Reactions of [60]fullerene with halides and amino acids to synthesize fulleropyrrolidines

Article abstract of DOI:10.1002/ejoc.201402655

The reactions of [60]fullerene with benzyl chlorides and amino acids in chlorobenzene (PhCl) were investigated. Fulleropyrrolidines bearing ArCH moieties originating from the corresponding benzyl chlorides through C-Cl bond cleavage were obtained from these reactions. Use of PhCl/DMSO instead of PhCl as the solvent significantly improved the reaction efficiency. A detailed investigation of these reactions resulted in the discovery of other halides - such as allyl chloride, methallyl chloride, cinnamyl chloride, propargyl bromide, ethyl bromoacetate, bromoacetonitrile, bromomethane, bromopropane and bromobutane - that could also react with [60]fullerene and amino acids to produce fulleropyrrolidines. This reaction could be an alternative to the Prato reaction for synthesizing fulleropyrrolidines when aldehydes are expensive or unavailable from commercial sources. A plausible reaction mechanism for product formation involving C-X bond cleavage in the halide to form the aldehyde is proposed.

Full text of DOI:10.1002/ejoc.201402655

FULL PAPER
DOI: 10.1002/ejoc.201402655
Reactions of [60]Fullerene with Halides and Amino Acids to Synthesize
Fulleropyrrolidines
Bo Jin,*[a,b] Juan Shen,[b] Rufang Peng,*[a,b] Congdi Chen,[b] and Shijin Chu[a]
Keywords: Fullerenes / Cycloaddition / Amino acids / Halides
The reactions of [60]fullerene with benzyl chlorides and
amino acids in chlorobenzene (PhCl) were investigated. Full-
eropyrrolidines bearing ArCH moieties originating from the
corresponding benzyl chlorides through C–Cl bond cleavage
were obtained from these reactions. Use of PhCl/DMSO
instead of PhCl as the solvent significantly improved the re-
action efficiency. A detailed investigation of these reactions
resulted in the discovery of other halides – such as allyl chlor-
ide, methallyl chloride, cinnamyl chloride, propargyl brom-
ide, ethyl bromoacetate, bromoacetonitrile, bromomethane,
bromopropane and bromobutane – that could also react with
[60]fullerene and amino acids to produce fulleropyrrolidines.
This reaction could be an alternative to the Prato reaction for
synthesizing fulleropyrrolidines when aldehydes are expens-
ive or unavailable from commercial sources. A plausible re-
action mechanism for product formation involving C–X bond
cleavage in the halide to form the aldehyde is proposed.
fulleropyrrolidine derivatives can be successfully generated
by the irradiation of tertiary amines and [60]fullerene.[8] In
1996, Gan’s group[9] explored direct reactions between α-
amino acid esters and [60]fullerene induced by photoirradi-
ation or in the presence of iodo reagents under ultrason-
ification conditions to provide fulleropyrrolidines. Sub-
sequently, direct reactions between [60]fullerene and N-sub-
stituted glycines under high-speed vibration milling condi-
tions to synthesize fulleropyrrolidines were also reported.[10]
Recently, our group and Wang’s group have reported direct
thermal reactions, affording fulleropyrrolidine derivatives,
between [60]fullerene and a series of α-amino acids and
amino acid esters in the absence of aldehyde.[11] In addition,
Wang and co-workers reported thermal reactions between
[60]fullerene and α-amino acid ester hydrochlorides in the
presence of triethylamine in o-dichlorobenzene at reflux,
obtaining fulleropyrrolidine derivatives.[12]
Introduction
Fullerenes were first discovered by Kroto, Smalley, and
Curl in 1985. Since then, fullerenes, particularly [60]fuller-
ene, have received considerable attention because of their
interesting spherical structures and unique physical and
chemical properties. The functionalization of [60]fullerene
with various functional groups provides a variety of poten-
tial molecular materials for biological, optical, and elec-
tronic devices.[1] Numerous methods for the chemical modi-
fication of [60]fullerene have been developed during the last
few decades; they include various cycloadditions, nucleo-
philic additions, radical additions, hydrogenations, and
halogenations.[2]
Among a large number of functionalized [60]fullerene
compounds, fulleropyrrolidine derivatives are one of the
most intensively studied classes.[3] Pioneering work on
fulleropyrrolidine derivatives based on cycloaddition of
[60]fullerene, sarcosine, and formaldehyde was conducted
by Prato’s group.[4] Then, reactions between azomethine
ylides and [60]fullerene to prepare fulleropyrrolidine deriva-
tives were extensively studied.[5–7] Later it was found that
In previous work we synthesized some polynitro fullero-
pyrrolidine derivatives[13] and unexpectedly discovered reac-
tions between [60]fullerene, α-amino acids, and quaternary
ammonium salts.[14] We suspected that the reaction mecha-
nism initially involved C–N heterolytic bond cleavage. As
such, we assumed that other molecules containing polar C–
[a] State Key Laboratory Cultivation Base for Nonmetal
Composites and Functional Materials, Southwest University of X bonds might also react with [60]fullerene to form similar
Science and Technology,
products. As is well known, the carbon–halogen bond is a
59 Qinglong Road, Mianyang, Sichuan 621010, P. R. China
polar bond and is prone to heterolytic cleavage. To substan-
tiate our assumption, reactions of [60]fullerene, α-amino
acids, and alkyl halides, such as benzyl chlorides, allyl
chloride, and methallyl chloride, were investigated. The re-
sults showed that [60]fullerene can also react with α-amino
acids and alkyl halides to provide fulleropyrrolidine deriva-
tives containing RCH moieties originating from the alkyl
E-mail: jinbo0428@163.com
rfpeng2006@163.com
http://www.swust.edu.cn/
[b] Department of Chemistry, School of Materials Science and
Engineering, Southwest University of Science and Technology,
Mianyang 621010, China
59 Qinglong Road, Mianyang, Sichuan 621010, P. R. China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201402655.
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Eur. J. Org. Chem. 2014, 6252–6262

Fulleropyrrolidines from [60]Fullerene, Halides, and Amino Acids
halides through C–X bond cleavage. A reaction mechanism originating from the corresponding benzyl chloride 3a–3e.
