Bisaziridine tetracarboxylates as building blocks in the stereoselective synthesis of C60-fullerene diads and dumbbell-like bis-C 60-fullerene triads

Article abstract of DOI:10.1021/jo2009627

The synthesis of alkoxycarbonyl-substituted bisaziridines with the two aziridine units connected by conjugated p-phenylene, partly conjugated 1,1′-biphenyl-4,4′-diyl, and nonconjugated 4,4′- methylenediphenyl linkers was developed. The reaction of azometh

Full text of DOI:10.1021/jo2009627

ARTICLE
pubs.acs.org/joc
Bisaziridine Tetracarboxylates as Building Blocks in the
Stereoselective Synthesis of C60-Fullerene Diads and Dumbbell-like
Bis-C60-fullerene Triads
Alexander S. Konev,† Alexander F. Khlebnikov,*,† and Holm Frauendorf ‡
†Department of Chemistry, Saint Petersburg State University, Universitetskii pr. 26, 198504 St. Petersburg, Russia
‡Institute of Organic and Biomolecular Chemistry of Georg-August-University, Tammannstrasse 2, D37077 G€ottingen, Germany
S Supporting Information
b
ABSTRACT: The synthesis of alkoxycarbonyl-substituted bisa-
ziridines with the two aziridine units connected by conjugated
p-phenylene, partly conjugated 1,10-biphenyl-4,40-diyl, and non-
conjugated 4,40-methylenediphenyl linkers was developed. The
reaction of azomethine ylides derived from the bisaziridines with
fullerene C60 was optimized and used for the stereoselective
preparation of both the monoadducts (C60ꢀlinkerꢀaziridine
dicarboxylate), and the dumbbell bisadducts (C60ꢀlinkerꢀC60).
The reasons for the observed selectivity of the azomethine ylide formation and cycloaddition were theoretically studied at the DFT
B3LYP/6-31G(d) level or at the ONIOM B3LYP/6-31G(d):B3LYP/STO-3G level for fullerene-containing molecules.
’ INTRODUCTION
was another problem, which could be overcome by the incor-
poration of long aliphatic chains into the aromatic core of the
linker.1b These difficulties, along with the increasing interest to
dumbbell-like bisfullerene triads,1b stimulate the search for other
routes for their synthesis. A good methodology for the synthesis
of linkers of different geometry and molecular conductance,
which can be effectively fastened to fullerene, could contribute to
the development of the aforementioned fields of nanoscience.
The Prato reaction, 1,3-dipolar cycloaddition of azomethine-
ylides across the [6,6]-juncture of the fullerene core to form
fulleropyrrolidine derivatives, is one of the most widely used
methods for the construction of fullerene diads and triads.6 Three
methods are mostly used for the generation of azomethine-ylides
in this reaction: (1) condensation of carbonyl compounds with
R-amino acids followed by decarboxylation and dehydration of
the primary products,2,6,7 (2) condensation of carbonyl com-
pounds with amines followed by imineꢀylide tautomerization or
dehydration of the primary products,6e,7l,8 and (3) thermal
electrocyclic ring-opening of aziridines.1b,7a,9 This last approach
is less investigated than the other two, but this method can be
expected to provide a stereoselective route to fulleropyrrolidine
derivatives, because the configuration of the aziridine determines
the configuration of the ylide resulting from the ring-opening,10
while prediction of the configuration of the ylide is rather difficult
in the first two cases. Relatively mild conditions for the ring-opening
of suitably substituted aziridines can be an additional advantage of
the aziridine approach to fulleropyrrolidines.
Dumbbell-like compounds containing two fullerene C60 moi-
eties draw attention as candidates for applications in molecular
electronics1 and in the construction of photovoltaic devices.2
Thus, fullerene-based compounds with fullerenes as anchoring
groups have been recently designed and applied as a single-
molecule junction for molecular electronic devices. These junc-
tions showed a lower spread in low-bias conductance and
increased stretching length before breaking compared to com-
monly used thiol-based junctions.1 Significant interest has been
also developed in fullerene-containing diads and triads for
photovoltaic applications. It is marked that the rates of forward
and back electron transfer in fullerene-containing hybride do-
norꢀacceptor systems depend on the molecular geometry, i.e., it
is possible to modulate these properties by varying the separation
or spatial orientation of the donor and acceptor units by means of
the appropriate linker.3 Fullerenes C60 are known to form stable
monolayers on Au surfaces.4 This, along with the reported
increased stability of bisfullerene junctions,1 allows us to imagine
a possible application of dumbbell-like fullerene molecules as
seeds for growing gold nanorods, such as in the published
experiments with thiol derivatives.5 Application of rigid full-
erene-capped linkers-seeds would provide a synthesis of nanos-
tructures of predefined architecture.
A number of dumbbell-like fullerene compounds have been
previously synthesized by reaction of fullerene, carbonyl com-
pounds, and suitable diamines.1 Unfortunately, the yields of the
products were only about 5ꢀ14%, presumably due to the harsh
reaction conditions. The described reaction of bisaziridines with
fullerene C60 resulted in low yields of 5% for bisfullerene-adduct
as well.1b Extremely low solubility of the synthesized bisadducts
Received: May 12, 2011
Published: June 07, 2011
r
2011 American Chemical Society
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Scheme 1
Figure 1. Geometry of some dumbbell-like fullerene ensembles available via the bisaziridine synthetic approach optimized at the DFT ONIOM
B3LYP/6-31G(d):B3LYP/STO-3G level.
In the framework of our research concerning the synthesis of
heterocycles via N-ylide reactions,9f,g,11 compounds with two
aziridine units connected by different linkers have been devel-
oped, which allow the construction of dumbbell-like fullerene
ensembles with predefined geometry and variable conjugation.
We have chosen conjugated p-phenylene, partly conjugated 1,
10-biphenyl-4,40-diyl, and nonconjugated 4,40-methylenediphenyl
as the linkers that allow the creation of products with linear
or bent geometry and with different molecular conductance
(Figure 1, Scheme 1).
Varying the substituents on the aziridine ring allows the
solubility of the fullerene ensembles to be modified and also
provides the additional possibility of modulating their shape. The
developed approach is also potentially suitable for the preparation
of unsymmetrical fullerene-containing diads using fullereneꢀ
bisaziridine monoadducts.
We present here the synthesis and characterization of alkyl
bisaziridine tetracarboxylates, the reaction of azomethine ylides
generated from them with fullerene C60, and the preparation and
characterization of new fullerene-containing diads and dumbbell-
like triads.
’ RESULTS AND DISCUSSION
The target bisaziridines were prepared according to the se-
quence presented in the retrosynthetic Scheme 1. Freshly pre-
pared aldehyde 1a from the oxidation of diethyl tartrate with
periodic acid12 was condensed with p-phenylene diamine 2a to
give bisimine 3a. After simple workup, the crude imine was
immediately reacted with ethyl diazoacetate 4a in the presence of
a catalytic amount of BF3 OEt2 to yield a mixture of the bis-
3
aziridines 5a and 6a (Table 1, Scheme 2). The bisaziridines
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decompose slowly under the reaction conditions, and a pro-
longed reaction time in the second step decreases the product
yields (Table 1, entries 1ꢀ4). The best results were obtained in
experiments where a benzene solution of 3 equiv of 1a was stirred
with 1 equiv of 2a in the presence of anhyd Na2SO4 for 0.5 h at rt
and then reacting the resulting imine with the catalyst and
2.2 equiv of 4a in ether for 4 h at rt (Table 1, entry 5), yielding
5a (55%) and 6a (27%). The preferred formation of cis-aziridines
A further goal was to find optimal conditions for the synthesis
of the monoadducts of bisaziridines 5, 6 to fullerene C60, because
the aziridine moiety, remaining in the monoadduct, can also be
used as a joining tool for the construction of C60-based hybrid
ensembles. The thermally allowed conrotatory opening of one
aziridine ring in the bisaziridine 5 leads to the formation of only
the S-ylide10b cis-A-SY. Provided no isomerization of the S-ylide
cis-A-SY occurs under the reaction conditions, cycloaddition of
this ylide to C60 should give the adduct 7 as the sole stereoisomer
(Scheme 3).
in BF3 OEt2-catalyzed reactions of diazo compounds with imines
3
is well documented.13
In contrast, the thermally allowed conrotatory opening of one
aziridine ring in the bisaziridine 6 can lead to the formation of
three ylides: the S-ylide trans-A-SY, the W-ylide cis-A-WY, and
the U-ylide cis-A-UY (Scheme 4). The cycloaddition of the
W-ylide cis-A-WY and the U-ylide cis-A-UY to C60 will lead to
two conformers of adduct 8, which can interconvert via the
nitrogen inversion. The cycloaddition of the S-ylide trans-A-SY
to C60 will lead to the two stereoisomeric adducts 9, 10.
To evaluate the possible selectivity of the discussed reactions,
we performed DFT B3LYP/6-31G(d) model calculations of
energy profiles for transformations of diethyl 1-phenylaziridin-
2,3-dicarboxylates cis- and trans-A and the corresponding ylides
SY, UY, and WY (Figure 2). According to the results obtained,
the barriers to the conrotatory opening of the aziridine ring in
model compound cis-A, leading to S-ylide SY, and compound
trans-A, leading to U-ylide UY and W-ylide WY, are very close.
The barriers to interconversion of the ylides SY, UY, and WY
have the same order of values as the barriers to the ring-opening.
The reaction of fullerene with the above-mentioned aziridines
will, therefore, be selective only if the barriers to cycloaddition of
the ylides to C60 are lower than the barriers to interconversion of
the ylides. The barriers to cycloaddition of the ylides SY, UY, and
WY to C60 were computed at the ONIOM B3LYP/6-31G(d):
B3LYP/STO-3G level.16 Earlier we found9f for similar systems
that the ONIOM simplification for the fullerene moiety, except-
ing common atoms of fullerene and pyrrolidine rings, is valid.
