Cycloaddition of diazoketones to [60]fullerene in the presence of the catalytic system Pd(acac)2-PPh3-Et3Al

Article abstract of DOI:10.1007/s11172-010-0124-1

A method for the selective and efficient synthesis of methanofullerenes by cycloaddition of diazoketones to [60]fullerene in the presence of a three-component catalytic system Pd(acac)₂-PPh₃-Et ₃Al has been developed.

Full text of DOI:10.1007/s11172-010-0124-1

Russian Chemical Bulletin, International Edition, Vol. 59, No. 3, pp. 611—614, March, 2010
611
Cycloaddition of diazoketones to [60]fullerene in the presence
of the catalytic system Pd(acac)2—PPh3—Et3Al
A. R. Tuktarov, A. R. Akhmetov, L. M. Khalilov, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Bashkortostan, Russian Federation.
Fax: +7 (347) 284 2750. Eꢀmail: ink@anrb.ru
A method for the selective and efficient synthesis of methanofullerenes by cycloaddition
of diazoketones to [60]fullerene in the presence of a threeꢀcomponent catalytic system
Pd(acac)2—PPh3—Et3Al has been developed.
Key words: metal complex catalysis, cycloaddition, [60]fullerene, diazoketones, methanoꢀ
fullerenes.
Functionally substituted fullerenes are of particular inꢀ
terest and practical value. A great number of publications
is devoted to the synthesis and physicochemical properties
of these compounds.1—7 The main part of these works is
focused on the synthesis and study of the properties of
homoꢀ and methanofullerenes, which synthesized by the
Bingel reaction8 as well as by thermal9 or catalytical10
cycloaddition of diazo compounds to [60]fullerene. The
known synthetic methods toward cyclopropafullerenes by
reaction of [60]fullerene with diazo compounds, includꢀ
ing diazoketones,11—14 have little preparative significance
due to low yields of the target methanofullerenes or reꢀ
quire stoichiometric amounts of such expensive promotꢀ
ers as ruthenium complexes.9,10
known that the reaction of 2ꢀoxoꢀ2ꢀphenyldiazoethane
with [60]fullerene at ~20 °C for 1 week resulted in a mixꢀ
ture of cycloadducts 1—3 in the yield of ~30%
(1 : 2 : 3 = 1 : 1 : 3).14
We found that the reaction of 2ꢀoxoꢀ2ꢀphenyldiazoꢀ
ethane with [60]fullerene (reactant ratio 5 : 1, respectively)
in the presence of a threeꢀcomponent catalytic system
Pd(acac)2—PPh3—Et3Al (1 : 2 : 4, 20 mol.%) at 80 °C (1 h,
oꢀdichlorobenzene) furnished exclusively 6,6ꢀclosed cyꢀ
cloadduct 1 in ~40% yield (Scheme 1). No increase in the
Scheme 1
Recently,15—18 we have reported the synthesis of homoꢀ
and methanofullerenes in high yields by cycloaddition
of diazo compounds (diazomethane,15 diazoalkanes,16 and
diazoacetates17,18) to [60]fullerene in the presence of palꢀ
ladium complexes. In continuation of this research, in the
present work we studied cycloaddition of diazoketones to
[60]fullerene in the presence of palladium complexes. The
effect of the substituent in the starting diazoketone on the
selectivity of the reaction and the yields of the target funcꢀ
tionalized methanofullerenes have also been studied.
Results and Discussion
Among a number of tested transition metal complexes,
a threeꢀcomponent catalyst prepared from Pd(acac)2,
PPh3, and Et3Al (1 : 2 : 4) was found most efficient and
selective in the reactions under study and in the reactions
of [60]fullerene with diazoacetates as well. In this regard,
all subsequent experiments were carried out using this catꢀ
alytic system. Cycloaddition of 2ꢀoxoꢀ2ꢀphenyldiazoꢀ
ethane to [60]fullerene was used as a model reaction. It is
i. N2CHC(O)Ph, Pd(acac)2—PPh3—Et3Al (1 : 2 : 4); ii. N2CHC(O)Ph
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 598—601, March, 2010.