involving C–X bond cleavage in the alkyl halide to form the Among them, product 4a was a known compound, and its
corresponding aldehyde is also proposed.
structure was substantiated by comparison of spectroscopic
data with those reported previously.[15] Compounds 4b–4e
exhibited correct molecular weights in their mass spectra
and the expected chemical shifts, as well as splitting pat-
terns, for all protons in their 1H NMR spectra. The 1H
NMR spectra of compounds 4b–4e each show a singlet at
δ = 2.76 to 2.82 ppm, two doublets at δ = 4.27 to 4.99 ppm,
and a singlet at δ = 4.89 to 5.30 ppm, attributable to the
pyrrolidine N-substituted methyl protons (N-CH3), non-
equivalent methylene protons, and methine protons, respec-
tively.
Results and Discussion
We first explored the reactions of [60]fullerene, benzyl
chloride, and α-amino acids. When [60]fullerene, benzyl
chloride, and α-amino acids 1a–1c were added to chloro-
benzene (PhCl) and the mixtures were heated to 120 °C for
a given time, the corresponding adducts 2a–2c were pre-
pared, with yields of 22% to 33% (Scheme 1). Products 2a
and 2b were known compounds, and their structures were
confirmed by comparison of their spectroscopic data with
those reported in the literature.[15] The structure of product
1
2c was confirmed by its MS, H NMR, 13C NMR, FTIR,
1
and UV/Vis spectrometric and spectroscopic data. The H
NMR spectrum of 2c exhibits signals at δ = 7.79 (br. s, 2
H), 7.40 (t, J = 7.2 Hz, 2 H), and 7.32 ppm (t, J = 7.2 Hz,
1 H) for the phenyl group, two doublets at δ = 5.13 and
4.18 ppm with JAB = 9.2 Hz for the two nonequivalent
methylene protons in the pyrrolidine ring (PhCH), two mul-
tiplets at δ = 3.37 and 2.64 ppm and a triplet at δ =
1.55 ppm (J = 7.2 Hz) for the N-substituted ethyl group,
and a singlet at δ = 5.08 ppm for the methine proton in the
PhCH. The 13C NMR spectrum of 2c reveals 53 peaks in
the 135–157 ppm range and three peaks at 129.46, 128.82,
and 128.56 ppm for the 58 sp2 carbons of the [60]fullerene
cage and the six sp2 carbons of the benzene ring. The other
two (sp3) carbons of the [60]fullerene skeleton appeared at
δ = 76.78 and 68.82 ppm, consistently with its C1 molecular
symmetry.
Scheme 2. Synthesis of adducts 4a–4e through reactions of [60]ful-
lerene, substituted benzyl chlorides 3a–3e, and sarcosine in PhCl.
We suspected that the reaction mechanism would initially
involve C–Cl heterolytic bond cleavage of the benzyl chlor-
ide to afford a benzyl carbonium ion, and that the benzyl
carbonium ion would then react with α-amino acids to form
azomethine ylides, which would in turn react with [60]fuller-
ene to produce the corresponding adducts 2a–2c. Of these
steps, the C–Cl heterolytic bond cleavage of the benzyl
chloride to afford the benzyl carbonium ion should be rate-
determining. Dimethyl sulfoxide (DMSO) is well known to
sustain carbon–halogen heterolytic bond cleavage.[16] As
such, a PhCl/DMSO mixed solvent system was used to de-
termine whether the reaction would become more efficient
than in PhCl alone. As shown in Table 1, the reaction tem-
peratures required for [60]fullerene, benzyl chlorides 3a–3e,
and amino acids 1a–1c were reduced from 120 °C to 70–
90 °C, and the corresponding yields of products 2a–2c and
4a–4e were increased from 22% to 39% and from 25% to
45%, respectively, in PhCl/DMSO.
Scheme 1. Synthesis of adducts 2a–2c through reactions of [60]ful-
lerene, benzyl chloride, and amino acids 1a–1c in PhCl.
Adducts 2a–2c each possessed a common PhCH moiety,
We examined the generality of this type of reaction for
which presumably originated from the benzyl chloride. To other active alkyl halides, allyl chloride, methallyl chloride,
substantiate this assumption, the different substituted cinnamyl chloride, propargyl bromide, ethyl bromoacetate,
benzyl chlorides 3a–3e were used in corresponding reac- and bromoacetonitrile in place of benzyl chlorides. The re-
tions to determine whether products in which the PhCH actions of [60]fullerene, allyl chloride, and N-substituted α-
group had been replaced by the corresponding ArCH moi- amino acids 1b–1d are shown in Scheme 3. When [60]fuller-
ety could be obtained. When [60]fullerene, substituted ene, allyl chloride, and α-amino acids 1b–1d were placed in
benzyl chlorides 3a–3e, and sarcosine were added to PhCl the PhCl/DMSO mixed solvent and the mixtures were
and the mixtures were heated to 120 °C for a given time, heated to 80 °C for a given time, the corresponding adducts
the corresponding adducts 4a–4e were prepared, with yields 5b–5d were prepared, with yields of 36–42%. Adducts 5b–
of 22% to 39% (Scheme 2). Adducts 4a–4e were identified 5d were identified as fulleropyrrolidines and each possessed
as fulleropyrrolidines and each possessed an ArCH moiety a CH2=CHCH moiety originating from allyl chloride.
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B. Jin, J. Shen, R. Peng, C. Chen, S. Chu
Table 1. Reaction conditions and product yields for the reactions of [60]fullerene, benzyl chlorides, and amino acids.