The calculated barrier to cycloaddition of the ylides SY, UY, and
Having found the optimal conditions, we next synthesized a
number of cis,cis- and cis,trans-bisaziridines 5 and 6 (Table 2).
Octyl glyoxylate 1b and octyl diazoacetate 4b, which are required
for the preparation of aziridines 5dꢀf and 6dꢀf, were prepared
analogously to published procedures.12,14 The structures of bis-
aziridines 5aꢀf and 6aꢀf were verified by 1H and 13C NMR and
IR spectroscopy, elemental analysis, and HRMS. The 1H NMR
spectra of compounds 5 contain only one set of signals for the
protons of the aziridine rings, alkyl chains, and aromatic cores,
meaning either a cis,cis or trans,trans configuration of aziridine
1
fragments. The H NMR spectra of compounds 5 show the
doubletꢀdoublet satellite signals for the aziridine protons with
3
the JHH constant in the range 6.2ꢀ7.0 Hz, proving cis,cis-
configuration of 5, after taking into consideration that 3JHH are
0ꢀ3 Hz in trans-aziridines and 6ꢀ7 Hz in cis-aziridines.13b,15 In
contrast, the 1H NMR spectra of compounds 6 contain two sets
of signals for the protons of aziridine rings, alkyl chains, and
aromatic cores, unambiguously attesting to nonequivalence of
the aziridine rings and C1 symmetry of the molecules, which
therefore are cis,trans-bisaziridines. Thus, compounds 6aꢀf show
a singlet signal at 3.04ꢀ3.11 ppm, which corresponds well to the
value of the chemical shift for aziridine protons of cis,cis-
bisaziridines 5 (3.05ꢀ3.12 ppm), and it can thus be attributed
to the cis-aziridine ring in 6. The characteristic value of a
spinꢀspin coupling constant of 6.9 Hz found for the satellite
signals of cis-aziridine protons (at 3.06 ppm) in 6c provides
independent proof. Along with the signal for the cis-aziridine
rings, a singlet at 3.43ꢀ3.50 ppm for the protons of the trans-
aziridine ring was observed in compounds 6 having the char-
acteristic trans-3JHH = 2.4 Hz for the satellite signals.
WY to C60 (ΔGq kcal molꢀ1) are 20.3, 19.5, 19.2, respectively.
3
The barrier to cycloaddition of the ylide SY to ethylene calculated
at the B3LYP/6-31G(d) level for comparison equals 22.3 kcal
3
molꢀ1. From this data one can conclude that the reaction of
Table 1. Optimization of the Synthesis of Bisaziridines 5a, 6a
Table 2. Synthesis of Bisaziridines 5 and 6
yield, %
R
X
1
2
4
yield of 5, % yield of 6, %
entry
ratio 1a:4a:2a
reaction time, h
5a
6a
Et
Et
Et
1,4-C6H4
4,40-(C6H4)2
4,40-(C6H4)2CH2 1a 2c 4a
1a 2a 4a
1a 2b 4a
5a, 55
5b, 24
5c, 38
5d, 61
5e, 38
5f, 58
6a, 27
6b, -
1
2
3
4
5
4:3:1
24; 6
24; 6
24; 12
24; 6
0.5; 4
39
36
30
2
ꢀ
ꢀ
11
ꢀ
27
4:2.2:1
6c, 20
6d, 14
6e, 10
6f, 25
2.2:2.2:1
oct-1-yl 1,4-C6H4
oct-1-yl 4,40-(C6H4)2
oct-1-yl 4,40-(C6H4)2CH2 1b 2c 4b
1b 2a 4b
2.2:2.2:1 (“old” aldehyde)
3:2.2:1
1b 2b 4b
55
Scheme 2
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Scheme 3
Scheme 4
bisaziridines 5 in not very harsh conditions will give only one
cycloadduct 7, whereas the reaction of bisaziridines 6 under the
same conditions will give a mixture of monoadducts 8ꢀ10. After
analysis of these computation results, we have chosen bisaziridine
5a as the best candidate for finding optimal conditions of the
synthesis of monoadducts.
temperatures higher than 80 °C, further reactions of the aziridine
ring in the primary product lead to the formation of bisadducts or
polymers. Changing o-DCB to 1MN has only a minor effect on
the yield. The optimized reaction conditions were used for the
synthesis of monoadducts 7aꢀd,f (Table 4).
The 1H NMR spectra of compounds 7aꢀf contain signals for
cis-aziridine protons at 3.11ꢀ3.18 and signals for the pyrrolidine
protons at 6.49ꢀ6.60 ppm. The constant 3JHH = 6.7 Hz for the
Caziridine-2/3 satellite signals in the 1H NMR spectrum of
compound 7b also suggests a cis-configuration of the aziridine
fragment. This means that the configuration of the surviving
The reaction of the bisaziridine 5a with C60 was performed
at various temperatures under conventional heating or under
microwave irradiation, in o-dichlorobenzene (o-DCB) or 1-methyl-
naphthalene (1MN) (Table 3). The conditions of choice are
the slow dropwise addition of the o-DCB solution of the
bisaziridine 5a to the solution of 3.3 equiv of C60 in o-DCB at
80 °C followed by stirring the reaction mixture at this tem-
perature for several hours until all the aziridine is consumed.
Under these conditions, monoadduct 7a was isolated in 65%
yield. No products were detected at lower temperatures (Table 3,
entries 1, 2). Increasing the temperature decreases the yield
significantly (Table 3, entries 4ꢀ6). Thus, though the reaction
proceeded at 100 °C much faster than at 80 °C, the yield of the
monoadduct 7a was only 32%. The soluble polymer of unknown
composition was the only product when the reaction was
performed at 120 °C. Analogously, only polymerization occurred
when the reaction was conducted under microwave irradiation.
But the polymerization seems to proceed to a higher degree in
this case, as the reaction yielded a substance insoluble in any
solvent and swelling in o-DCB without solution. The opening of
aziridine rings does not occur at low temperatures, while at
1
aziridine ring was not changed. The H NMR spectra of com-
pounds 7aꢀf also demonstrate nonequivalence of the alkoxy-
carbonyl group at the pyrrolidine ring. This then implies C1
symmetry for the molecules that can be possible only if the
configurations of the pyrrolidine and aziridine rings are different,
that is the pyrrolidine fragment of 7aꢀf has trans-configuration.
Formation of the trans-adduct in the reaction of cis,cis-bisazir-
idines 5 with C60 suggests that the cycloaddition reaction of the
S-ylide, resulting from thermally allowed conrotatory opening of
a cis-aziridine ring, proceeds with a higher rate than the isomer-
ization of the formed ylide. Thus, the experimental results agree
completely with the model calculations.
The reaction of bisaziridine 6a with fullerene C60 gave
predictably three isomeric monoadducts 8 (11%), 9, and 10
(the last two are inseparable, common yield 34%) (Scheme 4,
X = 1,4-C6H4, R = Et) under the same conditions. The cis,cis-adduct
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Figure 2. Energy profiles for transformations of diethyl 1-phenylaziridin-2,3-dicarboxylates cis- and trans-A and the corresponding ylides SY, UY, and
WY. Relative free energies [kcal molꢀ1, 298 K] computed at the DFT B3LYP/6-31G(d) level.
3
Table 3. Optimization of Monoadduct 7a Synthesis
Table 4. Synthesis of Monoadducts 7aꢀd,f
C60
entry 5a: C60 solvent
T, °C
time, h
yield, %
5aꢀd; f
f
7aꢀd; f
o ꢀDCB, 80 °C
R
X
5
yield of 7, %
1
1: 1.67
1: 1.67
1: 1.67
1:6.7
1:3.3
1:10
o-DCB 20
o-DCB 50
48
10
1
no reaction
2
no reaction
Et
Et
Et
1,4-C6H4
4,40-(C6H4)2
4,40-(C6H4)2CH2
5a
5b
5c
5d
5f
7a, 65
7b, 50
7c, 53
7d, 44
7f, 44
3
o-DCB mw, 160 W
o-DCB 120
insoluble polymer
4
5
soluble polymer
5
o-DCB 100ꢀ110
o-DCB 100ꢀ110
o-DCB 100
5
35
20
32
65
59
53
59
oct-1-yl
oct-1-yl
1,4-C6H4
4,40-(C6H4)2CH2
6
4
7
1:3.3
1:3.3
1:3.3
1:3.3
1:3.3
6
8
o-DCB 80
19
31
36
26
insoluble in organic solvents and could not be properly char-
acterized, although their formation was detected by TLC anal-
ysis. The presence of a carbonyl group was indicated by the
intensive bands at 1757, 1735, and 1730 cmꢀ1 in the IR spectra of
the brown solid isolated by column chromatography from the
reaction mixture. Fortunately, the substitution of the ethyl group
by an octyl group in the ester moiety of the starting aziridine
allowed us to solve this problem of solubility. The reaction of
bisaziridines 5d,f with C60 in o-DCB at 80 °C gave mixtures of the
monoadduct 7d (44%) with the bisadducts 11a, 12a (total yield
26%) and of the monoadduct 7f (44%) with the bisadducts 12a,c
(total yield 16%), respectively (Scheme 5).
The bisadducts become the main reaction products at higher
temperatures. Thus, the reaction of aziridine 5d with fullerene C60 at
100 °C yielded isomeric trans,trans-bisadducts 11a and 12a in 27%
and 34% yield, respectively, along with monoadduct 7d in 31% yield,
which means a total conversion of aziridine into fullerene adducts
of more than 90% (Scheme 5, Table 5). The reaction of 6d with
C60 under the same conditions yielded only cis,trans-bisadduct 13a
(R = oct-1-yl, X = 1,4-C6H4) in 32% yield (Scheme 5).