1066ꢀ5285/10/5903ꢀ0611 © 2010 Springer Science+Business Media, Inc.

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Tuktarov et al.
Scheme 2
total yield (~43%) was observed when the reaction time
was prolonged up to 2 h. When the reaction under study
was carried out under the same conditions but without
catalytic system, a mixture of 6,6ꢀclosed (1) and 5,6ꢀopen
(2, 3) adducts was obtained in 1 : 1 : 3 ratio in ~35% total
yield. No formation of bisꢀadducts and dihydrofuranoꢀ
fullerene, which formed usually in the thermal reaction of
[60]fullerene with diazoketones,11—13 were observed in our
experiments.
1
The H NMR spectrum of compound 1 exhibited the
singlet signal (δH 5.65), which was attributed to the proꢀ
ton at the bridging C atom, doublet signal (δH 8.48
(J = 7.6 Hz)) and two triplet signals (δH 7.70 (J = 7.6 Hz)
and 7.72 (J = 7.6 Hz)) characteristic of the protons of the
phenyl group. These spectral data are in good accord with
previously published data14 on the cycloaddition of 2ꢀoxoꢀ
2ꢀphenyldiazoethane to [60]fullerene and confirmed the
formation of methanofullerene 1.
The data obtained from the 1H and 13C NMR spectra
and 2D experiments (HHCOSY, HSQC, HMBC) of
a mixture of compounds 1—3 indicated that the studied
reaction carried out under described conditions without
catalyst resulted in 6,6ꢀclosed (1) and stereoisomeric
5,6ꢀopen (2, 3) monoadducts.
i. Pd(acac)2—PPh3—Et3Al (1 : 2 : 4), 80 °C, 1 h.
fullerenes 4—6 revealed intensive peaks of molecular ions
with m/z 802.734, 816.734, and 830.824, respectively,
which also confirmed the formation of monoadducts.
With the aim to extend the applicability of the reaction
under investigation and study the activity of the complex
catalytic system as well, we involved diazoacetylꢀsubstiꢀ
tuted Oꢀ, Sꢀ, and Nꢀheterocycles in the cycloaddition
with [60]fullerene. It was found that the reaction of
[60]fullerene with 2ꢀoxoꢀ2ꢀ(furanꢀ2ꢀyl)ꢀ, 2ꢀoxoꢀ2ꢀ(thioꢀ
phenꢀ2ꢀyl)ꢀ, 2ꢀoxoꢀ2ꢀ(pyridinꢀ2ꢀyl)ꢀ, and 2ꢀoxoꢀ2ꢀ
(phenylquinolinꢀ4ꢀyl)diazoethanes (80 °C, 1 h) in the
presence of Pd(acac)2—PPh3—Et3Al (1 : 2 : 4, 20 mol.%)
resulted in 6,6ꢀclosed cycloadducts 7—10 in the yields of
30—60% (Scheme 3). The Nꢀheterocyclic diazoketones
gave the highest yields of the target products (~60%).
The structures of the resulting compounds 7—10 were
confirmed by the NMR, IR, and UV spectroscopy and the
high resolution mass spectrometry.
In accordance with the 1H NMR spectral data,
5,6ꢀopen adduct 3 was the main component in the mixꢀ
ture of compounds 1—3 (signal ratio 1 : 1 : 3). The singlet
signal for the proton at the bridging C atom of compound
3 is shifted to the higher filed (δH 4.53) than those of
stereoisomer 2 (δH 8.14) and methanofullerene 1 (δH 5.65).
1
The H and 13C NMR spectral data of compounds 1—3
are consistent with the data documented.14
On the next step of our research, we extended the deꢀ
veloped conditions (80 °C, 1 h, oꢀdichlorobenzene, a threeꢀ
component catalytic system Pd(acac)2—PPh3—Et3Al
(1 : 2 : 4, 20 mol.%)) on the reactions of 2ꢀoxoꢀ2ꢀcycloꢀ
propylꢀ, 2ꢀoxoꢀ2ꢀcyclobutylꢀ, and 2ꢀoxoꢀ2ꢀcyclopentylꢀ
diazoethanes with [60]fullerene. The corresponding
methanofullerenes 4—6 were obtained in ~45% total yield
(Scheme 2). No effects of the size of the carbocycle proxiꢀ
mal to the carbonyl C atom in the starting diazo comꢀ
pound on the direction of the reaction and the yields of
cycloadducts were found.
