; 142.4 (3 С); 142.6;
142.7; 143.1; 143.2; 143.4; 143.6; 144.9; 145.0; 145.7; 145.8;
146.00; 146.09; 146.13; 146.21; 146.24; 146.3; 146.5 (3 С); 146.8;

870
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This work was financially supported by the Russian
Foundation for Basic Research (Project No 11ꢀ03ꢀ00186),
St. Petersburg State University (Grant 12.38.78.2012), and
the Federal GrantꢀinꢀAid Program "Human Capital for
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Received October 16, 2011