Deoxygenation of some α-dicarbonyl compounds by tris(diethylamino) phosphine in the presence of fullerene C60

Article abstract of DOI:10.1021/jo102332e

The reactions of such cyclic α-diketones as acenaphthenequinone, aceanthrenequinone, and N-alkylisatins, with hexaethyltriaminophosphine in the presence of the fullerene C₆₀, lead to the formation of methanofullerene derivatives under mild cond

Full text of DOI:10.1021/jo102332e

ARTICLE
pubs.acs.org/joc
Deoxygenation of Some r-Dicarbonyl Compounds by
Tris(diethylamino)phosphine in the Presence of Fullerene C60
Irina P. Romanova, Andrey V. Bogdanov,* Vladimir F. Mironov, Gulnara R. Shaikhutdinova,
Olga A. Larionova, Shamil K. Latypov, Alsu A. Balandina, Dmitry G. Yakhvarov, Aidar T. Gubaidullin,
Alina F. Saifina, and Oleg G. Sinyashin
A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center of the Russian Academy of Sciences, Arbuzov str., 8
Kazan 420088 Russia
S Supporting Information
b
ABSTRACT: The reactions of such cyclic R-diketones as
acenaphthenequinone, aceanthrenequinone, and N-alkylisatins,
with hexaethyltriaminophosphine in the presence of the full-
erene C60, lead to the formation of methanofullerene derivatives
under mild conditions. This process proceeds via deoxygena-
tion of the dicarbonyl compound by the P(III) derivative and is
likely to involve the intermediate formation of R-ketocarbenes.
The structure of some methanofullerenes has been confirmed
by NMR and XRD. The electrochemical behavior of the
methanofullerenes was also investigated.
’ INTRODUCTION
compounds (cyclic anhydrides or acids thioanhydrides) is sup-
posed to proceed through the formation of carbenes.18,19
A
The deoxygenation of organic compounds by trivalent phos-
phorus compounds is a widely used process in organic
chemistry.1,2 For example, it is known that compounds having
nitrogen-oxygen or oxygen-oxygen bonds can be deoxyge-
nated fully or partially by trialkyl or triaryl phosphites.3-9 The
three-component reaction of o-nitrobenzaldehyde with aniline
derivatives in the presence of the triethyl phosphite leading to
various 2-arylindazoles may also be considered as such a
processes.10 Sulfoxides can also be transformed to the corre-
sponding sulfides under the action of triphenyl or trimethyl
phosphites, although tris(trimethylsilyl) phosphite is a more
effective reagent for the sulfoxide deoxygenation.11-13 Phos-
phine oxides can be reduced by using the HSiCl3/PPh3 system to
the tertiary phosphines.14
Among a great variety of the deoxygenation reactions, those of
carbonyl compounds with trivalent phosphorus derivatives can
be considered as a separate class. They have been used in the
synthesis of a variety of organic compounds including biologi-
cally active ones. For example, the interactions of trialkyl
phosphites or sodium diethyl phosphite with some oxiranes or
benzaldehyde derivatives lead to the formation of olefins such as
ethylenes or stilbenes in moderate yields.15,16 2,20-Diformylbi-
phenyl and its derivatives undergo an intramolecular cyclization
with tris(dimethylamino)phosphine to give the correspond-
ing epoxides.17 The deoxygenation of some 1,3-dicarbonyl
number of publications deal with the reactions of aroyl- and
heteroaroylphosphonates with the trialkyl phosphites. These
reactions proceed under mild conditions and are also presumed
to involve anionic intermediates or carbene intermediates which
undergo intramolecular insertion into multiple bond or inter-
molecular reactions.20-26 However, there is no unambiguous
proof of carbenes formation in the deoxygenation reaction of
organic compounds under the action of phosphorus(III)
derivatives.
The above-mentioned reactions are well studied, but at the
same time there are only two articles16,27 devoted to the
deoxygenation of R-dicarbonyl compounds by phosphorus(III)
reagents. Here we report new results concerning the reaction of
cyclic R-diketones, such as acenaphthenequinone, aceanthrene-
quinone, and N-alkylisatins, with tris(diethylamino)phosphine
in the presence of the fullerene C60 as a third component to
confirm the structure of the possible carbene intermediates.
Fullerene is known to be a remarkable trap of carbenes prepar-
ing by various methods, methanofullerenes forming as a result
of these processes.28,29 The latest investigations show that the
Received: December 6, 2010
Published: March 10, 2011
r
2011 American Chemical Society
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Scheme 1. Synthesis of Methanofullerene 5 via Three-Component Reaction
methanofullerenes are prospective pharmacophores, antioxi-
dants, and reagents for photodynamic therapy.29-35
the regiochemistry of the reaction we have explored the reactions
of the aminophosphine 2 with 1,2-naphthoquinone 6, acean-
threnequinone 7, 1-methylisatin 8, 1-allylisatin 9, 1-acetylisatin 3,
and 1-(30,50-di-tert-butyl-40-hydroxybenzyl)isatin 4 in the pre-
sence of the fullerene C60.
’ RESULTS AND DISCUSSION
The addition of the fullerene was achieved in the following
way: the phosphine 2 was added to the mixture of the R-diketone
with the fullerene C60 in o-dichlorobenzene (o-DCB) at -10 °C.
The temperature was gradually increased to 20-25 °C over 8 h.
The separation of the reaction products by the column chroma-
tography on silica gel gave unreacted fullerene, fullerene mono-
adducts, and nonseparated polyadduct mixtures.
The reaction of 1,2-naphthoquinone 6 with aminophosphine
2 and fullerene does not lead to the formation of any fullerene
adducts. Only the initial fullerene was isolated by column
chromatography from the reaction mixture in quantitative yield.
Attempts to reveal any fullerene products by HPLC failed.
It should be noted that 1,2-naphthoquinone 6 reacts with
aminophosphine 2 to form 2-hydroxy-4-[tris(diethylamino)phos-
phonium]naphthyl-1-ate.41
Information about the reactions of o-quinones with P(III)
reagents is rather limited. It has been shown that the reaction
of 2-R2N-2,5-dimethyl-1,3,2-diazaphospholanes with ace-
naphthenequinone 1 leads to an oligomer with undefined
structure.36 To investigate the influence of the nature of the
substituent at phosphorus in this reaction, we took hexaethyl-
triaminophosphine 2 instead of the diazaphospholane. As a
result, 1,10-bis(acenaphthen-1-ylidene)-2,20-dionewas obtained.37
Furthermore, we have established that the reactions of the
aminophosphine 2 with N-acetyl- and N-1-(30,50-di-tert-butyl-
40-hydroxybenzyl)isatin (3 and 4, respectively) led to the isatin
dimerization product as well as for quinone 1.38 We concluded
that carbenes had been generated from the dicarbonyl com-
pounds 1, 3, and 4 under the action of phosphine 2. To provide
support for this hypothesis, we attempted to use alkenes such as
trichloroethylene, hex-1-ene, and some enamines to trap the
proposed carbene intermediate. However, our attempts failed.
On the other hand, we were successful at trapping the inter-
mediate by using of the fullerene C60 in the two-component
system of acenaphthenequinone 1 and aminophosphine 2.