FULL PAPER
Entry
Substrates
Product Solvent[a]
Temp. [°C]
Time [h]
Yield[b] [%]
Benzyl chloride
C6H5CH2Cl
Amino acid
NH2CH2COOH
1
2
3
4
5
6
7
8
2a
2b
PhCl
PhCl/DMSO (2:1)
PhCl
PhCl/DMSO (2:1)
PhCl
PhCl/DMSO (2:1)
PhCl
PhCl/DMSO (2:1)
PhCl
PhCl/DMSO (2:1)
PhCl
PhCl/DMSO (2:1)
PhCl
PhCl/DMSO (2:1)
PhCl
130
80
120
90
120
70
120
90
120
70
120
80
120
80
120
80
24
24
24
24
24
24
24
14
24
16
20
24
20
24
20
24
22 (79)
35 (84)
32 (75)
33 (85)
33 (68)
42 (80)
22 (74)
25 (86)
24 (70)
27 (81)
39 (74)
45 (80)
36 (69)
43 (78)
35 (65)
40 (78)
C6H5CH2Cl
C6H5CH2Cl
CH3NHCH2COOH
CH3CH2NHCH2COOH 2c
p-NO2C6H4CH2Cl CH3NHCH2COOH
4a
4b
4c
4d
4e
p-ClC6H4CH2Cl
p-CH3C6H4CH2Cl
o-CH3C6H4CH2Cl
CH3NHCH2COOH
CH3NHCH2COOH
CH3NHCH2COOH
m-CH3C6H4CH2Cl CH3NHCH2COOH
PhCl/DMSO (2:1)
[a] Values in parentheses are the volume ratio of PhCl and DMSO. [b] Isolated yields; values in parentheses are based on consumed
[60]fullerene.
Scheme 3. Synthesis of adducts 5b–5d through reactions of [60]ful-
lerene, allyl chloride, and N-substituted α-amino acids 1b–1d in
PhCl/DMSO.
Scheme 5. Synthesis of the cis isomers 5e and 5g through the reac-
tion of [60]fullerene, allyl chloride, and alanine (1e) in PhCl/
During the reactions of [60]fullerene, allyl chloride, and
N-unsubstituted α-amino acids 1a and 1e, we observed that
both N-unsubstituted fulleropyrrolidines and the corre-
sponding N-allyl-substituted fulleropyrrolidines were ob-
tained. A mixture of [60]fullerene, allyl chloride, and glycine
was dissolved in 30 mL of PhCl/DMSO mixed solvent and
heated to 80 °C for 15 h. The N-unsubstituted product 5a
and the N-substituted product 5f were obtained, with yields
of 18% and 29%, respectively (Scheme 4). When [60]fuller-
ene, allyl chloride, and alanine were added to PhCl/DMSO
and heated to 80 °C for 17 h, the cis isomers 5e and 5g
were obtained, with yields of 21% and 12%, respectively
(Scheme 5).
DMSO.
The structures of products 5a–5g were unambiguously
1
confirmed by their MS, H NMR, 13C NMR, FTIR, and
UV/Vis spectrometric and spectroscopic data. The 1H
NMR spectra of compounds 5a–5e each show a multiplet
at δ = 6.31 to 6.61 ppm, a doublet at δ = 5.75 to 5.84 ppm
with JAB = 17.0 to 17.2 Hz, and a doublet at δ = 5.56 to
5.69 ppm with JAB = 10.0 to 10.4 Hz for the vinyl group.
Product 5f exhibits two multiplets at δ = 6.25 to 6.33 ppm
and 6.33 to 6.43 ppm and four double doublets at δ = 5.77
(JAB = 17.2 and 1.2 Hz), 5.63 (JAB = 10.0 and 1.6 Hz), 5.57
(JAB = 17.2 and 1.2 Hz), and 5.41 ppm (JAB = 10.0 and
1.6 Hz) for the two vinyl groups. The six vinyl protons of
product 5g appeared at δ = 6.20 to 6.40 ppm (m, 2 H),
5.78 ppm (dd, J = 1.2 and 17.2 Hz, 1 H), 5.62 ppm (dd, J
= 1.6 and 10.0 Hz, 1 H), 5.56 ppm (dd, J = 1.6 and 17.2 Hz,
1 H), and 5.49 ppm (dd, J = 0.8 and 10.4 Hz, 1 H). The two
pyrrolidine ring methine protons of product 5g appeared at
δ = 4.79 (d, J = 9.2 Hz, 1 H) and 4.37 ppm (q, J = 6.4 Hz,
1 H), and the two N-substituted methylene protons
(NCH2CH=CH2) and the three 2-substituted methyl pro-
tons (CHCH3) appeared at δ = 3.96 (dd, J = 6.8 and
15.2 Hz, 1 H), 3.88 (dd, J = 6.8 and 15.2 Hz, 1 H), and
2.02 ppm (d, J = 6.4 Hz, 3 H), respectively. The stereochem-
Scheme 4. Synthesis of the N-unsubstituted fulleropyrrolidine 5a
and the N-allyl fulleropyrrolidine 5f through the reaction of
[60]fullerene, allyl chloride, and glycine (1a) in PhCl/DMSO.
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Fulleropyrrolidines from [60]Fullerene, Halides, and Amino Acids
Figure 1. (a) NOESY spectrum of product 5e and partial NOEs involving the hydrogens in 5e. (b) NOESY spectrum of product 5g and
partial NOEs involving the hydrogens in 5g.
istry of products 5e and 5g was also revealed by 1H nuclear new compounds 8a, 8b, and 8d were unambiguously char-
1
Overhauser effect spectroscopy (NOESY). The NOESY acterized by their MS, H NMR, 13C NMR, FTIR, and
spectra of products 5e and 5g are shown in Figure 1, and UV/Vis spectrometric and spectroscopic data. The 1H
the nuclear Overhauser effects (NOEs) involving the NMR spectra of compounds 8a, 8b, and 8d each show a
hydrogens are indicated by the curved arrows. As shown in singlet at δ = 2.92 to 3.14 ppm for the N-CH3 group. Prod-
Figure 1, products 5e and 5g each show correlation between uct 8a exhibits a doublet at δ = 7.44 ppm (d, J = 7.8 Hz, 2
H1 and H2 and no correlation between H1 and methyl H. H), two multiplets at δ = 7.29 to 7.34 ppm (m, 2 H) and
Evidently, the NOESY spectra indicate that products 5g 7.20 to 7.28 ppm (m, 1 H), a doublet at δ = 7.06 ppm (d, J
and 5e are cis isomers.