9
o-DCB 80
10
11
o-DCB 80
1MN
80
8 possesses Cs symmetry and characteristic signals for the cis-
aziridine protons at 3.21 ppm, and those for the pyrrolidine
protons at 5.80 ppm are visible in its 1H NMR spectrum. The cis,
trans-adducts 9 and 10 possess C2 symmetry and show char-
acteristic signals for the trans-aziridine protons at 3.54 ppm and
3.55 ppm, and for the pyrrolidine protons signal at 6.50 ppm. The
signal corresponding to the pyrrolidine protons of trans-cycload-
ducts is significantly shifted downfield with respect to that of cis-
cycloadducts, and this corresponds well to literature data.17 Thus,
the reaction of bisaziridine 6a with fullerene C60 leads to the
cycloaddition products of S/U/W-ylides, in perfect consistence
with the aforementioned calculation results.
Our next task was the optimization of the synthesis of
the dumbbell-like fullerene triads. The bisadducts formed in
the reaction of bisaziridine 5a with fullerene C60 were almost
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Scheme 5
Table 5. Yields of the Products of Reaction the Bisaziridines 5
with Fullerene C60 in o-DCB at 100 °C
desorption mass spectrometry (FD-MS, see Experimental Sec-
tion and Supporting Information).
The formation of two isomers of the bisadduct from the cis,cis-
aziridine 5 and only one isomer of the bisadduct from the cis,
trans-aziridine 6 is in full accordance with the expected stereo-
chemical outcome of the reactions when taking into account the
aforementioned results of the model calculation. Indeed, addi-
tion of fullerene C60 to the ylide trans-P-SY, resulting from the
thermally allowed conrotatory opening of the cis-aziridine ring of
the monoadduct 7, leads to the stereoisomeric bisadducts 11, 12
(Scheme 5). At the same time, in the reaction of the cis,trans-
aziridine 6, the primary product 8 gives the ylide cis-P-SY,
whereas the primary products 9, 10 give the ylide trans-P-UY
and trans-P-WY. The addition of these ylides to fullerene C60,
however, leads to only one bisadduct (bisadduct 13), the same
one from each ylide (Scheme 5).
R
X
5
yield of 11, 12, %
yield of 7, %
oct-1-yl
oct-1-yl
oct-1-yl
oct-1-yl
oct-1-yl
oct-1-yl
1,4-C6H4
d
e
e
e
f
27,a 11a; 34,a 12a
12,a 11b; 12,a 12b
33,a 11b + 12b
47,b 11b + 12b
15,a 11c; 16,a 12c
56,b 11c + 12c
31, 7d
30, 7e
30, 7e
4,40-(C6H4)2
4,40-(C6H4)2
4,40-(C6H4)2
4,40-(C6H4)2CH2
4,40-(C6H4)2CH2
b
ꢀ
54,a 7f
b
f
ꢀ
a Reaction time 8 h. b Reaction time 20 h.
Whereas the fullerene monoadducts of bisaziridines could be
measured by electrospray mass spectrometry using dichloro-
methane and methanol with formic acid as solvents, ionization of
the dumbbell-like fullerene bisadducts could not be achieved by
ESI. Field desorption (FD) ionization was, therefore, applied for
mass spectrometric detection of these compounds. Under the
soft ionization conditions used for field desorption, M+ 3 molec-
ular ions were formed by removal of an electron under exposure
to a high voltage (10 kV) without extensive fragmentation.18 This
technique proves to be suitable even for the mass spectrometric
characterization of the fullerene bisadducts with molecular
weights above 2000 u and represents a promising alternative
for such kinds of compounds. Thus, the molecular ion peaks of
the fullerene bisadducts 11, 12, and 13 were obtained by field
Hence, already the number of products in each case permits
the partial assignment of the stereochemistry of the bisadducts.
Additional proof was obtained by comparing proton NMR
1
spectra of the compounds 11a, 12a, and 13a. The H NMR
spectrum of compound 13a contains three singlets for pyrroli-
dine protons at 5.92, 5.96, and 6.64 ppm and an AB system for the
aromatic protons. This unequivocally proves nonequivalence of
the pyrrolidine fragments and aromatic protons and suggests C1
symmetry and cis,trans-configuration of the product. A compar-
ison with the data for the compounds 7aꢀf allows the assign-
ment of the singlets at 5.92 and 5.96 ppm to the cis-substituted
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Scheme 6
Figure 3. Geometry of the adducts of fullerene C60 and ylides SY, UY,
and WY, derived from diethyl 1-phenylaziridine-2,3-dicarboxylates cis-
and trans-A (see Figure 2), and relative free energies (ΔΔG
[kcal molꢀ1, 298 K] computed at the DFT ONIOM B3LYP/6-31G-
3
(d):B3LYP/STO-3G level. Hydrogen atoms on ethyl groups are
fulleropyrrolidine fragments in the trans,trans-bis-adducts 11
and 12 by recording their 1H NMR spectra using tris[3-(hepta-
fluorpropyl-hydroxymethylene)-D-camphorato]praseodymium
as a shift reagent were unsuccessful, as the spectra revealed
no difference. Chromatography on a chiral column, however,
allowed them to be distinguished. Thus, chromatography of
compound 11a shows two peaks of equal intensity with reten-
tion times of 6.3 and 5.9 min, suggesting that 11a is a dl-pair, 1:1
mixture of enantiomers (S,S,S,S) and (R,R,R,R). There is only
one peak, however, with retention time of 7.2 min, in the case of
compound 12a, suggesting that this is the meso-isomer of Cs
symmetry. The configuration of bisadducts 11b,c (dl-pair) and
12b,c (meso) was established in the same way.
Analogously, the reaction of aziridines 5e,f with C60 under the
same conditions yielded a pair of isomeric trans,trans-bisadducts
11b,c and 12b,c (Scheme 5, Table 5). The yields are significantly
decreased after the chromatographic separation of the trans,
trans-bisadducts 11 and 12. The mixtures of compounds 11b,
12b and 11c, 12c can be isolated in a larger common yield of 33%
(50% based on reacted fullerene C60) and 29% (54% based on
reacted fullerene C60), respectively. The corresponding mono-
adducts 7 were also isolated in all cases, with 30% yield for 7e and
54% yield for 7f, when the reaction time was 8 h. A prolonged
reaction time of 20 h permits the completion of the reaction of
monoadduct with fullerene, yielding the desired isomeric trans,
trans-bisadducts in 47% yield (11b, 12b) and 56% yield (11c,
12c, 97% based on consumed C60).
omitted for clarity.
pyrrolidine ring, and the singlet at 6.64 ppm to the trans-sub-
stituted pyrrolidine ring.
The cis-pyrrolidine ring in compound 13a can be formed by
addition to fullerene of the U- or W-ylides that, according to
model calculations at the DFT ONIOM B3LYP/6-31G(d):
B3LYP/STO-3G level, leads to adducts with different conforma-
tions of one of the pyrrolidine rings (Adduct-WY and Adduct-
UY, conformations I, II, Figure 3). The calculated barrier to
cycloaddition of the U- and W-ylides to C60 are practically equal
(vide supra), but Adduct-WY is less stable than Adduct-UY by
6.8 kcal molꢀ1 (Figure 3) and the barrier to transformation of
3
the first to the second via inversion is only 1.5 kcal molꢀ1
.
3
Therefore, according to the calculations, the cis-pyrrolidine ring
in all adducts should have conformation II, such as in Adduct-
UY. There are two possible characteristic through-space inter-
1
actions shown by the 2D H-NOESY spectra of the adducts
containing the cis-pyrrolidine stereochemistry which can be used
for distinguishing between conformations of type I and II.
Namely, in conformation I an interaction between the pyrroli-
dine protons (distance 2.5 Å) should be present, while the
interaction of these protons and ortho-protons of the Ph ring
should be absent; in conformation II the contary should be true,
that is, the interaction of the pyrrolidine protons with ortho-
protons of the Ph ring should be present, while that between the
pyrrolidine protons (distance 4.0 Å) should be absent. The
Thus, the synthesized bisaziridines represent the starting
material that allows us to direct the reaction with fullerene C60
toward formation of monoadduct, bisadduct, or polymer by
changing the reaction temperature. The theoretical calculations
are in agreement with experimental observations (Scheme 6).
The calculated barrier to conrotatory opening of the cis-aziridine
ring in the bisaziridine 5a is lower than the corresponding barrier
1
analysis of the 2D H-NOESY spectrum of compound 13a
(see Supporting Information) shows that the cis-pyrrolidine ring
of compound 13a has the conformation of type II.
1H NMR spectra of compounds 11a and 12a contain a sole
singlet for the pyrrolidine protons at 6.91 ppm and singlets for
aromatic protons at 7.63 and 7.67 ppm, suggesting high sym-
metry of the compounds and equivalence of the aromatic protons
and pyrrolidine ring protons. This can be true either for a cis,cis-
or a trans,trans-configuration, but only one cis,cis-bisadduct can
in the monoadduct 7a by 2 kcal molꢀ1. To the best of our
3
knowledge, such selectivity can hardly be achieved by implication
of either amino- or imino-based variants of the Prato reaction.
1
exist, while two trans,trans-bisadducts are possible. As the H
NMR and 13C NMR spectra of 11a and 12a are almost identical,
supposition that they constitute cis,cis- and trans,trans-pair
seemed to be improbable, while their being a pair of trans,
trans-bisadducts seemed to be most possible. The value of 6.91
ppm for the signal of the pyrrolidine protons, which is shifted
downfield with respect to the value of 5.92ꢀ5.96 ppm in the
cis-pyrrolidine ring, further supports this assignment. The at-
tempts to determine the relative configuration of the two
’ CONCLUSIONS
The synthesis of alkoxycarbonyl-substituted bisaziridines with
two aziridine units connected by different linkers (conjugated
p-phenylene, partly conjugated 1,10-biphenyl-4,40-diyl, and non-
conjugated group 4,40-methylenediphenyl) was optimized. It was
demonstrated that the reaction of the bisaziridines with fullerene
C60 can be used for selective preparation of both monoadducts
and bisadducts in moderate to good yields with a high degree of
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The Journal of Organic Chemistry
ARTICLE
stereocontrol. The reasons for the observed selectivity of the
azomethine ylide formation and cycloaddition have been theo-
retically studied at the DFT B3LYP/6-31G(d) level or at the
ONIOM B3LYP/6-31G(d):B3LYP/STO-3G level for fullerene-
containing molecules. The developed synthetic approach makes
possible the construction of dumbbell-like fullerene ensembles
with predefined geometry, variable conjugation, and good solu-
bility in common organic solvents.