Methanofullerene 5 was obtained as a result of this three-
component reaction (Scheme 1).39
Two fractions were obtained after the separation of the
reaction components in the three-component system of acean-
threnequinone 7, hexaethyltriaminophosphine 2, and fullerene
C60. The first fraction contained unreacted fullerene. The
13C NMR, IR, and UV-vis spectroscopy data show that
both unreacted fullerene and 2-(30-cyclopropa[100,900](C60-Ih)-
[5,6]fulleren-30-yl}-1-aceanthrenone 10 were present in the
second fraction. Unfortunately, the attempted separation of these
compounds by repeated column chromatography failed. On the
one hand, this fact may be connected with a similar adsorption
activity of the fullerene and compound 10. On the other hand,
the fullerene and compound 10 could have formed a molecular
complex (Scheme 2). The fullerene is known to form complexes
with polycyclic compounds.42
It is well-known that cycloaddition to the fullerene sphere
can lead to the formation of the various monoadducts, namely,
[6,6]- and [5,6]methanofullerenes or [6,6]- and [5,6] homo-
fullerenes.28,29 [5,6]Methanofullerenes and [5,6]homofullerenes are
supposed to form by the dipolarophile cycloaddition of an
addend to a CdC bond on the fullerene sphere. A pathway to the
[6,6]-opened adducts is not clear at the present time. As for
[6,6]-methanofullerenes, the most probable pathway for their
formation is thought to be via generation of the carbene from an
addend. The physical data for four fullerene isomers are in many
ways similar and the plausible determination of an adduct
structure from this information is a nontrivial task.40 To deter-
mine the structure of methanofullerene 5 we have obtained its IR,
UV, NMR, and mass confirmed by XRD.
To try to separate compound 10 and C60 p-But-calix[8]arene
11 was added to the second fraction, resulting in the complex 12
precipitating (Scheme 2).
After separation and drying in vacuo, this complex had a
mustard color. Elemental analysis and the IR spectroscopic data
showed that complex 12 was the known 1:1 molecular complex
of C60 with compound 11.43 Bands for the bonds in both the
fullerene and the calixarene 11 were shown in the IR spectrum of
the complex 12. Meanwhile, a slight shift of the C60 vibrational
mode at 528, 578, 1184, 1429 cm-1 and some bands of the
calixarene 11 at 729, 782, 876, 1485, 2960 cm-1 was observed in
the IR spectrum of 12 as compared with the pure C60 (525, 577,
These results, which were published as brief reports,37-39
allowed us to conclude that the reactions of the hexaalkyltriami-
nophosphines with dicarbonyl compounds are likely to pass
through carbene intermediates. To determine the affect of the
structure of the dicarbonyl compound’s aromatic fragments on
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Scheme 2. Synthesis of Compound 10 in Detail
Scheme 3. Novel Indolin-2-one-Containing Methanofullerenes
1181, 1427 cm-1) and calixarene 11 (728, 784, 874, 1487,
2957 cm-1). In addition, the bands of the calixarene 11 had lost
their intensity and had broadened in the spectrum of the complex
12. These data are in good agreement with those reported
previously.43 Complex 12 breaks down to the fullerene C60 in
CDCl3, which precipitated as a black sediment and was identified
by IR spectroscopy. Only fullerene bands were found in the IR
spectrum.
fullerene. The mass spectrum of the methanofullerene 10 con-
tains the molecular ion peak at m/z 937 and a peak for its
degradation product [Mþ - CO] (calcd for C75H8 909, found
1
908). The IR and H NMR spectroscopic data for the metha-
nofullerene 10 prove that the structure of the aceanthrene
fragment remains unchanged. The IR spectrum of this com-
pound showed a band at 527 cm-1 which is characteristic for
organofullerenes. There is both a narrow low-intensity band at
λmax 433 nm characteristic for [6,6]-closed fullerene structures28
and a band for the aceanthrene fragment at 405 nm in the UV
spectrum.
The methanofullerene 10 was obtained by repeated column
chromatography of the filtrate after separation of the complex
12. The yield of 10 was 20% with respect to the starting
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carried out by a variety of correlation NMR methods (COSY
1H-1H, HSQC 1H-13C, HMBC 1H-13C, see the Supporting
Information).44 For example, for 5 from the 2D COSY spectrum
two spin systems of protons can be easily assigned in the
heterocyclic moiety. Then all hydrogenated carbons can be
determined from the 2D HSQC spectrum. Finally, from HMBC
correlations all carbons of the acenaphthenone fragment can be
unequivocally assigned (Figure 1).
In the 13C NMR spectra of 5 there are 28 peaks in the range
138-147 ppm corresponding to the fullerene moiety (21 signals
with 2C intensity, 4 lines with 1C, and 3 signals with 4C). There
is also one peak (76.48 ppm) with an intensity corresponding to
two carbons and having four-bond scalar HMBC connectivity
from the H3 proton of the acenaphthenone (8.56 ppm). Thus,
the fullerene sphere is of the closed type and the cycloaddition
has occurred to the CdC bond.
Figure 1. Structure of 5 with the principal HMBC correlations from the
protons of the acenaphthenone moiety (in gray-bold) to the fullerene
carbons.
The methanofullerenes 13-16 were isolated by column
chromatography on silica gel from the reaction mixtures of
isatins 3, 4, 8, and 9 and phosphine 2 in the presence of the
fullerene C60 (Scheme 3). The yields of compounds 13-16 are
within 30-35%. UV, IR, and NMR spectroscopies confirmed
their structure. The composition was established by MALDI-
TOF mass spectrometry.
The mass spectra of compounds 13-16 show the molecular
ion peaks at m/z 866, 892, 894, and 1070 correspondingly. The
IR spectra include both a band characteristic for the fullerene
sphere at 526-527 cm-1 and bands for the addends (13: 1724,
1611, 1468, 1372, 1344, 742 cm-1; 14: 1721, 1609, 1464, 1354,
987, 920, 743 cm-1; 15: 1773, 1745, 1713, 1608, 1552, 1460,
1378, 1336, 1307, 1265, 1212, 1166, 1095, 1039, 981, 749,
598 cm-1; 16: 3438, 2955, 2922, 2864, 1722, 1636, 1611,
1466, 1431, 1356, 1236,1186, 1157, 1112, 744 cm-1). A narrow
low-intensity band at λmax 430-427 nm characteristic of the
[6,6]-closed fullerene structures was observed in the UV spectra
of these compounds. The UV spectra of compounds 13-16
show a broad band at λmax 500 nm which is a superposition of
both bands of the fullerene sphere and ones of the indolinone
fragment.
For the methanofullerene 10 there are 44 peaks in 13C NMR
spectra from which the 16 signals were exactly assigned to the
carbons of aceanthrene fragment by a variety of 2D NMR
correlation techniques. The fullerene sphere of 10 is character-
ized by signals, whose number and intensity (22 signals with the
intensity 2C, three signals with 4C and four signals corresponding to
1C) indicate Cs symmetry of the sphere. Thus, the sp3-carbon of the
C60 cage appeared at 76.6 ppm corresponding to the [6,6]-type of
addend linkage.
For compounds 13-16 the addend nuclei (up to C3) were
unambiguously assigned by a variety of 2D NMR correlation
methods. For example, for 13 the NOE between N-CH3 and
H7 allows a direct assignment of all protons in the “benzo” frag-
ment. HMBC correlations between the CH3 protons and the
CdO (C2, 169.09 ppm) and between the H4 and sp3 carbon
Finally, the structures of the methanofullerenes 5, 10, and
13-16 were determined by NMR. In addition, an XRD analysis
was carried out for compounds 5 and 13.