= 15.6 Hz, 1 H), and a double doublet at δ = 6.68 ppm
1
The reactions of [60]fullerene, methallyl chloride, and N- (dd, J = 9.0 and 15.6 Hz, 1 H) in its H NMR spectrum,
substituted α-amino acids 1b–1d are shown in Scheme 6. corresponding to the styryl group. Product 8b exhibits a
1
When [60]fullerene, methallyl chloride, and α-amino acids singlet at δ = 2.86 ppm (s, 1 H) in its H NMR spectrum,
1b–1d were placed in the PhCl/DMSO mixed solvent and corresponding to the ethynyl group. In the 13C NMR spec-
the mixtures were heated to 80 °C for a given time, the cor- trum of compound 8d, the peak for the –CN carbon ap-
responding adducts 6b–6d were prepared, with yields of pears at δ = 114.75 ppm, whereas the peaks for the two
24% to 30%. Structural characterization showed that ad- ethynyl carbons of compound 8b appear at δ = 74.20 and
ducts 6b–6d were fulleropyrrolidines and each possessed a 68.99 ppm.
CH2=C(CH3)CH moiety originating from methallyl chlor-
ide.
Scheme 7. Synthesis of adducts 8a–8d through the reactions of
[60]fullerene, active halides 7a–7d, and sarcosine in PhCl/DMSO.
Scheme 6. Synthesis of adducts 6b–6d through reactions of [60]ful-
lerene, methallyl chloride, and α-amino acids 1b–1d in PhCl/
To expand the scope of the use of this method, alkyl
DMSO.
halides such as bromoethane (9a), n-bromopropane (9b),
The reactions of [60]fullerene, active halides 7a–7d, and and n-bromobutane (9c) were also employed in the reaction
sarcosine are shown in Scheme 7. When [60]fullerene, sarco- to determine whether the corresponding fulleropyrrolidines
sine, and active halides 7a–7d were placed in PhCl/DMSO would be obtained. As desired, treatment of [60]fullerene
and the mixtures were heated to 80 °C to 90 °C for a given with alkyl bromides 9a–9c and α-amino acids 1b–1d pro-
time, the corresponding adducts 8a–8d were prepared, with vided adducts 10a–10e, with yields of 22% to 38%
yields of 22% to 35%. Product 8c was a known compound, (Scheme 8). The spectroscopic data for adducts 10a–10e
and its identity was confirmed by comparison of its spectro- were in agreement with the depicted structures. The spectro-
scopic data with those reported in the literature.[11b] The scopic data for adducts 10a and 10e were fully consistent
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B. Jin, J. Shen, R. Peng, C. Chen, S. Chu
FULL PAPER
Scheme 8. Synthesis of adducts 10a–10e through the reactions of [60]fullerene, alkyl halides 9a–9c, and α-amino acids 1b–1d in PhCl/
DMSO.
Scheme 9. Proposed reaction mechanism for the formation of fulleropyrrolidine derivatives.
1
with those reported previously.[14] The H NMR spectra of the corresponding aldehyde is expensive or unavailable from
adducts 10b–10d each show two multiplets at δ = 2.45 to commercial sources. In addition, a possible mechanism in-
2.97 ppm and a triplet at δ = 1.45 to 1.51 ppm for the volving the formation of the aldehyde through halide C–X
–CH2CH3 group originating from n-bromopropane.
bond cleavage has been proposed.
A mechanistic explanation for these reactions is shown
in Scheme 9. An aldehyde can be generated from the corre-
sponding primary halide through the action of DMSO as
oxidation reagent and base as catalyst.[16,17] Hence, we can
Experimental Section
General Methods: NMR spectra were recorded with a Bruker
conclude that alkoxysulfonium ions 11 are obtained in the AC 300/400/600 spectrometer with CS2/CDCl3 as the solvent. At-
mospheric pressure chemical ionization mass spectra were taken
with a Varian 1200LC/MS mass spectrometer. HRMS was per-
formed with an IonSpec 4.7T MALD-FTMS mass spectrometer.
Infrared spectra were measured with a Nicolet 380 FTIR spectrom-
eter (KBr pellet) with a resolution of 4 cm–1, in the range from
4000 cm–1 to 400 cm–1. UV/Vis spectra were recorded with a UN-
ICON UV-2102 PCS spectrometer with CHCl3 as the solvent.
Chromatographic purifications were conducted with 300 to
400 mesh silica gel. [60]Fullerene was prepared by the arc discharge
method. All other commercially available reagents were analytical
first step through attack by the nucleophilic oxyanion of
DMSO at the alkyl halide and subsequent displacement of
halide. After that, alkoxysulfonium ions 11 undergo depro-
tonation at the methyl group in the presence of α-amino
acids to form ylides 12, which then eliminate dimethyl sulf-
ide to form the corresponding aldehydes 13. Next, alde-
hydes 13, through condensation with α-amino acids and eli-
mination of H2O and CO2, produce azomethine ylides 14,
which react with [60]fullerene to afford the corresponding
fulleropyrrolidines 2a–2c, 4a–4e, 5b–5f, 6b–6d, 8a–8d, and grade.
10a–10e.
Synthesis of 2-Phenylfulleropyrrolidine (2a) in PhCl: A mixture of
[60]fullerene (36.0 mg, 0.05 mmol), glycine (1a, 22.7 mg, 0.3 mmol),
and benzyl chloride (381.0 mg, 3.0 mmol) was heated to 120 °C for
24 h in chlorobenzene (30 mL). After removal of the solvent in
vacuo, flash chromatography of the residue was performed on a
silica gel column. Carbon disulfide first eluted unreacted [60]fuller-
ene (26.0 mg, 72%). Toluene then eluted 2a[15] (9.2 mg, 22% yield,
Conclusions
In summary, we have demonstrated a new and straight-
forward approach for the preparation of fulleropyrrolidine
derivatives through one-pot, three-component reactions of
[60]fullerene, halides, and α-amino acids. In these reactions,
various halides, including active halides and alkyl halides,
were used to obtain the corresponding fulleropyrrolidines.