(t, J = 7.3 Hz, 12H, CH3), 3.12 (4H, CH) (satellite signals: 3.12 (dd,
1JCH = 172.9 Hz, 3JHH = 6.5 Hz), 4.31 (q, J = 7.3 Hz, 8H, CH2), 7.09
(pseudo d, J = 8.0 Hz, 4H, Harom), 7.45 (pseudo d, J = 8.0 Hz, 4H,
H
arom). 13C NMR (CDCl3, 75 MHz): δ, 14.1 (CH3), 43.0 (CHN), 61.9
(CH2), 120.4 (HCarom), 127.5 (HCarom), 136.3 (Carom-C),150.0 (Carom
-
N), 166.9 (CdO). HR-ESI-MS: 525.2239 (MH+, C28H33N2O8; calcd
525.2231), 547.2055 (MNa+, C28H32N2O8Na+; cacld 547.2051.
Diethyl cis,cis-1-[4-[[4-[2,3-Bis(ethoxycarbonyl)aziridin-1-yl]-
phenyl]methyl]phenyl]-2,3-aziridinedicarboxylate 5c. Yield:
38% (103 mg from 99 mg of 2c). Reaction time: 3.5 h. Colorless crystals:
mp 106ꢀ110 °C. IR (CHCl3, NaCl): 1750 (CdO). 1H NMR (CDCl3,
300 MHz): δ 1.34 (t, J = 7.1 Hz, 12H, CH3), 3.07 (4H, CH) (satellite
signals: 3.06 dd (1JCH = 172.6 Hz, 3JHH = 7.0 Hz), 3.88 (2H, CH2C),
4.30 (q, J = 7.1 Hz, 8H, CH2O), 6.96 (pseudo d, J = 8.3, 4H, Harom), 7.05
(pseudo d, J = 8.3, 4H, Harom). 13C NMR (CDCl3, 75 MHz): δ 14.1
(CH3), 40.4 (CH2C), 42.9 (CHN), 61.7 (CH2O), 120.0 (HCarom),
129.5 (HCarom), 136.7 (Carom-C), 149.0 (Carom-N), 166.9 (CdO). HR-
’ EXPERIMENTAL SECTION
General Methods. Melting points were determined on a hot stage
1
microscope and are uncorrected. H (300 MHz) and 13C (75 MHz)
NMR spectra were determined in CDCl3 or C6D6 with a DPX 300
spectrometer. Chemical shifts (δ) are reported in ppm downfield from
tetramethylsilane. ESI-HRMS was performed using a 7T-FTICR mass
spectrometer equipped with an electrospray ion source applying an
electrospray voltage of 4.2 kV and micrOTOF 10223 mass spectrometer.
Samples were injected via syringe pump injection. Field desorption
(FD) measurements were carried out on a TOF mass spectrometer
AccuTOF GCv using an FD emitter with an emitter voltage of 10 kV.
The reactions under microwave irradiation at 160 W were carried out in
a sealed flask in a Minotavr-2 microwave oven for laboratory experi-
ments. Chiral chromatography was performed on a Chiralpak IA HPLC
column (250 mm ꢁ 4.6 mm, particle size 5 μm) with a CH2Cl2/hexane
mixture (50/50) as eluent and a flow of 0.8 mL/min.
General Procedure for the Synthesis of Bisaziridines 5, 6.
As a representative example, the synthesis of diethyl cis,cis- and cis,
trans-1-[4-[2,3-di(ethoxycarbonyl)aziridin-1-yl]phenyl]-2,3-aziridi-
nedicarboxylate 5a, 6a is described here. A mixture of aldehyde 1a (306
mg, 3 mmol), amine 2a (108 mg, 1 mmol), and anhyd Na2SO4 (1.0 g) in
dry C6H6 (25 mL) was stirred at rt for 30 min and filtered, and the
solvent was removed in vacuo. The resulting yellowish oil consisting
mostly of the imine 3a was dissolved in dry Et2O (18 mL). A catalytic
+
ESI-MS: 539.2388 (MH+, C29H35N2O8 ; calcd 539.2388), 561.2221
(MNa+, C29H34N2O8Na+; calcd 561.2207).
Diethyl cis,trans-1-[4-[[4-[2,3-Bis(ethoxycarbonyl)aziridin-1-yl]-
phenyl]methyl]phenyl]-2,3-aziridinedicarboxylate 6c. Yield: 20%
(54 mg from 99 mg of 2c). Reaction time: 3.5 h. Yellow oil. IR (CHCl3,
NaCl): 1750 (CdO). 1H NMR (CDCl3, 300 MHz), δ: 1.19 (t, J = 7.3 Hz,
6H, CH3), 1.33 (t, J = 7.3 Hz, 6H, CH3), 3.06 (2H, CH) (satellite signals:
3.06 (dd, 1JCH = 172.5 Hz, 3JHH = 6.9 Hz), 3.45 (2H, CH) (satellite signals:
3.45 (dd, 1JCH = 181.3 Hz, 3JHH = 2.4 Hz), 3.85 (2H, CH2C), 4.15 (q, J =
7.3 Hz, 4H, CH2O), 4.28 (q, J= 7.3 Hz, 4H, CH2O), 6.82 (pseudo d, J= 8.0
Hz, 2H, Harom), 6.93 (pseudo d, J = 8.0 Hz, 2H, Harom), 7.00ꢀ7.15 m (4H,
Harom). 13C NMR (CDCl3, 75 MHz): δ 13.9 (CH3), 14.1 (CH3), 40.4
(CH2C), 42.1 (CHN), 42.9 (CHN), 61.72 (CH2O), 61.74 (CH2O), 119.8
(HCarom), 120.0 (HCarom), 129.3 (HCarom), 129.5 (HCarom), 136.0 (Carom
-
C), 137.0 (Carom-C), 145.3 (Carom-N), 148.9 (Carom-N), 166.9 (CdO),
167.0 (CdO). HR-ESI-MS: 539.2393 (MH+, C29H35N2O8 ; calcd
+
539.2388), 561.2222 (MNa+, C29H34N2O8Na+; calcd 561.2207).
Dioctyl cis,cis-1-[4-[2,3-Bis(octyloxycarbonyl)aziridin-1-yl]-
phenyl]-2,3-aziridinedicarboxylate 5d. Yield 61% (120 mg from
27 mg of 2a). Reaction time: 4 h. Colorless crystals: mp 33ꢀ35 °C. IR
(KBr): 1754, 1734 (CdO). 1H NMR (CDCl3, 300 MHz): δ 0.90 (t, J =
6.7 Hz, 12H, CH3), 1.20ꢀ1.45 (m, 40H, CH2), 1.60ꢀ1.80 (m, 8H,
CH2CH2O), 3.05 (4H, CH), 4.21 (t, J = 6.9 Hz, 8H, CH2), 6.94 (4H,
Harom). 13C NMR (CDCl3, 75 MHz): δ 14.0 (CH3), 22.6, 25.7, 28.4,
29.12, 29.15, 31.7 (CH2), 43.1 (CHN), 66.0 (CH2O), 120.7 (Carom-C),
147.1 (Carom-N), 166.9 (CdO). Anal. Calcd for C46H76N2O8: C, 70.37;
H, 9.76; N, 3.57. Found: C, 70.44; H, 9.74; N, 3.66.
amount of BF3 OEt2 (2 drops, ca. 14 mg) was added to the imine
3
solution followed by dropwise addition of an ethyl diazoacetate (251 mg,
2.2 mmol) solution in Et2O (2 mL). The reaction mixture was stirred at
rt for 4 h and quenched with Et3N (4 drops, ca. 0.3 mL) and water
(1 mL), the water layer was pipetted off, and the reaction mixture was
dried over Na2SO4. The desiccant was filtered off, the solvent was
removed in vacuo, and the crude product was purified by column
chromatography (silica gel, hexaneꢀethyl acetate), to give bisaziridines
5a (251 mg, 55%) and 6a (122 mg, 27%).
Bisaziridine 5a. Colorless crystals: mp 88ꢀ91 °C. IR (CHCl3,
NaCl): 1736 (CdO). 1H NMR (CDCl3, 300 MHz): δ 1.33 (t, J = 7.1
Hz, 12H, CH3), 3.05 (4H, CH) (satellite signals: 3.05 (dd, 1JCH = 172.3
Hz, 3JHH = 6.5 Hz)), 4.28 (q, J = 7.1 Hz, 8H, CH2), 6.94 (4H, Harom).
13C NMR (CDCl3, 75 MHz): δ 14.1 (CH3), 43.1 (CHN), 61.8 (CH2),
120.7 (Carom-C), 147.1 (Carom-N), 166.8 (CdO). Anal. Calcd for
C22H28N2O8: C, 58.92; H, 6.29; N, 6.25. Found: C, 58.77; H, 6.25;
N, 6.14.
Dioctyl cis,trans-1-[4-[2,3-Bis(octyloxycarbonyl)aziridin-
1-yl]phenyl]-2,3-aziridinedicarboxylate 6d. Yield 14% (28 mg from
27 mg of 2a). Reaction time: 4 h. Yellow oil. IR (KBr): 1730 (CdO).