Selective formation of methanofullerenes 4—6 in the
reactions of [60]fullerene with the corresponding diazokeꢀ
tones was confirmed by the 1H NMR spectra and HMBC
experiments. Thus, the protons at the bridging C atom
exhibited the singlet signals in the range of δ 5; in the
HMBC experiments, these signals gave cross peaks with
the sp3ꢀhybridized C atoms of the fullerene core in the
range of δ 72. The UV spectra of the individual compounds
4—6 exhibited narrow absorption band of moderate inꢀ
tensity in the range of 430 nm, which is fairly simple
and reliable demonstration of the formation of 6,6ꢀclosed
adducts. The mass spectra (MALDI—TOF) of methanoꢀ
Thus, the structure of cycloadduct 7 was confirmed by
the 1D and 2D NMR spectroscopy. The threeꢀspin sysꢀ
tem of the furan ring exhibited the doublet signal at δH 7.63
(3J = 3.5 Hz), the doubletꢀofꢀdoublet signal at δH 6.81 (3J
3
= 3.5 Hz, J = 1.7 Hz), and the triplet signal at δH 7.86
with the line halfꢀwidth measured at halfꢀheight (Δw1/2
)
equal to 4.3 Hz. In the shiftꢀcorrelated HSQC spectra,
these signals exhibited the crossꢀpeaks with the C atoms at
δC 118.43, 113.46, and 147.10, respectively. In the HMBC
experiment, the crossꢀpeaks of the proton at the bridging
C atom (δH 5.65) with the quaternary C atom of the furan ring
(δC 148.65) and the sp3ꢀhybridized C atoms of the fullerene
core (δC 72.09) were observed, which confirmed the formaꢀ
tion of 6,6ꢀclosed adduct. In the 13C NMR spectra, low
intensity signal for the carbonyl group appeared at δC 190.10.
It was found that under developed conditions (80 °C,
1 h, Pd(acac)2 : PPh3 : Et3Al (1 : 2 : 4, 20 mol.%)), 2ꢀoxoꢀ
2ꢀ(adamantanꢀ1ꢀyl)diazoethane reacted very selectively
with [60]fullerene giving monoadduct 11 in ~40% yield
(Scheme 4). In these experiments, no formation of the
regioisomeric bisꢀadducts were observed.

Cycloaddition of diazoketones to [60]fullerene
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
613
Scheme 3
Experimantal
Commercially available [60]fullerene (99.5% pure, G. A.
Razuvaev Institute of Organometallic Chemistry, Russian Acadꢀ
emy of Sciences, Nizhniy Novgorod) was used. The reaction
products were analyzed using an HPLC chromatograph Altex
(model 330) (USA) equipped with an UV detector (340 nm).
The mixtures were separated on a metal halfꢀpreparative colꢀ
umn Cosmosil Buckyprep Waters (250×10 mm) at ~20 °C. Toluꢀ
ene was used as the eluent, the flow rate was 2.0 mL min–1. The
IR spectra were registered on a Specord 75 IR (Carl Zeiss Jena)
spectrophotometer in KBr pellets. The UV spectra were recordꢀ
ed on Specord Mꢀ40 and Specord Mꢀ80 instruments in CHCl3.
The 1H and 13C NMR spectra were run on a Bruker Avanceꢀ400
spectrometer at 400.13 and 100.62 MHz, respectively. The mixꢀ
ture of CDCl3 and CS2 (1 : 5) was used as a solvent. The negaꢀ
tiveꢀion mass spectra were obtained on a MALDI TOF/TOF
AutoflexꢀIII Bruker mass spectrometer without a matrix operatꢀ
ing in a linear mode. Samples were dissolved in toluene prior to
application on a metal target.