This approach might be an alternative route, instead of the
1
79% based on consumed [60]fullerene). H NMR (300 MHz, CS2/
CDCl3): δ = 7.79 (d, J = 7.2 Hz, 2 H), 7.50–7.39 (m, 2 H), 7.37–
7.30 (m, 1 H), 5.79 (s, 1 H), 5.12 (d, J = 10.3 Hz, 1 H), 4.90 (d, J
= 10.3 Hz, 1 H) ppm.
Synthesis of N-Methyl-2-phenylfulleropyrrolidine (2b) in PhCl:
Prato reaction, for the synthesis of fulleropyrrolidines when Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with sarcosine (1b,
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Fulleropyrrolidines from [60]Fullerene, Halides, and Amino Acids
26.7 mg, 0.30 mmol) and benzyl chloride (381.0 mg, 3.0 mmol) at
120 °C for 24 h by the same procedure as above gave unreacted
[60]fullerene (20.7 mg, 58%) and 2b[15] (13.6 mg, 32% yield, 75%
based on consumed [60]fullerene). 1H NMR (600 MHz, CS2/
Synthesis of N-Methyl-2-(p-methylphenyl)fulleropyrrolidine (4c) in
PhCl: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with sarco-
sine (26.7 mg, 0.30 mmol) and p-methylbenzyl chloride (3c,
423.0 mg, 3.0 mmol) at 120 °C for 20 h by the same procedure as
CDCl3): δ = 7.73 (s, 2 H), 7.36 (t, J = 7.8 Hz, 2 H), 7.27 (t, J = above gave unreacted [60]fullerene (17.0 mg, 47%) and 4c (16.9 mg,
7.2 Hz, 1 H), 4.94 (d, J = 9.0 Hz, 1 H), 4.89 (s, 1 H), 4.23 (d, J =
9.0 Hz, 1 H), 2.78 (s, 3 H) ppm.
39% yield, 74% based on consumed [60]fullerene). 1H NMR
(400 MHz, CS2/CDCl3): δ = 7.67 (d, J = 8.0 Hz, 2 H), 7.22 (d, J =
8.0 Hz, 2 H), 4.98 (d, J = 9.2 Hz, 1 H), 4.91 (s, 1 H), 4.27 (d, J =
9.2 Hz, 1 H), 2.82 (s, 3 H), 2.38 (s, 3 H) ppm. 13C NMR (100 MHz,
CS2/CDCl3): δ = 156.37, 154.02, 153.48, 153.53, 147.34, 147.33,
146.86, 146.53, 146.39, 146.37, 146.31, 146.27, 146.22, 146.18,
146.15, 145.99 (2 C), 145.84, 145.65, 145.57, 145.50, 145.43, 145.35,
145.31, 145.29, 145.26, 145.20, 144.76, 144.70, 144.45 (2 C), 143.21,
143.07, 142.74, 142.66, 142.63 (2 C), 142.35, 142.32, 142.22, 142.20,
142.16, 142.10, 142.07, 142.02, 141.88, 141.75, 141.61, 140.27,
140.22, 139.99, 139.60, 138.15 (2 C), 136.88, 136.67, 135.87, 135.83,
135.96 (2 C), 129.56 (2 C), 129.34 (2 C), 83.56, 70.15, 69.03 (2 C),
Synthesis of N-Ethyl-2-phenylfulleropyrrolidine (2c) in PhCl: Treat-
ment of [60]fullerene (36.0 mg, 0.05 mmol) with N-ethylglycine (1c,
30.9 mg, 0.30 mmol) and benzyl chloride (381.0 mg, 3.0 mmol) at
120 °C for 24 h by the same procedure as above gave unreacted
[60]fullerene (18.7 mg, 52%) and 2c (14.2 mg, 33% yield, 68%
based on consumed [60]fullerene). 1H NMR (400 MHz, CS2/
CDCl3): δ = 7.79 (br. s, 2 H), 7.40 (t, J = 7.2 Hz, 2 H), 7.32 (t, J
= 7.2 Hz, 1 H), 5.13 (d, J = 9.2 Hz, 1 H), 5.08 (s, 1 H), 4.18 (d, J
= 9.2 Hz, 1 H), 3.42–3.32 (m, 1 H), 2.69–2.60 (m, 1 H), 1.55 (t, J
= 7.2 Hz, 3 H) ppm. 13C NMR (100 MHz, CS2/CDCl3): δ = 156.42,
154.22, 153.53, 153.45, 147.35, 147.34, 146.84, 146.52, 146.39,
146.32, 146.27 (2 C), 146.24, 146.19, 146.16, 146.00 (2 C), 145.84,
145.67, 145.60, 145.58, 145.51, 145.47, 145.36, 145.32, 145.29,
145.27, 145.20, 144.79, 144.72, 144.46, 143.23, 143.09, 142.76,
142.68, 142.65 (2 C), 142.35 (2 C), 142.23 (2 C), 142.18, 142.16,
142.11, 142.08, 142.01, 141.90, 141.77, 141.61, 140.32, 140.27,
139.99, 139.55, 137.27 (2 C), 136.94, 136.74, 135.89, 135.81, 129.46,
128.82, 128.56, 82.45, 76.78, 68.82, 66.63, 47.42, 13.76 ppm. FTIR
40.06, 21.54 ppm. FTIR (KBr): ν = 3036, 2944, 2919, 2850, 2777,
˜
1540, 1512, 1461, 1427, 1332, 1262, 1177, 1106, 1030, 821, 800,
770, 600, 571, 526, 479 cm–1. UV/Vis: λmax = 263, 306, 431 nm. MS
(APCI): m/z = 868 [M + 1]+, 720 [C60]+. HRMS (MALDI FT-
ICR): calcd for C70H13N [M]+ 867.1048; found 867.1053.