Thus, the reactions of quinones 1 and 7 and isatins 3, 4, 8, and
9 with aminophosphine 2 in the presence of the fullerene go
through the formation of [6,6]-closed fullerene adducts, metha-
nofullerenes 5, 10, and 13-16. 1,2-Naphthoquinone 6, in
contrast, does not enter into such a three-component reaction.
This compound also behaves unusually in the reaction with
aminophosphine 2.41 Whereas quinone 1 and isatins 3 and 4 give
the ketocarbene dimerization products, naphthoquinone 6 under-
goes phosphorylation at the four position of the naphthalene frag-
ment. This is likely to be related to the peculiarity of the naphtho-
quinone’s electronic structure which easy turns into the aromatic
dihydroxynaphthalene system. The formation of similar aromatic
compounds is impossible for derivatives 1, 3, 4, and 7-9. These
compounds are likely to give the ketocarbenes under the action of
aminophosphine 2, which easily add to the fullerene.
Electron transfer from the phosphine 2 to the R-diketone is
most likely to occur to give the ion-radical pair A (Scheme 4,
example for isatins). Then this pair generates carbene B step by
step with the elimination of the hexaethyltriamidophosphate.
These carbenes then undergo dimerization in the absence of the
fullerene or add to CdC bond of the fullerene to form methano-
fullerenes in three-component reactions.
Figure 2. ORTEP view of the molecular structure of compound 5.
Displacement ellipsoids are drawn at the 30% probability level. H atoms
are represented by circles of arbitrary size. Carbon disulfide molecules
are omitted for clarity. Selected bonds lengths (Å): C(1)-C(61)
1.51(1), C(1)-C(2) 1.63(1), C(2)-C(61) 1.59(1), C(62)-O(62)
1.17(1), C(62)-C(63) 1.32(1), C(62)-C(61) 1.65(1), C(63)-
NMR Studies of Compounds 5, 10, and 13-16. The com-
plete structure elucidation of compounds 5, 10, and 13-16 was
ꢀ
C(64) 1.398(8), C(61)-C(65) 1.48(1) Å.
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(C3, 42.08 ppm) led us to conclude that for 13 the addend
linkage to the fullerene sphere is in the C3 position and not at C2.
An almost perfect correlation of the calculated (GIAO B3LYP/
6-31G(d)//HF/6-31G)45-48 versus experimental 13C chemical
shifts (R2 = 0.998, see the Supporting Information) provides
additional support for the validity of the above conclusion about
the structure. The same is also true for compounds 14-16. The
number of peaks observed for compounds 14-16 in the range
138-146 ppm is due to the 58 sp2-carbons of the C60 sphere,
consistent with the Cs symmetry of their molecular struc-
tures. Moreover, the C60 cage sp3carbons resonate at 75.1-
75.4 ppm in these compounds, thus proving the [6,6]-type of the
addend linkage.
Crystal Structures of 5 and 13. Crystals of 5 were obtained by
a slow evaporation of the compound from a carbon disulfide
solution. The structure was studied by the XRD analysis, which
showed that compound 5 forms a 1:2 inclusion complex with
carbon disulfide molecules. It should be noted that the metha-
nofullerene 5 molecule has noncrystallographic Cs symmetry but
loses it in the crystal and is located at a general position; the
molecular structure and selected bonds lengths are shown in
Figure 2.
Figure 4. ORTEP view of the molecular structure of methanofullerene
13. Displacement ellipsoids are drawn at the 30% probability level.
Chloroform molecule is omitted for clarity. Selected bonds lengths (Å):
C(1)-C(61) 1.526(3), C(1)-C(2) 1.589(3), C(2)-C(61) 1.540(3),
C(61)-C(69) 1.492(3), C(61)-C(62) 1.516(3), C(62)-O(62)
1.215(3), C(62)-N(63) 1.358(3), C(63)-N(63) 1.443(3), C(64)-
The aromatic acenaphthene fragment of the methanofullerene
5 appears planar within the experimental error. The dihedral
angles between the cyclopropane C(1)-C(61)-C(2) plane and
the planes of the two six-membered rings of the fullerene
fragment are 64.7° and 66.3°.
ꢀ
C(65) 1.389(3), C(64)-N(63) 1.395(3), C(64)-C(69) 1.400(3) Å.
The supramolecular structure of the methanofullerene 5 in the
crystal is determined mainly by the interplay of two type of π-
electronic interactions: fullerene fullerene and fullerene
planes of aromatic rings of the neighboring fullerenes are 3.32
ꢀ
and 3.37 Å.
3 3 3
3 3 3
aromatic substituents.
The presence of a large aromatic substituent at the fullerene
Interactions between aromatic-ring systems of the methano-
fullerene 5 molecules result in continuous zigzag chain formation
along the 0a crystallographic axis in the crystal with two alter-
nating distances between the fullerene centroids of 10.11 and
10.04 Å (Figure 3, a), and the angle between the centroids of
three fullerene fragments is 83.74°. The fullerene molecules are
assembled in zigzag chains due to π-π interactions of the six-
membered rings “face to face”; the shortest distances between the
core and solvent molecules in the crystal hinders the fullerene
3 3 3
fullerene interactions and leads to the obligatory participation
of the substituents in the π-electronic interactions. As a result,
each methanofullerene 5 molecule additionally participate in the
four π-interactions between aromatic substituents and fullerene
fragments (the distances between interacting planes are 3.11 and
ꢀ
3.23 Å) and the one π-π interaction between aromatic substit-
uents of two neighboring fullerenes with the shortest distances
Figure 3. (a) Zigzag fullerene arrangement in the crystal of 5, view along 0a axis. Dashed lines indicate the fullerene fullerene interactions. (b) View
3 3 3
along 0b axis on the honeycomb-like arrangement of the methanofullerene molecules in the crystal of 5. The solvent molecules are omitted for clarity.
Dashed lines indicate the all type of π-electronic interactions. The solvent molecules are distributed between 1 and 3 fullerene molecules in zigzag chains
and in the cavities of the honeycomb-like supramolecular structure in such a manner that close contacts between them are not detected. Such types of
mutual arrangement of the molecules in the crystal of 5 lead to a high packing coefficient (73.3%).
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ꢀ
between interacting planes 3.48 Å. These contacts link the zigzag
chains into a three-dimensional honeycomb-like networks with
pseudocavities arranged along the 0a crystallographic axis in the
crystal (Figure 3, b).
The crystals of 13 were obtained by the evaporation of a
chloroform solution as an inclusion compound with the solvent
chloroform molecule in a 1:1 stoichiometry. The molecules with
Cs-symmetry are located in the general position of the monoclinic
unit cell, and the chloroform molecule is disordered over 2
positions with relative occupancies 0.6: 0.4. The planarity of
cyclic fragment in the molecule (standard deviation within
0.02(1) Å, Figure 4) is caused by the lack of large substituents
in the ‘benzo‘ fragment of the bicyclic moiety. The dihedral angles
between the cyclopropane ring plane and the planes of two six-
membered cycles of fullerene fragment are 64.9° and 64.3°.
The quality of the experiments allowed us to analyze the
distributions of the bonds lengths in the fullerene cores of both
molecules, methanofullerenes 5 and 13 (Figure 5). It is interest-
ing to note that there is an averaging of the bond lengths
in molecule 5, but for 13, despite the rather wide range of
bonds lengths, the most typical are those corresponding to the
carbon-carbon bonds in 5-membered cycles (1.45-1.46 Å) and
6-membered cycles (1.37-1.39 Å). This result can be considered
as unambiguous proof of the cyclic substituent's influence on a
fullerene fragment in the methanofullerene 13 molecule.