1H NMR (CDCl3, 300 MHz): δ 0.85ꢀ0.95 (m, 12H, CH3), 1.20ꢀ1.45
(m, 40H, CH2), 1.55ꢀ1.64 (m, 4H, CH2CH2O), 1.64ꢀ1.75 (m, 4H,
CH2CH2O), 3.04 (2H, CH), 3.43 (2H, CH), 4.00ꢀ4.20 (m, 4H, CH2O),
4.20 (t, J = 6.9 Hz, 4H, CH2O), 6.80 (pseudo d, J = 8.4 Hz, 2H, Harom), 6.91
(pseudo d, J = 8.4 Hz, 2H, Harom). 13C NMR (CDCl3, 75 MHz): δ 14.1
(CH3), 22.6, 25.7, 28.36, 28.43, 29.10, 29.13, 29.17, 31.72, 31.75 (CH2),
42.2, 43.1 (CHN), 65.99, 66.02 (CH2O), 120.4, 120.5 (Carom-C), 143.5,
146.6 (Carom-N), 166.91, 166.96 (CdO). HR-ESI-MS: 785.5660 (MH+,
Bisaziridine 6a. Yellow oil. IR (CHCl3, NaCl): 1750 (CdO). 1H
NMR (CDCl3, 300 MHz): δ 1.23 (t, J = 7.3 Hz, 6H, CH3), 1.34 (t, J =
7.3 Hz, 6H, CH3), 3.06 (2H, CH), 3.44 (2H, CH), 4.10ꢀ4.25 (m, 4H,
CH2), 4.29 (q, J = 7.3 Hz, 4H, CH2), 6.82 (pseudo d, J = 8.7 Hz, 2H,
Harom), 6.93 (pseudo d, J = 8.7, 2H, Harom). 13C NMR (CDCl3, 75
MHz): δ 13.98 (CH3), 14.02 (CH3), 42.1 (CHN), 43.0 (CHN), 61.7
(CH2), 61.8 (CH2), 120.42 (Carom-C), 120.44 (Carom-C), 143.4 (Carom-N),
146.4 (Carom-N), 166.7 (CdO), 166.9 (CdO). HR-ESI-MS: 449.1929
(MH+, C22H29N2O8+; calcd 449.1918).
+
C46H77N2O8 ; calcd 785.5674), 807.5497 (MNa+, C46H76N2O8Na+;
807.5494).
Dioctyl cis,cis-1-[40-[2,3-Bis(octyloxycarbonyl)aziridin-1-yl]-
[1,10-biphenyl]-4-yl]-2,3-aziridinedicarboxylate 5e. Yield 38%
(82 mg from 46 mg of 2b). Reaction time: 4 h. Oily crystals. IR (KBr):
1748 (CdO). 1H NMR (CDCl3, 300 MHz): δ 0.90 (t, J = 6.5 Hz, 12H,
CH3), 1.20ꢀ1.45 (m, 40H, CH2), 1.60ꢀ1.80 (m, 8H, CH2CH2O), 3.12
(4H, CH) (satellite signals: 3.12 (dd, 1JCH = 172.1 Hz, 3JHH = 6.5 Hz), 4.23
(t, J = 6.9 Hz, 8H, CH2), 7.09 (pseudo d, J = 8.7 Hz, 4H, Harom), 7.45
Diethyl
cis,cis-1-[40-[2,3-Bis(ethoxycarbonyl)aziridin-1-
yl][1,10-biphenyl]-4-yl]-2,3-aziridinedicarboxylate 5b. Yield:
24% (139 mg from 205 mg of 2b). Reaction time: 8 h. Yellow oil.
1
IR (KBr): 1730, 1712 (CdO). H NMR (CDCl3, 300 MHz): δ 1.35
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The Journal of Organic Chemistry
ARTICLE
(pseudo d, J = 8.7 Hz, 4H, Harom). 13C NMR (CDCl3, 75 MHz): δ 14.1
(CH3), 22.6, 25.8, 28.4, 29.15, 29.17, 31.8 (CH2), 43.1 (CHN), 66.1
(CH2O), 120.4, 127.5 (HCarom), 136.3 (Carom-C), 150.1 (Carom-N), 166.9
142.23, 142.7, 142.8, 143.08, 143.13, 144.5, 144.6, 145.3, 145.4,
145.60, 145.64, 145.67, 145.8, 146.1, 146.4, 146.5, 147.5, 150.4, 153.2
(Csp2), 166.98, 167.00, 170.1 (CdO). HR-ESI-MS: 1169.1923 (MH+,
C82H29N2O8; calcd: 1169.1918).
(CdO). HR-ESI-MS: 861.5985 (MH+, C52H80N2O8 ; calcd 861.5987),
+
883.5809 (MNa+, C52H80N2O8Na+; calcd 883.5807).
Compound 8. Yield from 6a: 11% (4 mg from 13 mg of 6a).
1
Dioctyl cis,trans-1-[40-[2,3-Bis(octyloxycarbonyl)aziridin-1-
yl][1,10-biphenyl]-4-yl]-2,3-aziridinedicarboxylate 6e. Yield 10%
(21 mg from 46 mg of 2b). Reaction time: 4 h. Yellow oil. IR (KBr): 1740
Reaction time: 36 h. Brown solid. IR (KBr): 1739 (CdO). H NMR
(CDCl3, 300 MHz): δ 1.18 (t, J = 7.2 Hz, 6H, CH3), 1.39 (t, J = 7.1 Hz,
6H, CH3), 3.21 (2H, CHaz), 4.25 (q, J = 7.1 Hz, 4H, CH2O), 4.35 (q, J =
7.2 Hz, 4H, CH2O), 5.80 (2H, CHpyr), 7.20 (pseudo d, J = 8.7, 2H,
Harom), 7.63 (pseudo d, J = 8.7 Hz, 2H, Harom). 13C NMR (CDCl3, 75
MHz): δ 14.18, 14.20 (CH3), 43.1 (Caz), 61.92, 61.94 (CH2O), 67.2
(Cpyr), 71.3 (HCpyr), 121.0, 124.1 (HCarom), 135.3, 137.7, 140.0, 141.80,
141.88, 141.96, 141.99, 142.21, 142.24, 142.74, 142.76, 143.1, 144.4,
144.6, 145.3, 145.4, 145.5, 145.6, 145.8, 145.9, 146.11, 146.13, 146.3,
146.5, 147.5, 148.0, 150.6, 152.6, (Csp2), 166.9, 168.5 (CdO). HR-ESI-
1
(CdO). H NMR (CDCl3, 300 MHz): δ 0.80ꢀ0.95 (m, 12H, CH3),
1.20ꢀ1.45 (m, 40H, CH2), 1.50ꢀ1.65 (m, 4H, CH2CH2O), 1.65ꢀ1.80
(m, 4H, CH2CH2O), 3.11 (2H, CH), 3.50 (2H, CH), 4.05ꢀ4.25 (m, 4H,
CH2), 4.24(t, J=6.9Hz, 4H, CH2,), 6.95 (pseudo d, J=8.4Hz, 2H, Harom),
7.08 (pseudo d, J = 8.4 Hz, 2H, Harom), 7.35ꢀ7.50 (m, 4H, Harom.). 13
C
NMR (CDCl3, 75 MHz): δ 14.1 (CH3), 22.6, 25.74, 25.78, 28.38, 28.47,
29.11, 29.16, 31.73, 31.76 (CH2), 42.2, 43.1 (CHN), 66.1 (CH2O), 120.1,
120.3, 127.3, 127.5 (HCarom), 135.6(Carom-C), 136.5 (Carom-C), 146.5
(Carom-N), 149.9 (Carom-N), 166.97, 167.03 (CdO). HR-ESI-MS:
+
MS: 1169.1914 (MH+, C82H29N2O8 ; calcd 1169.1918), 1191.1729
(MNa+, C82H28N2O8Na+; calcd 1191.1738).
+
861.5989 (MH+, C52H81N2O8 ; calcd 861.5987), 883.5826 (MNa+,
Compounds 9 + 10. Yield from 6a: 34% (12 mg from 13 mg of 6a).
C52H80N2O8Na+; calcd 883.5807), 899.5565 (MK+, C52H80N2O8K+;
calcd 899.5546).
1
Reaction time: 36 h. Brown solid. H NMR (CDCl3 + C6D6), 300
MHz): δ 1.18 (t, J = 7.1 Hz,12H, CH3), 1.26 (t, J = 7.2 Hz, 6H, CH3),
1.29 (t, J = 7.2 Hz, 6H, CH3), 3.546 (2H, CHaz), 3.551 (2H, CHaz),
4.15ꢀ4.35 (m, 16H, CH2O), 6.50 (4H, CHpyr), 7.04 (pseudo d, J =
8.6 Hz, 2H, Harom), 7.06 (pseudo d, J = 8.7 Hz, 2H, Harom), 7.27
(pseudo d, J = 8.7 Hz, 4H, Harom). HR-ESI-MS: 1169.1916 (MH+,
C82H29N2O8+; calcd 1169.1918).
Dioctyl cis,cis-1-[4-[[4-[2,3-Bis(octyloxycarbonyl)aziridin-
1-yl]phenyl]methyl]phenyl]-2,3-aziridinedicarboxylate 5f.
Yield 58% (125 mg from 50 mg of 2c). Reaction time: 4 h. Yellow oil.