Synthesis of N-Methyl-2-(o-methylphenyl)fulleropyrrolidine (4d) in
PhCl: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with sarco-
sine (26.7 mg, 0.30 mmol) and o-methylbenzyl chloride (3d,
423.0 mg, 3.0 mmol) at 120 °C for 20 h by the same procedure as
above gave unreacted [60]fullerene (17.3 mg, 48%) and 4d (15.5 mg,
36% yield, 69% based on consumed [60]fullerene). 1H NMR
(400 MHz, CS2/CDCl3): δ = 8.06 (d, J = 8.0 Hz, 1 H), 7.28–7.33
(m, 1 H), 7.20 (d, J = 4.0 Hz, 2 H), 5.30 (s, 1 H), 4.99 (d, J =
9.6 Hz, 1 H), 4.31 (d, J = 9.2 Hz, 1 H), 2.76 (s, 3 H), 2.60 (s, 3
H) ppm. 13C NMR (100 MHz, CS2/CDCl3): δ = 156.50, 154.01,
153.81, 153.70, 147.34 (2 C), 146.62, 146.35, 146.33,146.30, 146.24,
146.20 (2 C), 146.15, 146.00, 145.99, 145.82, 145.65, 145.52, 145.47,
145.42, 145.33, 145.29, 145.23 (2 C), 144.71 (2 C), 144.44, 144.40,
143.20, 143.05, 142.73, 142.68, 142.65, 142.38, 142.31 (2 C), 142.27,
142.16 (2 C), 142.11, 142.09, 141.96, 141.89, 141.73, 141.61, 140.38,
140.24, 139.93, 139.61, 137.19, 136.86, 136.65, 135.88, 135.42,
135.09, 131.06, 129.85, 128.02, 126.81, 78.83, 77.13, 70.00, 69.42,
(KBr): ν = 3057, 3025, 2963, 2922, 2850, 2785, 1603, 1540, 1492,
˜
1451, 1427, 1383, 1335, 1305, 1280, 1261, 1228, 1186, 1120, 1097,
1028, 799, 766, 740, 725, 705, 663, 598, 570, 553, 526, 477 cm–1.
UV/Vis (CHCl3): λmax = 257, 306, 431 nm. MS (APCI): m/z = 868
[M + 1]+, 720 [C60]+. HRMS (MALDI FT-ICR): calcd for
C70H13N [M]+ 867.1048; found 867.1032.
Synthesis of N-Methyl-2-(p-nitrophenyl)fulleropyrrolidine (4a) in
PhCl: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with sarco-
sine (26.7 mg, 0.30 mmol) and p-nitrobenzyl chloride (3a, 516.0 mg,
3.0 mmol) at 120 °C for 24 h by the same procedure as above gave
unreacted [60]fullerene (25.5 mg, 71%) and 4a[15] (9.7 mg, 22%
yield, 74% based on consumed [60]fullerene). 1H NMR (300 MHz,
CS2/CDCl3): δ = 8.31 (d, J = 9.0 Hz, 2 H), 8.07 (d, J = 9.0 Hz, 2
H), 5.10 (s, 1 H), 5.06 (d, J = 9.8 Hz, 1 H), 4.37 (d, J = 9.8 Hz, 1
H), 2.88 (s, 3 H) ppm.
39.94, 20.79 ppm. FTIR (KBr): ν = 3035, 2957, 2921, 2857, 2780,
˜
1535, 1509, 1459, 1429, 1333, 1265, 1181, 1105, 1095, 1035, 740,
572, 526, 477 cm–1. UV/Vis: λmax = 258, 307, 429 nm. MS (APCI):
m/z = 868 [M + 1]+, 720 [C60]+. HRMS (MALDI FT-ICR): calcd
for C70H13N [M]+ 867.1048; found 867.1044.
Synthesis of N-Methyl-2-(p-chlorophenyl)fulleropyrrolidine (4b) in
PhCl: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with sarco-
sine (26.7 mg, 0.30 mmol) and p-chlorobenzyl chloride (3b,
486.0 mg, 3.0 mmol) at 120 °C for 24 h by the same procedure as
Synthesis of N-Methyl-2-(m-methylphenyl)fulleropyrrolidine (4e) in
above gave unreacted [60]fullerene (23.6 mg, 66%) and 4b (10.7 mg, PhCl: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with sarco-
24% yield, 70% based on consumed [60]fullerene). 1H NMR
sine (26.7 mg, 0.30 mmol) and m-methylbenzyl chloride (3e,
(400 MHz, CS2/CDCl3): δ = 7.50 (br. s, 2 H), 7.39 (d, J = 8.4 Hz, 423.0 mg, 3.0 mmol) at 120 °C for 20 h by the same procedure as
2 H), 4.99 (d, J = 9.2 Hz, 1 H), 4.93 (s, 1 H), 4.29 (d, J = 9.6 Hz, above gave unreacted [60]fullerene (16.6 mg, 46%) and 4e (15.2 mg,
1 H), 2.82 (s, 3 H) ppm. 13C NMR (100 MHz, CS2/CDCl3): δ = 35% yield, 65% based on consumed [60]fullerene). 1H NMR
156.04, 153.78, 153.06, 152.76, 147.38 (3 C), 146.55, 146.41 (2 C),
146.36, 146.30, 146.27, 146.23, 146.19, 146.04, 146.03, 146.01,
145.78, 145.69, 145.66, 145.54, 145.48, 145.41 (2 C), 145.37, 145.34,
145.32, 145.26, 144.79, 144.70, 144.48, 144.44, 143.25, 143.12,
142.80, 142.73, 142.69, 142.67, 142.34, 142.31, 142.24, 142.22,
142.17, 142.13, 142.11,142.09 (2 C), 141.78, 141.67, 140.34, 140.32,
140.10, 139.73, 137.03, 136.54, 136.00, 135.76, 135.63 (2 C), 134.74
(2 C), 130.62 (2 C), 129.10 (2 C), 82.95, 70.13, 68.96 (2 C),
(400 MHz, CS2/CDCl3): δ = 7.58 (br. s, 2 H), 7.29 (t, J = 7.6 Hz,