In the crystal, the methanofullerene 13 molecules are linked
Figure 6. Monolayer fullerene arrangement in the crystal of 13; the
view along the 0a-axis. H atoms and chloroform molecules are omitted
for clarity. Dashed lines indicate the fullerene fullerene interactions.
3 3 3
Table 1. Peak Potentials (Epred) and Currents (Ipred, μA) on
the CV Curves of C60 and Compounds 1, 5, 7-10, 13, and 14a
Epred V /(Ipred, μA)
compd conc, M
C1
C2
C3
C4
with chloroform molecules by C-H O-intermolecular inter-
3 3 3
C60
1
5.0 ꢀ 10-3 -0.83 (4.2) -1.24 (3.8) -1.70 (3.9) -2.16 (3.9)
1.7 ꢀ 10-3 -1.22 (11.3) -1.92 (8.0)
action between hydrogen H(70) of the solvent molecule and the
oxygen O(62) of the carboxyl group. The parameters of the
5
1.7 ꢀ 10-3 -0.90 (3.0) -1.22 (2.3) -1.41 (1.8) -1.84 (1.8)
1.7 ꢀ 10-3 -1.20 (6.4) -1.82 (2.8) -2.02 (2.8) -2.24 (2.8)
1.0 ꢀ 10-3 -0.88 (2.0) -1.22 (2.0) -1.40 (1.5) -1.82 (1.1)
6.7 ꢀ 10-3 -1.35 (10.5) -2.02 (8.8)
interaction are: distance H(70) O(62) 2.32 Å, angle C(70)-
3 3 3
H(70) O(62) 149.07°.
7
3 3 3
Each methanofullerene 13 molecule is in a hexagonal environ-
10
8
ment in the crystal but participates in the fullerene fullerene
3 3 3
interactions only with five neighboring fullerene fragments. The
corresponding packing diagram, which shows the intermolecular
interactions, is presented in Figure 6.
13
9
1.0 ꢀ 10-3 -0.89 (1.9) -1.22 (2.0) -1.43 (1.0) -1.85 (0.9)
5.7 ꢀ 10-3 -1.31 (9.8) -1.99 (7.0)
14
1.0 ꢀ 10-3 -0.90 (2.1) -1.24 (1.8) -1.44 (1.5) -1.88 (1.2)
These interactions form continuous goffered layers parallel to
the 0bc plane in crystal, the distances between the fullerene
a Supporting electrolyte, 0.1 M Bu4NBF4; cathode, glassy carbon (GC)
(Swork = 3.14 mm2); reference electrode, Ag/0.01 M AgNO3 in MeCN;
ꢀ
centroids are in the range of 10.07-10.15 Å. There are π
π
scan rate, Vpot = 50 mV s-1
.
3 3 3
interactions between the 5-membered aromatic rings (5/5
interactions, distance between the centers of interacting rings is
3.89 Å), 5- and 6-membered rings (5/6 interactions, distance
between the centers is 3.88 Å and the dihedral angle is 19.33°),
and 6-membered rings (6/6 interactions with distance 4.09 Å and
dihedral angle 18.08°). The goffered layers are surrounded by the
aromatic substituents and solvent molecules. The absence of the
hexagonal environment can be explaned by a steric factors and
the participation of this molecule in π π-interactions between
3 3 3
the aromatic substituents of two molecules of the neighboring
layers. Owing to such a type of π-electronic interaction and
fullerene aromatic substituents interactions the goffered
3 3 3
fullerene fullerene interactions with the sixth molecule in a
layers are linked in a three-dimensional network.
3 3 3
Figure 5. Bond lengths distribution in the fullerene fragments of (a) methanofullerene 5 and (b) methanofullerene 13 molecules.
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Electrochemical Study of 1, 5, 7-10, 13, 14, and C60.
Practical properties of the methanofullerenes, including their
biological activity, are connected generally with the ability to
accept electrons and form radicals. The electrochemical reduc-
tion of the methanofullerenes 5, 10, 13, and 14 and also the
starting quinones 1 and 7, isatins 8 and 9, and fullerene C60 was
studied by cyclic voltammetry (CV).
The results of electrochemical study of the methanofullerenes
5, 10, 13, and 14, as well as comparative data for C60, starting
quinones 1 and 7, and isatins 8 and 9, are shown in Table 1. Four
classical reversible one-electron reduction peaks are observed on
the CV curve of the fullerene C60. The reduction of the quinones
1 and 7 is a reversible process which is realized as two reversible
one-electron transfer steps. The first electron transfer of the
compounds 1 and 7 is observed at the same potential range as the
second reduction peak of free C60 molecule (Table 1).
equipped with a pulsed gradient unit capable of producing magnetic field
pulse gradients in the z-direction of 56 G cm-1. Chemical shifts are
3
reported on the δ (ppm) scale and are relative to the residual 1H and 13
C
signal of CHCl3 in the CDCl3.
In CV studies, a stationary glassy carbon (GC) disk electrode with a
working surface of 3.14 mm2 was used as the working electrode. The CV
curves were recorded in the three-electrode type electrochemical cell in
o-DCB/MeCN (3: 1 by volume) solution in the presence of Bu4NBF4
(0.1 M) and X-Y two-coordinate recorder with a potential sweep rate of
50 mV s-1. Silver electrode Ag/AgNO3 (0.01 M solution in MeCN) was
served as the reference electrodes (E°(Fc/Fcþ) = þ0.20 V). A Pt wire
with a diameter of 1 mm served as the auxiliary electrode. Measurements
were carried out under thermostatic conditions (20 °C) in a nitrogen
atmosphere.
’ COMPUTATIONAL METHODS
The electrochemical behavior of the isatins 8 and 9 at cathodic
potentials is also characterized as two reversible one-electron
processes which are negatively shifted with respect to the values
of the electroreduction of the quinones 1 and 7 (-1.35 and
-1.31 V versus Ag/0.01 M AgNO3 in MeCN). The electro-
reduction of the methanofullerenes 5, 10, 13, and 14 proceeds as
the reversible transfer of four electrons displaying four reversible
peaks on the CV curves (Table 1). A comparison of the potentials
and of the peak’s currents for C60, the quinones 1 and 7, the
isatins 8 and 9, and the methanofullerenes 5, 10, 13, and 14
shows that the first step of the methanofullerene reduction (C1)
involves an electron transfer onto fullerene sphere. At the same
time, the second peak of the reduction (C2) and the other
cathodic peaks (C3 and C4) that appeared on the CV curve of the
methanofullerenes 5, 10, 13, and 14 correspond to the reduction
of both the fullerene sphere and attached polycyclic addend.
A comparison of the reduction potentials demonstrates that
the first reduction peaks of all methanofullerenes are shifted on
50-70 mV to the cathodic region as compared with that of free
C60. It could be a result of the fullerene sphere electrophilicity
decreasing due to the opening of one CdC bond.49 It should be
noted that reversibility of the electrochemical reduction process
allows us to conclude that the methanofullerenes 5, 10, 13, and
14 are stable on the cyclic voltammetry time scale.
Chemical shifts of 13 were determined within the DFT framework
using a hybrid exchange-correlation functional, B3LYP, at the 6-31G(d)
level as implemented in Gaussian 98.51 Full geometry optimizations
were performed at the ab initio RHF/6-31G level. All data were referred
to TMS (1H and 13C) chemical shifts that were calculated under the
same conditions.