Cycloaddition of diazoketones to [60]fullerene (general proꢀ
cedure). A solutions of Pd(acac)2 (0.00278 mmol) in oꢀdichloꢀ
robenzene (0.4 mL) and PPh3 (0.00556 mmol) in oꢀdichlorobenꢀ
zene (0.4 mL) were mixed in the glas flask, then a solution of
Et3Al (0.01112 mmol) in toluene (0.1 mL) was added with stirꢀ
ring under stream of nitrogen at –5 °C. The color of the solution
changed from light yellow to light brown. A solution of [60]ꢀ
fullerene (0.0139 mmol) in oꢀdichlorobenzene (0.1 mL) was addꢀ
ed to the resulting catalyst at room temperature, the color of the
solution turned dark green. The mixture was heated to 80 °C and
a solution of the corresponding diazoketone (0.0695 mmol) in
CH2Cl2 (0.5 mL) was added dropwise over a period of 5 min.
The reaction mixture was stirred for 1 h at the corresponding
temperature, then cooled to room temperature, treated with
aqueous HCl, and extracted with toluene (7 mL). The organic
layer was passed through short column filled with silica gel. The
products 1—11 and [60]fullerene were separated by preparative
HPLC using toluene as the eluent. The structures of compounds
1—3 were established by comparing the spectral data with those
published previously.14
i. Pd(acac)2—PPh3—Et3Al (1 : 2 : 4)
Scheme 4
3´HꢀCyclopropa[1,9](C60ꢀIh)[5,6]fullerenꢀ3´ꢀyl(cycloproꢀ
pyl)methanone (4). IR, ν/cm–1: 540; 820; 1040; 1110; 1270; 1660.
1
UV (CHCl3), λmax/nm: 260, 327, 424. H NMR, δ: 1.15—1.40
(m, 4 H, 2 CH2,); 2.62—2.71 (m, 1 H, CH); 5.19 (s, 1 H, CH).
13C NMR, δ: 12.99; 22.66; 46.60; 72.42 (sp3); 138.17; 138.35;
140.29; 141.23; 142.08; 142.14; 142.24; 142.57; 142.81; 143.02;
143.12; 143.46; 143.75; 143.99; 144.37; 144.60; 144.70; 144.83;
145.20; 145.23; 145.25; 145.51; 146.31; 148.24, 190.02 (CO).
MS (MALDI—TOF), m/z: [M+], found 802.734, calculated
802.743, C65H6O.
Cyclobutylꢀ3´Hꢀcyclopropa[1,9](C60ꢀIh)[5,6]fullerenꢀ3´ꢀylꢀ
methanone (5). IR, ν/cm–1: 520; 1080; 1120; 1200; 1660. UV
(CHCl3), λmax/nm: 260, 330, 427. 1H NMR, δ: 2.00—2.80
(m, 6 H, CH2); 3.96—4.09 (m, 1 H, CH); 4.94 (s, 1 H, CH).
13C NMR, δ: 18.73; 25.08; 43.86; 47.52; 72.07; 139.70; 140.47;
140.99; 141.23; 142.03; 142.13; 142.31; 142.48; 142.78; 143.03;
143.40; 143.71; 143.78; 144.01; 144.11; 144.39; 144.59; 144.67;
145.06; 145.17; 145.45; 145.51; 145.60; 146.38; 147.99; 154.52;
155.34; 190.06 (CO). MS (MALDI—TOF), m/z: [M+], found
816.734, calculated 816.769, C66H8O.
i. N2CHCOAd, Pd(acac)2—PPh3—Et3Al (1 : 2 : 4), 80 °C, 1 h.
The exclusive formation of 6,6ꢀclosed cycloadduct 11
1
was confirmed based on the H and 13C NMR and 2D
NMR experiments (HHCOSY, HSQC, HMBC) of 11.