1 H), 7.13 (d, J = 7.2 Hz, 1 H), 4.98 (d, J = 9.2 Hz, 1 H), 4.89 (s,
1 H), 4.27 (d, J = 9.2 Hz, 1 H), 2.82 (s, 3 H), 2.40 (s, 3 H) ppm. 13
C
NMR (100 MHz, CS2/CDCl3): δ = 156.23, 154.10, 153.55, 153.45,
147.33, 146.84, 146.51, 146.37, 146.31, 146.27, 146.26, 146.22,
146.18, 146.14, 145.99 (2 C), 145.82, 145.65, 145.58 (2 C), 145.49,
145.43, 145.34, 145.30, 145.29, 145.24, 145.20, 144.76, 144.70,
144.44 (2 C), 143.21, 143.07, 142.75, 142.65, 142.64 (2 C), 142.34,
40.04 ppm. FTIR (KBr): ν = 3057, 2955, 2923, 2859, 2778, 1537, 142.30, 142.21 (2 C), 142.16, 142.15, 142.10, 142.08, 142.01, 141.89,
˜
1508, 1457, 1428, 1333, 1264, 1181, 1101, 1030, 832, 575, 526,
141.75, 141.61, 140.28, 140.23, 139.98, 139.58, 138.14, 136.88,
477 cm–1. UV/Vis: λmax = 260, 310, 430 nm. MS (APCI): m/z = 136.81, 136.67, 135.88, 135.81, 129.38 (2 C), 128.81, 126.53, 83.73,
888 [M + 1]+, 720 [C60]+. HRMS (MALDI FT-ICR): calcd for
C69H10ClN [M]+ 887.0502; found 887.0498.
77.19, 70.16, 69.05, 40.15, 21.84 ppm. FTIR (KBr): ν = 3037, 2952,
˜
2920, 2856, 2778, 1535, 1508, 1457, 1427, 1328, 1265, 1183, 1110,
Eur. J. Org. Chem. 2014, 6252–6262
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6257

B. Jin, J. Shen, R. Peng, C. Chen, S. Chu
FULL PAPER
1033, 800, 702, 575, 526, 479 cm–1. UV/Vis: λmax = 256, 306,
430 nm. MS (APCI): m/z = 868 [M + 1]+, 720 [C60]+. HRMS
(MALDI FT-ICR): calcd for C70H13N [M]+ 867.1048; found
867.1042.
(3e, 423.0 mg, 3.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 120 °C
for 20 h by the same procedure as above gave unreacted [60]fuller-
ene (17.5 mg, 49%) and 4e (17.4 mg, 40% yield, 78% based on
consumed [60]fullerene).
Synthesis of 2-Vinylfulleropyrrolidine (5a) and N-Allyl-2-vinyl-
fulleropyrrolidine (5f) in PhCl and DMSO: Treatment of [60]fuller-
ene (36.0 mg, 0.05 mmol) with glycine (1a, 22.7 mg, 0.30 mmol)
and allyl chloride (300.0 mg, 4.0 mmol) in PhCl/DMSO (20 mL/
10 mL) at 80 °C for 15 h by the same procedure as above gave unre-
acted [60]fullerene (11.0 mg, 31%), 5f (12.0 mg, 29% yield, 42%
based on consumed [60]fullerene), and 5a (7.1 mg, 18% yield, 26%
based on consumed [60]fullerene).
Synthesis of 2-Phenylfulleropyrrolidine (2a) in PhCl and DMSO: A
mixture of [60]fullerene (36.0 mg, 0.05 mmol), glycine (1a, 22.7 mg,
0.3 mmol), and benzyl chloride (381.0 mg, 3.0 mmol) was heated
to 80 °C for 24 h in chlorobenzene (20 mL) and DMSO (10 mL).
At the end of this time the reaction mixture was poured into water
(150 mL). The chlorobenzene layer was dried with anhydrous
Na2SO4 and concentrated under reduced pressure. The residue was
chromatographed on a silica gel column with carbon disulfide as
eluent to afford unreacted [60]fullerene (20.9 mg, 58%) and with
toluene as eluent to afford product 2a (14.7 mg, 35% yield, 84%
based on consumed [60]fullerene).
Compound 5a: 1H NMR (300 MHz, CS2/CDCl3): δ = 6.61–6.49 (m,
1 H), 5.79 (d, J = 17.0 Hz, 1 H), 5.58 (d, J = 10.3 Hz, 1 H), 5.23
(d, J = 7.1 Hz, 1 H), 4.99 (d, J = 11.5 Hz, 1 H), 4.77 (d, J =
11.5 Hz, 1 H) ppm. 13C NMR (150 MHz, CS2/CDCl3): δ = 155.47,
153.91, 153.59, 152.24, 146.92, 146.91, 146.47, 146.31, 146.13,
146.11, 146.05 (2 C), 145.92, 145.87, 145.79, 145.78, 145.53, 145.29,
145.27, 145.23, 145.21, 145.19, 145.17, 145.16, 145.06 (2 C), 145.02,
144.41, 144.33, 144.18, 144.14, 143.04, 142.90, 142.56, 142.53,
142.47 (3 C), 142.36, 142.23, 142.05 (2 C), 142.02, 141.90, 141.87 (2
C), 141.83, 141.65, 141.56, 140.16, 140.12, 140.02, 139.62, 136.54,
135.71, 135.61, 135.53, 135.11 (2 C), 118.89, 77.99, 76.39, 74.15,
Synthesis of N-Methyl-2-phenylfulleropyrrolidine (2b) in PhCl and
DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with
sarcosine (1b, 26.7 mg, 0.30 mmol) and benzyl chloride (381.0 mg,
3.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C for 24 h by the
same procedure as above gave unreacted [60]fullerene (21.9 mg,
61%) and 2b (14.2 mg, 33% yield, 85% based on consumed [60]-
fullerene).