The XRD analysis for the crystals of compounds 5 and 13 were
collected at 296 K using graphite-monochromated Mo KR (λ 0.71073 Å)
radiation. Data were corrected for the absorption effect using the
SADABS program.52 The structures were solved by direct methods and
refined by the full-matrix least-squares method using SHELXTL53 and
WinGX54 programs. All non-hydrogen atoms were refined anisotropi-
cally. All hydrogen atoms were placed in idealized positions and refined
by using the riding model. Data collections: images were indexed,
integrates, and scaled using the APEX255 data reduction package. All
figures were created using PLATON.56
Crystallographic data (excluding structure factors) for the structures 5
and 13 in this paper have been deposited with the Cambridge Crystal-
lographic Data Centre as supplementary publication numbers CCDC
772639-772640. Copies of the data can be obtained, free of charge, on
application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, (fax:
þ44-(0)1223-336033 or e-mail: deposit@ccdc.cam.ac.uk).
2-(3-Cyclopropa[1,9](C60-Ih)[5,6]fulleren-3-yl)-1-ace-
naphthenone (5).39. Hexaethyltriaminophosphine 2 (0.093 g, 0.375
mmol) was added dropwise to a mixture of acenaphthenequinone 1
(0.023 g, 0.126 mmol) and C60 (0.090 g, 0.125 mmol) in anhydrous
o-dichlorobenzene (40 cm3) at -10 °C. The mixture was stirred for 8 h
at -10 °C, after which time the temperature was allowed to warm to
25 °C. The solvent was removed under reduced pressure, and the
residue was purified by column chromatography on silica gel using mix-
ture of the toluene and petroleum ether 85:15 as eluent to give unreacted
C60 (0,027 g, 30%) and a fraction containing a mixture of the methanoful-
lerene 5 and polyproducts. The methanofullerene 5 (0.044 g, 40%) was
obtained by repeated column chromatography: νmax (KBr)/cm-1 1723,
1625, 1420, 1229, 1026, 774, 713, 526; λmax (CH2Cl2)/nm 258, 329,
’ CONCLUSION
Involvement of the fullerene in the reaction with phosphine 2
and a variety of R-diketones mentioned above has allowed us to
make an unambiguous conclusion about the intermediate for-
mation of carbenes in the deoxygenation reaction of the organic
compounds under the action of the phosphorus(III) derivatives.
New polycyclic methanofullerenes 5, 10, and 13-16 were
obtained in these three-component reactions. NMR and XRD
data confirm the [6,6]-type of addend linkage and the carbene
addition regiochemistry. It should be also noted that the
investigated reaction is the first example of useful application
of the deoxygenation methodology in the synthesis of the
methanofullerenes.
1
438 (ribbon), 504, 690; H NMR (600.13 MHz; mixture of CS2 and
CDCl3) δ 7.81 (1H, dd, J 7.4 and 7.8, C(4)H), 7.93 (1H, dd, J 7.4 and
7.0, C(7)H), 8.07 (1H, d, J 8.2, C(5)H), 8.23 (1H, d, J 7.0, C(8)H),
8.28 (1H, d, J 8.2, C(6)H), 8.56 (1H, d, J 7.0, C(3)H); 13C NMR
(150.94 MHz; mixture of CS2 and CDCl3) δ 47.73 (C(2)), 121.54
(C(3)), 122.30 (C(8)), 125.78 (C(5)), 128.20 (C(7)), 128.60 (C(4)),
130.41 (C(5a)), 131.79 (C(6)), 131.92 (C(8a)), 135.21 (C(2a)),
141.27 (C(8b)), 193.15 (C(1)), fullerene moiety: 76.48 (2C), 138.52
(2C), 140.74 (2C), 141.11 (2C), 141.25 (2C), 141.42 (2C), 141.83
(2C), 141.94 (2C), 142.02 (2C), 142.58 (2C), 142.75 (2C), 142.81
(2C), 142.83 (1C), 142.94 (1C), 143.37 (2C), 143.51 (2C), 143.91
(2C), 144.04 (1C), 144.15 (2C), 144.29 (2C), 144.43 (4C), 144.45
’ EXPERIMENTAL SECTION
The quinones 1 and 7 were purchased from a commercial supplier.
Isatins 3, 4, 8, and 9 were prepared as described previously.50 IR spectra
were recorded in KBr pellets. UV spectra were recorded in CH2Cl2. 1H
and 13C NMR spectra were recorded at room temperature (∼20 °C) in
deuterated chloroform (CDCl3) on 600 and 400 MHz spectrometers
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The Journal of Organic Chemistry
ARTICLE
(2C), 144.50 (2C), 144.66 (4C), 144.77 (1C), 144.91 (2C), 144.96
(4C), 145.25 (2C), 146.17 (2C); MS MS (MALDI) m/z calcd for
C72H6O 886, found 886.
for C69H7NO: C, 95.73, H, 0.81, N, 1.62. Found: C, 95.21, H,
0.80, N, 1.91.
1-Allyl-3-(3-cyclopropa[1,9](C60-Ih)[5,6]fulleren-3-yl)indo-
lin-2-one (14). Hexaethyltriaminophosphine 2 (0.100 g, 0.400 mmol)
was added dropwise to a mixture of the isatin 9 (0.025 g, 0.130 mmol)
and C60 (0.090 g, 0.125 mmol) in anhydrous o-dichlorobenzene
(40 cm3) at -10 °C. The mixture was stirred for 8 h at -10 °C, after
which time the temperature was allowed to 25 °C. The solvent was
removed under reduced pressure, and the residue was purified by
column chromatography on silica gel using a mixture of toluene and
petroleum ether 7:2 as the eluent to give unreacted C60 (0.006 g, 7%),
the methanofullerene 14 (0.036 g, 32%), and the polyadduct mix-
ture: νmax (KBr)/cm-1 1721, 1609, 1464, 1354, 987, 920, 743; λmax
(CH2Cl2)/nm 430 (ribbon), 500, 714; 1H NMR (600.13 MHz; mixture
of CS2 and CDCl3) δ 4.69 (2H, d, J 5.3, C(8)H2), 5.41 and 5.53 (2H, d, J
17.2 and 10.6, C(10)H2), 6.14-6.06 (1H, m, C(9)H), 7.20 (1H, d, J 7.9,
C(7)H), 7.26 (1H, m, C(5)H), 7.52 (1H, dd, J 7.9 and J 7.6, C(6)H),
8.34 (1H, d, J 7.6, C(4)H); 13C NMR (150.94 MHz; mixture of CS2 and
CDCl3) δ 42.05 C(3)), 43.24 (C(8)), 109.56 (C(7)), 118.57 (C(10)),
122.71 (C(5)), 123.91 (C(4)), 125.09 (C(3a)), 129.37 (C(6)), 131.28
(C(9)), 142.83 (C(7a)), 169.13 (C(2)), fullerene moiety: 75.29 (2C),
138.92 (2C), 140.98 (2C), 141.30 (2C), 141.43 (2C), 141.57 (2C),
142.13 (2C), 142.18 (2C), 142.22 (2C), 142.80 (2C), 142.99 (2C),
143.04 (2C), 143.07 (2C), 143.12 (2C), 143.57 (2C), 143.75 (2C),
144.14 (4C), 144.23 (1C), 144.41 (1C), 144.53 (2C), 144.75 (5C),
145.00 (4C), 145.05 (1C), 145.17 (2C), 145.20 (2C), 145.23 (2C),
145.46 (4C); MS MS (MALDI) m/z calcd for C71H9NO 892, found
892. Anal. Calcd for C71H9NO: C, 95.63; H, 1.01; N, 1.57. Found: C,
95.14,; H, 0.71; N, 1.95.