1
IR (KBr): 1757, 1735 (CdO). H NMR (CDCl3, 300 MHz): δ 0.89
(t, J = 6.5 Hz, 12H, CH3), 1.20ꢀ1.45 (m, 40H, CH2), 1.60ꢀ1.75 (m,
1
8H, CH2CH2O), 3.06 (4H, CH) (satellite signals: 3.06 (dd, JCH
=
Compound 7b. Yield: 50% (19 mg from 16 mg of 5b). Reaction
time: 75 h. Brown solid. IR (KBr): 1753 (CdO). 1H NMR (CDCl3, 300
MHz): δ 1.20 (t, J = 6.9 Hz, 6H, CH3), 1.38 (t, J = 7.3 Hz, 6H, CH3),
3.17 (2H, CHaz) (satellite signals: 3.17 (dd, 1JCH = 172.4 Hz, 3JHH = 6.7
Hz), 4.20ꢀ4.40 (m, 4H, CH2O), 4.35 (q, J = 7.3 Hz, 4H, CH2O), 6.59
(2H, CHpyr), 7.16 (pseudo d, J = 8.7 Hz, 2H, Harom), 7.39 (pseudo d, J =
8.4 Hz, 2H, Harom), 7.59 (pseudo d, J = 8.7 Hz, 2H, Harom), 7.67 (pseudo
d, J = 8.4 Hz, 2H, Harom). 13C NMR (CDCl3, 75 MHz): δ 14.1, 14.2
(CH3), 43.1 (Caz), 61.90, 61.92 (CH2O), 71.0 (Cpyr), 74.4 (HCpyr),
119.2, 120.5, 127.4, 127.8 (HCarom), 134.2, 136.2, 136.4, 136.9, 139.6,
140.2, 141.75, 141.81, 141.90, 141.94, 142.16, 142.23, 142.7, 142.8,
143.1, 144.49, 144.55, 144.60, 145.3, 145.4, 145.60, 145.64, 145.66,
145.8, 146.1, 146.39, 146.44, 147.5, 149.9, 150.4, 153.2 (Csp2), 166.9,
3
172.5 Hz, JHH = 6.2 Hz), 3.87 (2H, CH2C), 4.21 (t, J = 6.5 Hz, 8H,
CH2), 6.95 (pseudo d, J = 8.0 Hz, 4H, Harom), 7.04 (pseudo d, J = 8.0 Hz,
4H, Harom). 13C NMR (CDCl3, 75 MHz): δ 14.0 (CH3), 22.6, 25.8,
28.4, 29.14, 29.17, 31.7 (CH2), 40.4 (CH2Ar), 43.0 (CHN), 66.0
(CH2O), 120.1, 129.5 (HCarom), 136.7 (Carom-C), 149.1 (Carom-N),
167.0 (CdO). HR-ESI-MS. 875.6134 (MH+, C53H83N2O8; calcd
875.6144).
Dioctyl cis,trans-1-[4-[[4-[2,3-Bis(octyloxycarbonyl)aziridin-1-
yl]phenyl]methyl]phenyl]-2,3-aziridinedicarboxylate 6f. Yield
25% (55 mg from 50 mg of 2c). Reaction time: 4 h. Yellow oil. IR (KBr):
1738 (CdO). 1H NMR (CDCl3, 300 MHz): δ 0.80ꢀ1.00 (m, 12H, CH3),
1.20ꢀ1.45 (m, 40H, CH2), 1.55ꢀ1.65 (m, 4H, CH2CH2O), 1.65ꢀ1.80 (m,
4H, CH2CH2O), 3.06 (2H, CH), 3.44 (2H, CH), 3.86 (2H, CH2C),
4.00ꢀ4.20 (m, 4H, CH2O), 4.21 (t, J = 6.9 Hz, 4H, CH2O), 6.81 (pseudo d,
J = 8.3 Hz, 2H, Harom), 6.94 (pseudo d, J = 8.3 Hz, 2H, Harom), 7.01 (pseudo
d, J = 8.5 Hz, 2H, Harom), 7.04 (pseudo d, J = 8.5 Hz, 2H, Harom). 13C NMR
(CDCl3, 75 MHz): δ 14.0 (CH3), 22.6, 25.71, 25.73, 28.3, 28.4, 29.08,
29.11, 29.15, 31.7 (CH2), 40.4 (CH2Ar), 42.1, 43.0 (CHN), 65.9, 66.0
(CH2O), 119.8, 120.0, 129.3, 129.5 (HCarom), 135.9, 136.9 (Carom-C),
145.4, 149.0 (Carom-N), 167.0, 167.1 (CdO). HR-ESI-MS. 875.6148 (MH+,
C53H83N2O8; calcd 875.6144).
+
170.1 (CdO). HRMS: 1245.2226 (MH+, C88H33N2O8 ; calcd
1245.2231), 1267.2042 (MNa+, C88H32N2O8Na+; 1267.2051).
Compound 7c. Yield: 53% (20 mg from 16 mg of 5c). Reaction
time: 36 h. Brown solid. IR (KBr): 1756 (CdO). 1H NMR (CDCl3, 300
MHz): δ 1.16 (t, J = 7.3 Hz, 6H, CH3), 1.36 (t, J = 6.9 Hz, 6H, CH3),
3.12 (2H, CHaz), 3.98 (2H, CH2Ar), 4.20ꢀ4.40 (m, 4H, CH2O), 4.31
(q, J = 6.9 Hz, 4H, CH2O), 6.52 (2H, CHpyr), 7.01 (pseudo d, J = 8.7 Hz,
2H, Harom), 7.15 (pseudo d, J = 8.7 Hz, 2H, Harom), 7.2ꢀ7.4 (m, 4H,
Harom). 13C NMR (CDCl3, 75 MHz): δ 14.14, 14.16 (CH3), 40.5
(CH2Ar), 43.0 (Caz), 61.8 (CH2O), 71.1 (Cpyr), 74.4 (HCpyr), 119.0,
120.1, 129.7, 129.9 (HCarom), 134.9, 136.2, 136.9, 137.1, 139.6, 140.2,
141.78, 141.81, 141.92, 141.94, 142.17, 142.23, 142.7, 142.8, 143.1,
143.5, 144.5, 144.6, 145.3, 145.4, 145.63, 145.69, 145.71, 145.76, 146.1,
146.40, 146.44, 147.5, 149.0, 150.5, 153.3 (Csp2), 167.0, 170.2 (CdO).
General Procedure for the Synthesis of Monoadducts
7ꢀ10. As a representative example, the synthesis of 7a is described
here. A solution of bisziridine 5a (13 mg, 0.03 mmol) in o-DCB
(1ꢀ2 mL) was added dropwise very slowly (during 4ꢀ7 h) to a stirred
solution of C60 (72 mg, 1 mmol) in o-DCB (3ꢀ4 mL) at 80 °C, and the
heating was continued until the aziridine disappeared (TLC). In this
case, it took 19 h of overall heating. The reaction mixture was separated
by column chromatography (silica gel, benzene), which yielded mono-
adduct 7a (22 mg) in 65% yield along with 50 mg of unreacted C60.
Compound 7a. Yield: 65%. Brown solid. IR (CHCl3, NaCl):
+
HR-ESI-MS: 1259.2384 (MH+, C89H35N2O8 ; calcd 1259.2388),
+
+
1276.2657 (MNH4 , C89H38N3O8 ; calcd 1276.2653), 1281.2207
(MNa+, C89H34N2O8Na+; 1281.2207).
Compound 7d. Yield: 44% (19 mg from 23 mg of 5d). Brown solid.
IR (KBr): 1753, 1730 (CdO). 1H NMR (CDCl3, 300 MHz): δ 0.86 (t,
J = 6.7 Hz, 6H, CH3), 0.92 (t, J = 6.9 Hz, 6H, CH3), 1.15ꢀ1.50 (m, 40H,
CH2), 1.50ꢀ1.65 (m, 4H, CH2CH2O), 1.65ꢀ1.80 (m, 4H, CH2-
CH2O), 3.17 (2H, CHaz), 4.10ꢀ4.20 (m, 4H, CH2O), 4.25 (t, J = 6.9
Hz, 4H, CH2O), 6.51 (2H, CHpyr), 7.15 (pseudo d, J = 8.7 Hz, 2H,
Harom), 7.27 (pseudo d, J = 8.7 Hz, 2H, Harom). 13C NMR (CDCl3, 75
MHz): δ 14.1 (CH3), 22.6, 25.8, 25.9, 28.49, 28.51, 29.10, 29.16, 29.17,
29.22, 31.73, 31.79 (CH2), 43.1, 43.3 (Caz), 66.1 (CH2O), 71.1 (Cpyr),
1
1736(CdO). H NMR (CDCl3, 300 MHz): δ 1.18 (t, J = 7.1 Hz,
6H, CH3), 1.39 (t, J = 7.1 Hz, 6H, CH3), 3.18 (2H, CHaz), 4.15ꢀ4.30
(m, 4H, CH2O), 4.34 (q, J = 7.1 Hz, 4H, CH2O), 6.50 (2H, CHpyr), 7.17
(pseudo d, J = 8.7 Hz, 2H, Harom), 7.29 (pseudo d, J = 8.7 Hz, 2H,
Harom). 13C NMR (CDCl3, 75 MHz): δ 14.17, 14.21 (CH3), 43.1, 43.2
(Caz), 61.9 (CH2O), 71.1 (Cpyr), 74.5 (HCpyr), 120.0, 121.1 (HCarom),
136.2, 136.9, 139.7, 140.2, 141.77, 141.82, 141.90, 141.95, 142.17,
6226
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The Journal of Organic Chemistry
ARTICLE
74.6 (HCpyr), 120.0, 121.1 (HCarom), 136.2, 136.9, 139.7, 140.2, 141.75,
141.79, 141.90, 141.93, 142.16, 142.22, 142.7, 142.8, 143.1, 144.5, 144.6,
145.3, 145.4, 145.60, 145.62, 145.64, 145.70, 145.75, 146.1, 146.40, 146.45,
147.5, 150.4, 153.2 (Csp2), 167.03, 167.04, 170.2 (CdO). HR-ESI-MS:
145.92, 145.96, 146.1, 146.3, 146.4, 146.7, 146.8, 147.7, 151.5, 154.0
+
(Csp2), 170.3 (CdO). FD-MS: 2224.6 (M+, C166H76N2O8 ; calcd
2224.6).
Compound 13a. Yield from 6d: 32% (23 mg from 25 mg of 6d).
+
1505.5681 (MH+, C106H77N2O8 ; calcd 1505.5674).