In summary, it was shown that cycloaddition of 2ꢀoxoꢀ
2ꢀarylꢀ, 2ꢀoxoꢀ2ꢀcycloalkylꢀ, and 2ꢀoxoꢀ2ꢀheteroarylꢀ
diazoethanes to [60]fullerene in the presence of a threeꢀ
component catalytic system Pd(acac)2—PPh3—Et3Al
readily gives 6,6ꢀclosed cycloadducts in relatively high
yields. No influence of the structure of the substituent at the
carbonyl C atom on the direction of the reaction was found.

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Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
Tuktarov et al.
Cyclopentylꢀ3´Hꢀcyclopropa[1,9](C60ꢀIh)[5,6]fullerenꢀ3´ꢀ
(m, 15 H, CH2 and CH); 5.26 (s, 1 H, CH). 13C NMR, δ: 28.50;
36.85; 38.61; 42.29; 47.45; 72.10 (sp3); 138.09; 140.24; 140.97;
141.22; 142.10; 142.30; 142.77; 142.98; 143.17; 143.39; 143.71;
144.00; 144.34; 144.61; 145.08; 145.18; 145.29; 145.45; 145.97;
146.71; 148.36; 196.30 (CO). MS (MALDI—TOF), m/z: [M+],
found 896.848, calculated 896.897, C72H16O.
ylmethanone (6). IR, ν/cm–1: 530; 1130; 1180; 1200; 1230; 1670.
1
UV (CHCl3), λmax/nm: 261, 327, 425. H NMR, δ: 1.50—2.35
(m, 8 H, CH2); 3.30—3.45 (m, 1 H, CH); 5.06 (s, 1 H, CH).
13C NMR, δ: 26.65; 29.29; 45.29; 47.39; 72.39; 136.39; 138.20;
140.19; 140.51; 140.60; 140.89; 140.98; 141.23; 141.80; 142.04;
142.12; 142.33; 142.50; 142.80; 143.01; 143.22; 143.43; 143.71;
144.05; 144.59; 144.70; 145.07; 145.17; 145.51; 146.17; 146.48;
147.10; 148.29; 190.53 (CO). MS (MALDI—TOF), m/z: [M+],
found 830.812, calculated 830.796, C67H10O.
3´HꢀCyclopropa[1,9](C60ꢀIh)[5,6]fullerenꢀ3´ꢀyl(furanꢀ2ꢀ
yl)methanone (7). IR, ν/cm–1: 520; 780; 1220; 1380; 1460; 1670.
UV (CHCl3), λmax/nm: 260, 333, 430. 1H NMR, δ: 5.65 (s, 1 H,
CH); 6.81 (dd, 1 H, CH, 3J = 3.5 Hz, 3J = 1.7 Hz); 7.63 (d, 1 H,
CH, 3J = 3.5 Hz); 7.86 (t, 1 H, CH, Δw1/2 = 4.3 Hz). 13C NMR,
δ: 42.45; 72.09; 113.46; 118.43; 140.87; 140.97; 141.25; 142.00;
142.20; 142.35; 142.66; 142.83; 143.03; 143.08; 143.34; 143.80;
144.05; 144.44; 144.63; 144.69; 144.95; 145.07; 145.19; 145.22;
145.70; 146.35; 147.10; 148.65; 148.97; 149.51; 152.89;
190.10 (CO). MS (MALDI—TOF), m/z: [M+], found 828.724,
calculated 828.737, C66H4O2.
This work was financially supported by the Council on
Grants of the President of the Russian Federation (Proꢀ
gram for State Support of Leading Scientific Schools,
Grant NShꢀ2349.2008.3) and Federal Agency for Educaꢀ
tion (state contract No. P1218).
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3´HꢀCyclopropa[1,9](C60ꢀIh)[5,6]fullerenꢀ3´ꢀyl(thiophenꢀ
2ꢀyl)methanone (8). IR, ν/cm–1: 540; 750; 1220; 1380; 1480;
1
1660. UV (CHCl3), λmax/nm: 261, 326, 425. H NMR, δ: 5.54
(s, 1 H, CH); 7.39 (t, 1 H, CH, J = 4.4 Hz); 7.90 (d, 1 H, CH,
J = 3.2 Hz); 8.32 (d, 1 H, CH, J = 4.4 Hz). 13C NMR, δ: 44.06;
72.11; 128.83; 132.98; 135.36; 140.27; 141.06; 141.31; 142.13;
142.17; 142.35; 142.50; 142.83; 142.96; 143.04; 143.10; 143.19;
143.22; 143.40; 143.46; 143.75; 144.04; 144.47; 144.69; 144.77;
144.95; 145.10; 145.26; 145.33; 145.53; 146.20; 190.56 (CO).