2-(3-Cyclopropa[1,9](C60-Ih)[5,6]fulleren-3-yl)-1-acean-
threnone (10). Hexaethyltriaminophosphine 2 (0.093 g, 0.376 mmol)
was added dropwise to a mixture of aceanthrenequinone 7 (0.029 g,
0.125 mmol) and C60 (0.090 g, 0.125 mmol) in anhydrous o-dichlor-
obenzene (40 cm3) at -10 °C. The mixture was stirred for 8 h at
-10 °C, after which time the temperature was allowed to warm to 25 °C.
The solvent was removed under reduced pressure, and the residue was
purified by column chromatography on silica gel using mixture of the
toluene and petroleum ether 85:15 as eluent to give unreacted C60
(0.036 g, 40%), the fraction containing the methanofullerenes 10 and
C60, and the fraction containing the mixture of the polyadducts. The
p-But-calix[8]arene 11 was added to the fraction containing the metha-
nofullerenes 10 and C60, and the precipitate 12 occurred immediately.
The methanofullerene 10 (0.024 g, 20%) was obtained by column
chromatography of the filtrate after separation of the complex 12. The
data for the methanofullerene 10: νmax (KBr)/cm-1 1731, 1700, 1458,
1425, 1155 1107, 1079, 737, 7670, 527; λmax (CH2Cl2)/nm 258, 329,
405, 433 (ribbon), 517, 590, 610; 1H NMR (600.13 MHz; mixture of
CS2 and CDCl3) δ 7.71 (2H, m, C(4,8)H), 7.82 (1H, dd, J 7.2, C(9)H),
8.13 (1H, d, J 8.9, C(5)H), 8.23 (1H, d, J 8.5, C(7)H) 8.53 (1H, d, J 7.0,
C(3)H), 8.79 (1H, s, C(6)H), 9.34 (1H, d, J 8.5, C(10)H); 13C NMR
(150.94 MHz; mixture of CS2 and CDCl3) δ 47.39 (C(2)), 121.14
(C(3)), 122.62 (C(10)), 124.67 (C(10b)), 125.37 (C(5)), 126.95
(C(8)), 127.95 (C(5a)), 128.14 (C(4)), 128.74 (C(10a)), 129.11
(C(7)), 129.70 (C(9)), 132.06 (C(6)), 133.29 (C(6a)), 135.23
(C(2a)), 142.98 (C(10c)), 193.94 (C(1)), fullerene moiety: 76.61
(2C), 138.67 (2C), 140.86 (2C), 141.21 (2C), 141.26 (2C), 141.56
(2C), 141.85 (2C), 142.06 (2C), 142.13 (2C), 142.70 (2C), 142.88
(2C), 142.95 (2C), 143.06 (1C), 143.47 (2C), 143.63 (2C), 144.02
(2C), 144.15 (1C), 144.27 (2C), 144.42 (2C), 144.56 (5C), 144.62
(2C), 144.81 (2C), 144.90 (4C), 144.97 (1C), 145.02 (2C), 145.08
(4C), 145.37 (2C), 145.28 (2C); MS MS (MALDI) m/z calcd for
C76H8O 937, found 937. Anal. Calcd for C76H8O: C, 97.44; H, 0.85.
Found: C, 96.94; H, 0.83.
1-Acetyl-3-(3-cyclopropa[1,9](C60-Ih)[5,6]fulleren-3-yl)indo-
lin-2-one (15). Hexaethyltriaminophosphine 2 (0.110 g, 0.450 mmol)
was added dropwise to a mixture of the isatin 3 (0.020 g, 0.160 mmol)
and C60 (0.100 g, 0.140 mmol) in anhydrous o-dichlorobenzene
(40 cm3) at -10 °C. The mixture was stirred for 8 h at -10 °C, after
which the temperature was allowed to rise to 25 °C. The solvent was
removed under reduced pressure, and the residue was purified by
column chromatography on silica gel using a mixture of toluene and
petroleum ether 8:2 as eluent to give unreacted C60 (0.0160 g, 16%), the
methanofullerene 15 (0.038 g, 31%), and the polyadducts mixture: νmax
(KBr)/cm-1 1773, 1745, 1713, 1608, 1552, 1460, 1378, 1336, 1307,
1265, 1212, 1166, 1095, 1039, 981, 749, 598, 527; λmax (CH2Cl2)/nm
Data for complex 12: νmax (KBr)/cm-1 528, 578, 729, 782, 876,
1118, 1184, 1203, 1248, 1293, 1362, 1429, 1452, 1485, 1603, 2868, 2960.
Anal. Calcd for C148H112O8: C, 88.06, H, 5.57. Found: C, 89.26, H, 5.59.
1-Methyl-3-(3-cyclopropa[1,9](C60-Ih)[5,6]fulleren-3-
yl)indolin-2-one (13). Hexaethyltriaminophosphine 2 (0.120 g,
0.480 mmol) was added dropwise to a mixture of the isatin 8 (0.020
g, 0.124 mmol) and C60 (0.100 g, 0.138 mmol) in anhydrous
o-dichlorobenzene (40 cm3) at -10 °C. The mixture was stirred for 8 h
at -10 °C, after which time the temperature was allowed to rise to 25 °C.
The solvent was removed under reduced pressure, and the residue was
purified by column chromatography on silica gel using a mixture of
toluene and petroleum ether 7:2 as eluent to give unreacted C60 (0.014 g,
14%), the methanofullerene 13 (0.044 g, 37%), and a polyadducts
mixture: νmax (KBr)/cm-1 1724, 1611, 1468, 1322, 1344, 772, 527; λmax
(CH2Cl2)/nm 430 (ribbon), 500, 720; 1H NMR (600.13 MHz; mixture
of CS2 and CDCl3) δ 3.57 (3H, s, C(8)H3), 7.17 (1H, d, J 7.9, C(7)H),
7.26 (1H, m, C(5)H), 7.55 (1H, dd, J 7.9 and J 7.5, C(6)H), 8.32 (1H, d,
J 7.7, C(4)H); 13C NMR (150.94 MHz; mixture of CS2 and CDCl3)
δ 26.64 (C(8)), 42.08 (C(3)), 108.53 (C(7)), 122.66 (C(5)), 123.78
(C(4)), 125.01 (C(3a)), 129.43 (C(6)), 143.50 (C(7a)), 169.09
(C(2)), fullerene moiety: 75.18 (2C), 138.79 (2C), 140.90 (2C),
141.24 (2C), 141.32 (2C), 141.48 (2C), 142.10 (4C), 142.14 (2C),
142.73 (2C), 142.90 (2C), 142.98 (2C), 143.04 (2C), 143.66 (2C),
143.71 (1C), 144.05 (3C), 144.14 (1C), 144.32 (2C), 144.44 (2C),
144.66 (6C), 144.88 (2C), 144.93 (1C), 144.96 (2C), 145.08 (4C),
145.10 (2C), 145.13 (2C), 145.36 (2C), 145.42 (2C); MS MS
(MALDI) m/z calcd for C69H7NO 866, found 866. Anal. Calcd
1
432 (ribbon), 496, 702; H NMR (600.13 MHz; mixture of CS2 and
CDCl3) δ 2.91 (3H, s, C(9)H), 7.41 (1H, dd, J 7.8 and 7.8, C(5)H), 7.59
(1H, dd, J 7.8 and 8.3, C(6)H), 8.41 (1H, d, J 7.8, C(4)H), 8.62 (1H, d, J
8.3, C(7)H); 13C NMR (150.94 MHz; mixture of CS2 and CDCl3) δ
26.88 (C(9)), 41.90 (C(3)), 116.74 (C(7)), 122.93 (C(4)), 124.24
(C(3a)), 125.00 (C(5)), 129.68 (C(6)), 140.03 (C(7a)), 169.27
(C(8)), 169.42 (C(2)), fullerene moiety: 75.11 (2C), 138.96 (2C),
140.80 (2C), 140.90 (2C), 141.18 (4C), 141.97 (4C), 142.06 (2C),
142.63 (2C), 142.78 (4C), 142.89 (4C), 143.18 (2C), 143.33 (1C),
143.52 (2C), 143.88 (3C), 144.32 (6C), 144.59 (8C), 144.86 (2C),
144.98 (4C), 145.04 (4C); MS MS (MALDI) m/z calcd for C70H7NO2
894, found 894. Anal. Calcd for C70H7NO2: C, 94.07; H, 0.78; N, 1.57.