1
Brown solid. IR (KBr): 1755, 1732 (CdO). H NMR (CDCl3, 300
Compound 7e. Yield: 30% (13 mg). (7e was obtained as a
byproduct when 5e (23 mg, 0.026 mmol) was heated with C60 (72 mg,
0.1 mmol) in o-DCB at 100 °C for 8 h). Brown solid. IR (KBr): 1728
(CdO). 1H NMR (CDCl3, 300 MHz), δ: 0.84 (t, J = 6.7 Hz, 6H, CH3),
0.92 (t, J = 6.4 Hz, 6H, CH3), 1.15ꢀ1.50 (m, 40H, CH2), 1.50ꢀ1.65 (m,
4H, CH2CH2O), 1.65ꢀ1.80 (m, 4H, CH2CH2O), 3.16 (2H, CHaz),
4.10ꢀ4.30 (m, 4H, CH2O), 4.26 (t, J = 7.0 Hz, 4H, CH2O), 6.60 (2H,
CHpyr), 7.15 (pseudo d, J = 8.4 Hz, 2H, Harom), 7.38 (pseudo d, J = 8.5
Hz, 2H, Harom), 7.58 (pseudo d, J = 8.4 Hz, 2H, Harom), 7.66 (pseudo d,
J = 8.5 Hz, 2H, Harom). 13C NMR (CDCl3, 75 MHz): δ 14.1 (CH3),
22.62, 22.65, 25.8, 25.9, 28.5, 28.6, 29.13, 29.15, 29.18, 29.22, 31.7, 31.8
(CH2), 43.1 (Caz), 66.1 (CH2O), 71.1 (Cpyr), 74.6 (HCpyr), 119.2,
120.5, 127.4, 127.8 (HCarom), 134.2, 136.2, 136.4, 136.9, 139.7, 140.2,
141.8, 141.9, 142.0, 142.18, 142.25, 142.7, 142.8, 143.1, 144.51, 144.57,
144.63, 145.3, 145.4, 145.62, 145.64, 145.67, 145.71, 145.79, 146.2,
146.4, 146.5, 147.5, 150.0, 150.5, 153.3 (Csp2), 167.0, 170.3 (CdO).
HR-ESI-MS: 1603.5821 (MNa+, C112H80N2O8Na+; 1603.5807).
Compound 7f. Yield: 44% (15 mg from 19 mg of 5f). Brown solid.
IR (KBr): 1755, 1735 (CdO). 1H NMR (CDCl3, 300 MHz):
δ 0.8ꢀ0.95 (m, 12H, CH3), 1.15ꢀ1.45 (m, 40H, CH2), 1.50ꢀ1.65
(m, 4H, CH2CH2O), 1.65ꢀ1.80 (m, 4H, CH2CH2O), 3.11 (2H, CHaz),
3.97 (2H, CH2Ar), 4.15ꢀ4.25 (m, 4H, CH2O), 4.23 (t, J = 7.3 Hz, 4H,
CH2O), 6.54 (2H, CHpyr), 7.01 (pseudo d, J = 8.0 Hz, 2H, Harom), 7.16
(pseudo d, J = 8.0 Hz, 2H, Harom), 7.20ꢀ7.30 (m, 4H, Harom). 13C NMR
(CDCl3, 75 MHz): δ 14.07, 14.10, 22.62, 22.64, 25.8, 25.9, 28.47, 28.50,
29.09, 29.15, 29.19, 31.7, 31.8 (CH2), 40.5 (CH2Ar)), 43.1 (Caz),
66.0 (CH2O), 71.1 (Cpyr), 74.5 (HCpyr), 118.9, 120.1, 129.7, 129.8
(HCarom), 134.7, 136.2, 136.8, 136.9, 139.7, 140.1, 141.77, 141.79,
141.92, 142.15, 142.22, 142.7, 142.8, 143.1, 143.5, 144.49, 144.55,
145.29, 145.35, 145.60, 145.65, 145.70, 146.1, 146.39, 146.43, 147.5,
149.1, 150.6 (Csp2), 153.3, 167.1, 170.3 (CdO). HR-ESI-MS:
1617.5962 (MNa+, C113H82N2O8Na+; 1617.5964).
MHz): δ 0.87 (t, J = 6.5 Hz, 12H, CH3), 1.20ꢀ1.40 (m, 40H, CH2),
1.50ꢀ1.80 (m, 8H, CH2CH2O), 4.10ꢀ4.40 (m, 8H, CH2O), 5.92 (1H,
CHpyr), 5.96 (1H, CHpyr), 6.64 (2H, CHpyr), 7.47 (pseudo d, J = 8.4 Hz,
2H, Harom), 7.76 (pseudo d, J = 8.4 Hz, 2H, Harom). 13C NMR (C6D6, 75
MHz): δ 14.5 (CH3), 23.2, 26.41, 28.99, 29.07, 29.56, 29.63, 29.70,
29.72, 29.75, 32.24, 32.27 (CH2), 66.1, 66.2 (CH2O), 71.98, 72.05,
72.13 (Cpyr), 75.3, 77.1, 77.5 (HCpyr), 121.0, 123.7, (HCarom), 135.8,
136.8, 137.5, 138.4, 140.1, 140.4, 140.6, 140.7, 142.15, 142.19, 142.28,
142.34, 142.38, 142.43, 142.50, 142.56, 142.93, 143.07, 143.11, 143.17,
143.52, 143.55, 143.59, 144.62, 144.81, 144.85, 144.94, 144.96, 145.61,
145.66, 145.67, 145.93, 145.97, 146.01, 146.11, 146.20, 146.32, 146.36,
146.39, 146.44, 146.50, 146.70, 146.75, 146.83, 147.75, 147.79, 151.5,
151.74, 151.75, 153.50, 153.53, 154.1 (Csp2), 168.86, 168.91, 170.3
+
(CdO). FD-MS: 2224.6 (M+, C166H76N2O8 ; calcd 2224.6).
Compound 11b. Brown solid. Yield: 12% (7 mg from 22.5 mg of
1
5e). IR (KBr): 1740 (CdO). H NMR (CDCl3, 300 MHz): δ 0.86
(t, J = 6.5 Hz, 12H, CH3), 1.10ꢀ1.40 (m, 40H, CH2), 1.50ꢀ1.70 (m,
8H, CH2CH2O), 4.10ꢀ4.30 (m, 8H, CH2O), 6.624 (4H, CHpyr), 7.42
(pseudo d, J = 8.3 Hz, 4H, Harom), 7.76 (pseudo d, J = 8.3 Hz, 4H,
Harom). 13C NMR (CDCl3, 75 MHz): δ 14.1 (CH3), 22.7, 26.0, 28.6,
29.15, 29.19 31.8 (CH2), 66.2 (CH2O), 71.1 (Cpyr), 74.6 (HCpyr),
119.2, (HCarom), 127.7, 134.4, 136.3, 136.9, 139.7, 140.2, 141.8, 141.95,
141.98, 142.19, 142.26, 142.7, 142.8, 143.2, 144.46, 144.53, 144.58,
145.3, 145.4, 145.64, 145.69, 145.74, 145.8, 146.2, 146.4, 146.5, 147.5,
+
150.5, 153.3 (Csp2), 170.4 (CdO). FD-MS: 2300.6 (M+, C172H80N2O8 ;
calcd 2300.6).
Compound 12b. Brown solid. Yield: 12% (7 mg from 22.5 mg of
5e).IR (KBr): 1735 (CdO). 1H NMR (CDCl3, 300 MHz), δ: 0.86 (t,
J = 6.5 Hz, 12H, CH3), 1.10ꢀ1.40 (m, 40H, CH2), 1.50ꢀ1.70 (m, 8H,
CH2CH2O), 4.10ꢀ4.30 (m, 8H, CH2O), 6.623 (4H, CHpyr), 7.44
(pseudo d, J = 8.3 Hz, 4H, Harom), 7.78 (pseudo d, J = 8.3 Hz, 4H,
Harom). 13C NMR (CDCl3, 75 MHz): δ 14.1 (CH3), 22.7, 26.0, 28.6,
29.14, 29.17, 31.7 (CH2), 66.1 (CH2O), 71.1 (Cpyr), 74.6 (HCpyr),
119.2, (HCarom), 127.7, 134.4, 136.3, 136.9, 139.7, 140.2, 141.8, 141.95,
141.97, 142.19, 142.26, 142.7, 142. 8, 143.2, 144.47, 144.53, 144.59,
145.3, 145.4, 145.64, 145.66, 145.69, 145.7, 145.8, 146.2, 146.4, 146.5,
147.5, 150.5, 153.3 (Csp2), 170.4 (CdO). FD-MS: 2300.6 (M+,
General Procedure for Synthesis of Bisadducts 11ꢀ13. As a
representative example, the synthesis of bisadducts 11a, 12a is described
here. A solution of aziridine 5d (20 mg, 0.026 mmol) in o-DCB (2 mL)
was added dropwise very slowly (during 7ꢀ8 h) to a stirred solution of
C60 (72 mg, 1 mmol) in o-DCB (3 mL) at 100 °C, and the heating was
continued for an additional 1 h. The reaction mixture was separated by
column chromatography (silica gel, benzeneꢀpetroleum ether) to yield
bisadducts 11a (16 mg) and 12a (20 mg) in 27% and 34% yield,
respectively, along with 12 mg (31%) of monoadduct 7d and 40 mg of
unreacted C60.
+
C172H80N2O8 ; calcd 2300.6).
Compounds 11b + 12b. Reaction time: 20 h. Common yield:
47% (28 mg from 19 mg of 5e).