MS (MALDI—TOF), m/z: [M+], found 844.744, calculated
844.803, C66H4OS.
3´HꢀCyclopropa[1,9](C60ꢀIh)[5,6]fullerenꢀ3´ꢀyl(pyridinꢀ2ꢀ
yl)methanone (9). IR, ν/cm–1: 580; 800; 1250; 1470; 1670. UV
1
(CHCl3), λmax/nm: 260, 330, 427. H NMR, δ: 6.62 (s, 1 H,
CH); 7.68 (t, 1 H, CH, J = 7.2 Hz); 8.06 (t, 1 H, CH, J = 7.2 Hz);
8.34 (d, 1 H, CH, J = 7.6 Hz); 8.95 (d, 1 H, CH, J = 7.6 Hz).
13C NMR, δ: 41.45; 73.25; 122.64; 127.86; 137.21; 140.89;
140.96; 141.24; 141.99; 142.19; 142.35; 142.65; 142.85; 143.03;
143.07; 143.38; 143.79; 144.05; 144.41; 144.63; 144.69; 144.95;
145.05; 145.19; 145.26; 145.69; 146.30; 148.97; 149.51; 152.89;
192.02 (CO). MS (MALDI—TOF), m/z: [M+], found 839.724,
calculated 839.763, C67H5NO.
3´HꢀCyclopropa[1,9](C60ꢀIh)[5,6]fullerenꢀ3´ꢀyl(2ꢀphenylꢀ
quinolinꢀ4ꢀyl)methanone (10). IR, ν/cm–1: 520; 1180; 1210; 1430;
1
1630. UV (CHCl3), λmax/nm: 260, 329, 425. H NMR, δ: 5.67
(s, 1 H, CH); 7.45 (t, 1 H, CH, Ph, J = 7.2 Hz); 7.58 (t, 2 H, CH,
Ph, J = 7.2 Hz); 7.87 (t, 1 H, CH, C9H5N, J = 7.2 Hz); 8.32
(d, 2 H, CH, Ph, J = 7.2 Hz); 8.30—8.38 (m, 2 H, CH, C9H5N);
8.75 (s, 1 H, CH, C9H5N); 8.80 (d, 1 H, CH, C9H5N, J = 7.2 Hz).
13C NMR, δ: 45.74; 72.44; 118.47; 125.38; 128.70; 129.21;
130.17; 130.58; 132.08; 132.18; 136.79; 138.55; 140.60; 141.14;
141.38; 142.05; 142.13; 142.31; 142.45; 142.85; 143.06; 143.23;
143.42; 143.75; 144.03; 144.28; 144.57; 144.75; 145.11; 145.28;
145.34; 145.40; 145.61; 146.24; 146.38; 146.65; 147.60; 149.66;
156.72; 196.55 (CO). MS (MALDI—TOF), m/z: [M+], found
965.858, calculated 965.917, C77H11NO.
18. A. R. Tuktarov, A. R. Akhmetov, D. Sh. Sabirov, L. M.
Khalilov, A. G. Ibragimov, U. M. Dzhemilev, Izv. Akad.
Nauk, Ser. Khim., 2009, 1671 [Russ. Chem. Bull., Int. Ed.,
2009, 58, 1724].
(Adamantanꢀ1ꢀyl)ꢀ3´Hꢀcyclopropa[1,9](C60ꢀIh)[5,6]fulleꢀ
renꢀ3´ꢀylmethanone (11). IR, ν/cm–1: 520; 800; 1250; 1430; 1670.
1
UV (CHCl3), λmax/nm: 260, 320, 427. H NMR, δ: 1.40—2.00
Received September 17, 2009