Found: C, 93.60; H, 0.53; N, 1.82.
1-(30,50-Di-tert-butyl-40-hydroxybenzyl)-3-(300-cyclopro-
pa[1000,9000](C60-Ih)[5,6]fulleren-300-yl)indolin-2-one (16). Hex-
aethyltriaminophosphine 2 (0.100 g, 0.400 mmol) was added dropwise
to a mixture of the isatin 4 (0.050 g, 0.136 mmol) and C60 (0.100 g,
0.138 mmol) in anhydrous o-dichlorobenzene (40 cm3) at -10 °C. The
mixture was stirred for 8 h at -10 °C, after which time the temperature
was allowed to warm to 25 °C. The solvent was removed under reduced
pressure, and the residue was purified by column chromatography on
silica gel using mixture of the toluene and petroleum ether 8:2 as eluent
to give unreacted C60 (0.013 g, 13%), the methanofullerene 16 (0.069 g,
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ARTICLE
46%), and a polyadducts mixture: νmax (KBr)/cm-1 3438, 2955, 2922,
2864, 1722, 1636, 1611, 1466, 1431, 1356, 1236,1186, 1157, 1112, 744,
526; λmax (CH2Cl2)/nm 427 (ribbon), 494, 687; 1H NMR (400 MHz;
mixture of CS2 and CDCl3) δ 1.45 (18H, s, C(16-18)H and C(20-
22)H), 5.13 (2H, s, C(8)H), 5.20 (1H, s, C(12)OH), 7.23 (1H, d, J 7.4,
C(7)H), 7.24 (1H, dd, J 7.8 and 7.4, C(5)H), 7.35 (2H, s, C(10)H and
C(14H), 7.50 (1H, dd, J 7.4 and 7.4, C(6)H), 8.34 (1H, d, J 7.8, C(4)H);
13C NMR (100 MHz; mixture of CS2 and CDCl3) δ 30.18 (C(16-18),
C(20-22), 34.23 (C(15), C(19)), 42.30 (C(3)), 44.66 (C(8)), 109.91
(C(7)), 122.58 (C(5)), 123.84 (C(4)), 124.74 (C(9), C(10), C(14)),
125.15 (C(3a)), 129.28 (C(6)), 136.23 (C(11), C(13)), 143.12
(C(7a)), 153.49 (C(12)), 169.52 (C(2)), fullerene moiety: 75.38
(2C), 138.91 (2C), 140.96 (2C), 141.29 (2C), 141.44 (2C), 141.60
(2C), 142.18 (2C), 142.22 (4C), 142.83 (2C), 142.98 (2C), 143.06
(2C), 143.29 (2C), 143.56 (2C), 143.76 (2C), 144.14 (2C), 144.18
(2C), 144.24 (1C), 144.38 (2C), 144.53 (2C), 144.72 (2C), 144.73
(2C), 144.76 (2C), 144.97 (2C), 145.05 (3C), 145.16 (2C), 145.18
(2C), 145.22 (2C), 145.48 (2C), 145.57 (2C); MS MS (MALDI) m/z
calcd for C83H27NO2 1070, found 1070. Anal. Calcd for C83H27NO2: C,
93.18, H, 2.52, N, 1.31. Found: C, 92.68, H, 2.24, N, 1.68.
(14) Wu, H.-Ch.; Yu, J.-Q.; Spencer, J. B. Org. Lett. 2004,
6, 4675–4678.
(15) Scott, C. B. J. Org. Chem. 1957, 22, 1118–1119.
(16) Minami, T.; Matsuzaki, N.; Ohshiro, Y.; Agawa, T. J. Chem. Soc.,
Perkin Trans. 1 1980, 1731–1738.
(17) Newman, M. S.; Blum, S. J. Am. Chem. Soc. 1964,
86, 5598–5600.
(18) Ramirez, F.; Yamanaka, H.; Basedow, O. H. J. Am. Chem. Soc.
1961, 83, 173–178.
(19) Markgraf, H.; Heller, Ch. I.; Avery, N. L., III. J. Org. Chem. 1970,
35, 1588–1591.
(20) Griffiths, D. V.; Tebby, J. C. J. Chem. Soc., Chem. Commun.
1986, 871–872.
(21) Griffiths, D. V.; Griffiths, P. A.; Whitehead, B. J.; Tebby, J. C. J.
Chem. Soc., Perkin Trans. 1 1992, 479–484.
(22) Griffiths, D. V.; Griffiths, P. A.; Karim, Kh.; Whitehead, B. J. J.
Chem. Soc., Perkin Trans. 1 1996, 555–561.
(23) Griffiths, D. V.; Harrisa, J. E.; Karim, Kh.; Whitehead, B. J.
ARKIVOC 2000, 304–311.
(24) Cheong, Y.-K.; Duncanson, Ph.; Griffiths, D. V. Tetrahedron
2008, 64, 2329–2338.
(25) Griffiths, D. V.; Al-Jeboori, M. J.; Cheong, Y.-K.; Duncanson,
Ph.; Harris, J. E.; Salt, M. C.; Taylor, H. V. Org. Biomol. Chem. 2008,
6, 577–585.
’ ASSOCIATED CONTENT
(26) Chiusoli, G. P.; Cometti, G.; Bellotti, V. J. Chem. Soc., Chem.
Commun. 1977, 216–217.
(27) Lathourakis, G. E.; Litinas, K. E. J. Chem. Soc., Perkin Trans. 1
1996, 491–493.
(28) Hirsch, A.; Brettreich, M. In Fullerens: Chemistry and Reactions;
Wiley-VCH: Weinheim, 2005; Chapter 2, p 49.
(29) Troshin, P. A.; Lyubovskaya, R. N. Russ. Chem. Rev. 2008,
77, 305–349.
(30) Da Ros, T. In Carbon Materials: Chemistry and Physics, Medic-
inal Chemistry and Pharmacological Potential of Fullerenes and Carbon
Nanotubes; Cataldo, F., Da Ros, T., Eds.; Springer: New York, 2008; Vol.
1, pp 1-21.
(31) Kumar, A.; Menon, S. K. Eur. J. Med. Chem. 2009,
44, 2178–2183.
Supporting Information. 1H and 13C NMR spectra of
S
b
new compounds. This material is available free of charge via the
Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*Tel:þ7(843)2727384. Fax: þ7(843)2732253. E-mail: bogdanov@
iopc.ru.