Compound 11c. Brown solid. Yield: 16% (10 mg from 23 mg of
5f). IR (KBr), cmꢀ1: 1757, 1735 (CdO). 1H NMR (CDCl3, 300 MHz):
δ 0.87 (t, J = 6.6 Hz, 12H, CH3), 1.15ꢀ1.40 (m, 40H, CH2), 1.50ꢀ1.70
(m, 8H, CH2CH2O), 4.07 (2H, CH2Ar), 4.15ꢀ4.30 (m, 8H, CH2O),
6.586 (4H, CHpyr), 7.30 (pseudo d, J = 10.1 Hz, 4H, Harom), 7.34
(pseudo d, J = 10.1 Hz, 4H, Harom). 13C NMR (CDCl3, 75 MHz): δ 14.1
(CH3), 22.7, 26.0, 28.6, 29.15, 29.19, 31.8 (CH2), 40.5 (CH2Ar), 66.1
(CH2O), 71.1 (Cpyr), 74.5 (HCpyr), 118.9, (HCarom), 130.1, 134.9,
136.3, 136.9, 139.7, 140.2, 141.78, 141.82, 141.9, 142.17, 142.24, 142.70,
142.77, 143.1, 143.5, 144.5, 144.6, 145.3, 145.4, 145.6, 145.7, 145.8,
146.1, 146.41, 146.45, 147.5, 150.6, 153.3 (Csp2), 170.4 (CdO). FD-
Compound 11a. IR (KBr): 1757, 1730 (CdO). Brown solid.
1H NMR (C6D6, 300 MHz): δ 0.92 (t, J = 6.9 Hz, 12H, CH3),
1.10ꢀ1.40 (m, 40H, CH2), 1.40ꢀ1.60 (m, 8H, CH2CH2O), 4.16 (t,
J = 6.5 Hz, 8H, CH2O), 6.91 (4H, CHpyr), 7.63 (4H, Harom). 13C NMR
(C6D6, 75 MHz): δ 14.5 (CH3), 23.2, 26.5, 29.1, 29.6, 29.8, 32.3 (CH2),
66.1 (CH2O), 72.0 (Cpyr), 75.2 (HCpyr), 121.0, (HCarom), 136.8, 137.5,
140.2, 140.6, 141.1, 142.2, 142.31, 142.37, 142.45, 142.51, 142.57, 143.1,
143.2, 143.3, 143.6, 144.9, 145. 0, 145.6, 145.7, 145.98, 146.03, 146.2,
146.36, 146.38, 146.44, 146.75, 146.83, 147.8, 151.6, 154.1 (Csp2), 170.3
(CdO). FD-MS: 2224.6 (M+, C166H76N2O8 ; calcd 2224.6).
MS: 2314.7 (M+, C173H82N2O8 ; calcd 2314.6).
+
+
Compound 12a. Brown solid. IR (KBr): 1730 (CdO).1H NMR
(C6D6, 300 MHz): δ 0.91 (t, J = 6.9 Hz, 12H, CH3), 1.10ꢀ1.60
(m, 48H, CH2), 4.0ꢀ4.3 (m, 8H, CH2O), 6.91 (4H, CHpyr), 7.67 (4H,
Harom). 13C NMR (C6D6, 75 MHz): δ 14.4 (CH3), 23.1, 26.4, 29.0, 29.6,
29.7, 30.2 (CH2), 66.0 (CH2O), 71.9 (Cpyr), 75.4 (HCpyr), 121.3,
(HCarom), 136.8, 137.5, 140.1, 140.6, 141.3, 142.1, 142.2, 142.3, 142.38,
142.44, 142.5, 143.0, 143.1, 143.2, 143.5, 144.8, 144.9, 145.56, 145.60,
Compound 12c. Brown solid. Yield: 15% (9 mg from 23 mg of 5f).
1
IR (KBr), cmꢀ1: 1757, 1734 (CdO). H NMR (CDCl3, 300 MHz):
δ 0.88 (t, J = 6.7 Hz, 12H, CH3), 1.15ꢀ1.45 (m, 40H, CH2), 1.50ꢀ1.70
(m, 8H, CH2CH2O), 4.07 (2H, CH2Ar), 4.15ꢀ4.35 (m, 8H, CH2O),
6.589 (4H, CHpyr), 7.20ꢀ7.40 (m, 4H, Harom). 13C NMR (CDCl3, 75
MHz): δ 14.1 (CH3), 22.7, 26.0, 28.6, 29.16, 29.19, 31.8 (CH2), 40.4
(CH2Ar), 66.1 (CH2O), 71.1 (Cpyr), 74.5 (HCpyr), 118.9, (HCarom),
6227
dx.doi.org/10.1021/jo2009627 |J. Org. Chem. 2011, 76, 6218–6229

The Journal of Organic Chemistry
ARTICLE
130.1, 134.9, 136.3, 136.9, 139.7, 140.2, 141.79, 141.82, 141.9, 142.17,
142.24, 142.70, 142.78, 143.1, 143.5, 144.5, 144.6, 145.3, 145.4, 145.6,
145.7, 145.8, 146.1, 146.41, 146.45, 147.52, 150.6, 153.3 (Csp2), 170.4
F.; Roffia, S. Phys. Chem. Chem. Phys. 2001, 3, 3518. (f) Hua, J. L.; Ding,
F.; Meng, F. S.; Tian, H. Chin. Chem. Lett. 2004, 15, 1373. (g) Hua, J.;
Meng, F.; Ding, F.; Li, F.; Tian, H. J. Mater. Chem. 2004, 14, 1849. (h)
Gu, T.; Whitesell, J. K.; Fox, M. A. J. Org. Chem. 2004, 69, 4075. (i) Enes,
R. F.; Tomꢀe, A. C.; Cavaleiro, J. A. S.; Amoratti, R.; Fumo, M. G.; Pedulli,
G. F.; Valgimigli, L. Chem.—Eur. J. 2006, 12, 4646. (j) de la Escosura, A.;
Martnez-Daz, M. V.; Guldi, D. M.; Torres, T. J. Am. Chem. Soc. 2006,
128, 4112. (k) Zhou, Z.; Schuster, D. I.; Wilson, S. R. J. Org. Chem. 2006,
71, 1545. (l) Troshin, P. A.; Peregudov, A. S.; Troyanov, S. I.; Lyubovskaya,
R. N. Russ. Chem. Bull. 2008, 57, 887.
(CdO). FD-MS: 2314.6 (M+, C173H82N2O8 ; calcd 2314.6).
+
Compounds 11c + 12c. Reaction time: 20 h. Common yield: 56%
(34 mg from 23 mg of 5e).
’ ASSOCIATED CONTENT
Supporting Information. 1H and 13C NMR spectra for
S
b
(8) (a) Kawamura, Y. Int. J. Modern Phys. B 2003, 17, 1910. (b) Wu,
S.-H.; Sun, W.-Q.; Zhang, D.-W.; Shu, L.-H.; Wu, H.-M.; Xu, J.-F.; Lao,
X.-F. J. Chem. Soc., Perkin Trans. 1 1998, 1733.
all new compounds, the 2D-1H-NOESY spectrum of compound
13a, and mass spectra of compounds 7ꢀ13a. Computation
details: Energies of the reactants, transition states, and their
Cartesian coordinates. This material is available free of charge via
the Internet at http://pubs.acs.org.
(9) (a) Bianco, A.; Gasparrini, F.; Maggini, M.; Misiti, D.; Polese, A.;
Prato, M.; Scorrano, G.; Toniolo, C.; Villani, C. J. Am. Chem. Soc. 1997,
119, 7550. (b) Schergna, S.; Ros, T. D.; Linda, P.; Ebert, C.; Gardossi, L.;
Prato, M. Tetrahedron Lett. 1998, 39, 7791. (c) Gasparrini, F.; Misiti, D.;
Negra, F. D.; Maggini, M.; Scorrano, G.; Villani, C. Tetrahedron. 2001,
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J. Org. Chem. 2006, 2934. (e) Brunetti, F. G.; Herrero, M. A.; Muꢁnoz,
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: alexander.khlebnikov@pobox.spbu.ru.
ꢀ
J. d. M.; Giordani, S.; Diaz-Ortiz, A.; Filippone, S.; Ruaro, G.;
Meneghetti, M.; Prato, M.; Vꢀazquez, E. J. Am. Chem. Soc. 2007,
129, 14580. (f) Khlebnikov, A. F.; Novikov, M. S.; Petrovskii, P. P.;
Konev, A. S.; Yufit, D. S.; Selivanov, S. I.; Frauendorf, H. J. Org. Chem.
2010, 75, 5211. (g) Khlebnikov, A. F.; Novikov, M. S.; Golovkina, M. V.;
Petrovskii, P. P.; Konev, A. S.; Yufit, D. S.; Stoeckli-Evans, H. Org.
Biomol. Chem. 2011, 9, 3886.
(10) (a) Synthetic Application of 1,3-Dipolar Cycloaddition Chemistry
Toward Heterocycles and Natural Products; Padwa, A., Pearson, W. H.,
Eds.; John Wiley & Sons: New York, 2002. (b) Tsuge, O.; Kanemasa, S.
Adv. Heterocycl. Chem. 1989, 45, 231.
’ ACKNOWLEDGMENT
We gratefully acknowledge the financial support of the
Russian Foundation for Basic Research (project 11-03-00186),
Council for Grants of the President of Russian Federation (grant
no. MK-3112.2010.3), and Federal Grant-in-Aid Program “Hu-
man Capital for Science and Education in Innovative Russia”
(Governmental Contract no. 16.740.11.0442). We are very
grateful to Mr. Olaf Senge for chiral chromatography.
(11) (a) Khlebnikov, A. F.; Novikov, M. S.; Kostikov, R. R. Russ.
Chem. Rev. 2005, 74, 171. (b) Khlebnikov, A. F.; Novikov, M. S.;
Kostikov, R. R.; Kopf, J. Russ. J. Org. Chem. 2005, 41, 1341. (c) Voznyi,
I. V.; Novikov, M. S.; Khlebnikov, A. F. Synlett 2005, 1006. (d) Konev,
A. S.; Novikov, M. S.; Khlebnikov, A. F. Tetrahedron Lett. 2005, 46, 8337.
(e) Khlebnikov, A. F.; Novikov, M. S.; Amer, A. A.; Kostikov, R. R.;
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