’ ACKNOWLEDGMENT
(32) Yin, J.-J.; Lao, F.; Fu, P. P.; Wamer, W. G.; Zhao, Y.; Wang,
P. C.; Qiu, Y.; Sun, B.; Xing, G.; Dong, J.; Liang, X.-J.; Chen, C.
Biomaterials 2009, 30, 611–621.
(33) Enes, R. F.; Farinha, A. S. F.; Tome, A. C.; Cavaleiro,
J. A. S.; Amorati, R.; Petrucci, S.; Pedulli, G. F. Tetrahedron 2009,
65, 253–262.
(34) Gubskaya, V. P.; Berezhnaya, L. S.; Gubaidullin, A. T.; Faingold,
I. I.; Kotelnikova, R. A.; Konovalova, N. P.; Morozov, V. I.; Litvinov, I. A.;
Nuretdinov, I. A. Org. Biomol. Chem. 2007, 5, 976–981.
(35) Witte, P.; Beuerle, F.; Hartnagel, U.; Lebovitz, R.; Savouchkina,
A.; Sali, S.; Guldi, D.; Chronakis, N.; Hirsch, A. Org. Biomol. Chem. 2007,
5, 3599–3613.
(36) Ramirez, F.; Patwardhan, A. V.; Kugler, H. J.; Smith, P.
Tetrahedron 1968, 24, 2275–2287.
(37) Bogdanov, A. V.; Mironov, V. F.; Buzykin, B. I.; Konovalov, A. I.
Russ. J. Gen. Chem. 2005, 75, 825–826.
(38) Bogdanov, A. V.; Mironov, V. F.; Musin, L. I.; Buzykin, B. I.;
Konovalov, A. I. Rus. J. Gen. Chem. 2008, 78, 1977–1979.
(39) Romanova, I. P.; Bogdanov, A. V.; Mironov, V. F.; Larionova,
O. A.; Latypov, S. K.; Balandina, A. A.; Yakhvarov, D. G.; Sinyashin,
O. G. Mendeleev Commun. 2009, 19, 306–308.
We express our gratitude to Prof. Dr. Vaughan Griffiths for the
discussions and extremely valuable recommendations. This work
is supported by the Russian Foundation for Basic Research (Grant
Nos. 09-03-00259-a, 09-03-00123-a, 09-03-00931-a, and 09-03-
00933-a) and by Program No. 6 of the Division of Chemistry and
Material Sciences of Russian Academy of Sciences.
’ REFERENCES
(1) Holm, R. H. Chem. Rev. 1987, 87, 1401–1449.
(2) Firouzabadia, H.; Jamalianb, A. J. Sulfur Chem. 2008, 29, 53–97.
(3) Horner, L.; Jurgens, E. Ber. 1957, 90, 2184–2189.
(4) Cividino, P.; Dheu-Andries, M.-L.; Ou, J.; Milet, A.; Py, S.; Toy,
P. H. Tetrahedron Lett. 2009, 50, 7038–7042.
(5) Freeman, W.; Urvoy, M.; Criswell, M. E. J. Org. Chem. 2005,
70, 5014–5019.
(6) Sundberg, R. J. J. Org. Chem. 1965, 30, 3604–3610.
(7) Fischer, B.; Sheihet, L. J. Org. Chem. 1998, 63, 393–395.
(8) Davies, W.; Guner, V. A.; Houk, K. N. Org. Lett. 2004,
6, 743–746.
(40) Pimenova, A. S.; Kozlov, A. A.; Goryunkov, A. A.; Yu., V.;
Markov, P. A.; Khavrel, S. M.; Avdoshenko, V. A.; Vorobiev, I. N.; Ioffe,
S. G.; Sakharov, S. I.; Troyanov; Sidorov, L. N. Dalton Trans. 2007,
36, 5322–5328.
(9) Sawant, D.; Kumar, R.; Maulik, P. R.; Kundu, B. Org. Lett. 2006,
8, 1525–1528.
(10) Varughese, D. J.; Manhas, M. S.; Bose, A. K. Tetrahedron Lett.
2006, 47, 6795–6797.
(11) Reis, P. M.; Royo, B. Tetrahedron Lett. 2009, 50, 949–952.
(12) Oae, S.; Nakanishi, A.; Kozuka, S. Tetrahedron 1972,
28, 549–554.
(41) Bogdanov, A. V.; Mironov, V. F.; Khasiyatullina, N. R.;
Krivolapov, D. B.; Litvinov, I. A.; Konovalov, A. I. Mendeleev Commun.
2007, 17, 183–185.
(13) Sekine, M.; Yamagata, H.; Hata, T. Tetrahedron Lett. 1979,
20, 375–378.
(42) Sinyashin, O. G.; Romanova, I. P.; Yusupova, G. G.; Kovalenko,
V. I.; Yanilkin, V. V.; Azancheev, N. M. Mendeleev Commun. 2000, 10, 96–98.
2556
dx.doi.org/10.1021/jo102332e |J. Org. Chem. 2011, 76, 2548–2557

The Journal of Organic Chemistry
ARTICLE
(43) Konarev, D. V.; Lyubovskaya, R. N. Russ. Chem. Rev. 1999,
68, 19–38.
(44) Dimitriev, P.; Kazantseva, Z. I.; Lavrik, N. V. J. Inclusion Phenom,
Macrocycl. Chem. 1999, 35, 85–91.
(45) Derome, A. E. Modern NMR Techniques for Chemistry Research;
Pergamon: New York, 1988.
(46) Atta-ur-Rahman. One and Two Dimensional NMR Spectroscopy;
Elsevier: Amsterdam, 1989.
(47) Latypov, Sh.; Balandina, A.; Boccalini, M.; Matteucci, A.;
Usachev, K.; Chimichi, S. Eur. J. Org. Chem. 2008, 2008, 4640–4646.
(48) Latypov, Sh. K; Kozlov, A. V.; Hey-Hawkins, E.; Balueva, A. S.;
Karasik, A. A.; Sinyashin, O. G. J. Phys. Chem. A 2010, 114, 2588–2596.
(49) Ohno, T.; Moriwaki, K.; Miyata, T. J. Org. Chem. 2001,
66, 3397–3401.
(50) Tacconi, G.; Righetti, P. P.; Desimoni, G. J. Prakt. Chem. 1973,
315, 339–344.
(51) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.;
Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels,
A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.;
Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford,
S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.;
Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.;
Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.;
Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith,
T.; M. A. Al-Laham, Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.;
Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong,
M. W.; Andres, J. L.; Gonzalez, C.; M. Head-Gordon, Replogle, E. S.;
Pople, J. A., Gaussian 98, revision A.3; Gaussian, Inc.: Pittsburgh, PA,
1998.
(52) Sheldrick, G. M. SADABS, Program for empirical X-ray absorp-
tion correction, Bruker-Nonius, 2004.
(53) Sheldrick, G. M.. SHELXTL v.6.12, Structure Determination
Software Suite, Bruker AXS, Madison, WI, 2000.
(54) Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837–838. APEX2
(Version 2.1), SAINTPlus. Data Reduction and Correction Program
(Version 7.31A, Bruker Advansed X-ray Solutions, BrukerAXS Inc.,
Madison, WI, 2006.
(55) APEX2 (Version 2.1), SAINTPlus. Data Reduction and Cor-
rection Program (Version 7.31A, Bruker Advansed X-ray Solutions,
BrukerAXS Inc., Madison, WI, 2006.
(56) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7–13.
2557
dx.doi.org/10.1021/jo102332e |J. Org. Chem. 2011, 76, 2548–2557