Synthesis of N-Ethyl-2-phenylfulleropyrrolidine (2c) in PhCl and
DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with N-
ethylglycine (1c, 30.9 mg, 0.30 mmol) and benzyl chloride
(381.0 mg, 3.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 70 °C for
24 h by the same procedure as above gave unreacted [60]fullerene
(17.3 mg, 48%) and 2c (18.1 mg, 42% yield, 80% based on con-
sumed [60]fullerene).
62.56 ppm. FTIR (KBr): ν = 3074, 2917, 2848, 2789, 1637, 1462,
˜
1424, 1335, 1258, 1179, 1120, 989, 926, 804, 768, 703, 600, 575,
557, 526, 476 cm–1. UV/Vis (CHCl3): λmax = 257, 311, 431 nm. MS
(APCI): m/z = 790 [M + 1]+, 720 [C60]+. HRMS (MALDI FT-
ICR): calcd for C64H7N [M]+ 789.0578; found 789.0590.
Compound 5f: 1H NMR (400 MHz, CS2/CDCl3): δ = 6.43–6.33 (m,
1 H), 6.33–6.25 (m, 1 H), 5.77 (dd, J = 1.2, 17.2 Hz, 1 H), 5.63
(dd, J = 1.6, 10.0 Hz, 1 H), 5.57 (dd, J = 1.2, 17.2 Hz, 1 H), 5.41
(d, J = 10.0 Hz, 1 H), 4.90 (d, J = 9.2 Hz, 1 H), 4.50 (d, J = 9.2 Hz,
1 H), 4.09 (dd, J = 1.2, 13.6 Hz, 1 H), 4.04 (d, J = 9.9 Hz, 1 H),
3.27 (dd, J = 8.0, 13.2 Hz, 1 H) ppm. 13C NMR (150 MHz, CS2/
CDCl3): δ = 156.03, 154.27, 153.45, 153.52, 147.34 (2 C), 147.10,
146.86, 146.40, 146.39, 146.36, 146.30, 146.26, 146.21, 146.16,
146.05, 145.91, 145.64, 145.62 (2 C), 145.49, 145.45, 145.38, 145.28,
145.25, 144.81, 144.73, 144.48, 143.23, 143.11, 142.77, 142.74,
142.67, 142.38, 142.29, 142.24, 142.18 (2 C), 142.14, 142.11 (3 C),
142.05, 141.82, 141.74, 140.37, 140.27, 140.21, 139.68, 137.49,
Synthesis of N-Methyl-2-(p-nitrophenyl)fulleropyrrolidine (4a) in
PhCl and DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol)
with sarcosine (26.7 mg, 0.30 mmol) and p-nitrobenzyl chloride
(3a, 516.0 mg, 3.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 90 °C
for 14 h by the same procedure as above gave unreacted [60]fuller-
ene (25.5 mg, 74%) and 4a (11.2 mg, 25% yield, 86% based on
consumed [60]fullerene).
Synthesis of N-Methyl-2-(p-chlorophenyl)fulleropyrrolidine (4b) in
PhCl and DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol)
with sarcosine (26.7 mg, 0.30 mmol) and p-chlorobenzyl chloride
(3b, 486.0 mg, 3.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 70 °C 136.55 (3 C), 136.08, 135.71, 134.77 (3 C), 121.59, 118.47, 80.75,
for 16 h by the same procedure as above gave unreacted [60]fuller-
75.54, 69.09, 66.63, 55.88 ppm. FTIR (KBr): ν˜ = 3098, 3009, 2957,
ene (23.8 mg, 66%) and 4b (12.1 mg, 27% yield, 81% based on 2920, 2851, 1642, 1539, 1458, 1412, 1342, 1261, 1171, 1097, 1030,
consumed [60]fullerene).
922, 802, 726, 568, 526, 473 cm–1. UV/Vis (CHCl3): λmax = 257,
308, 431 nm. MS (APCI): m/z = 830 [M + 1]+, 720 [C60]+. HRMS
(MALDI FT-ICR): calcd for C67H11N [M]+ 829.0891; found
829.0883.
Synthesis of N-Methyl-2-(p-methylphenyl)fulleropyrrolidine (4c) in
PhCl and DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol)
with sarcosine (26.7 mg, 0.30 mmol) and p-methylbenzyl chloride
(3c, 423.0 mg, 3.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C
for 24 h by the same procedure as above gave unreacted [60]fuller-
ene (15.8 mg, 44%) and 4c (19.5 mg, 45% yield, 80% based on
consumed [60]fullerene).
Synthesis of N-Methyl-2-vinylfulleropyrrolidine (5b) in PhCl and
DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with
sarcosine (1b, 26.7 mg, 0.30 mmol) and allyl chloride (300.0 mg,
4.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C for 12 h by the
same procedure as above gave unreacted [60]fullerene (18.6 mg,
52%) and 5b (16.8 mg, 42% yield, 87% based on consumed
[60]fullerene). 1H NMR (400 MHz, CS2/CDCl3): δ = 6.41–6.31 (m,
1 H), 5.77 (dd, J = 1.2, 17.2 Hz, 1 H), 5.62 (dd, J = 1.2, 10.0 Hz,
1 H), 4.85 (d, J = 9.2 Hz, 1 H), 4.31 (d, J = 8.8 Hz, 1 H), 4.12 (d,
J = 9.6 Hz, 1 H), 2.88 (s, 3 H) ppm. 13C NMR (150 MHz, CS2/
CDCl3): δ = 155.86, 154.03, 153.34, 152.54, 147.34, 147.05, 146.82,
146.40, 146.36, 146.29, 146.26, 146.21, 146.16, 146.05, 145.90,
Synthesis of N-Methyl-2-(o-methylphenyl)fulleropyrrolidine (4d) in
PhCl and DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol)
with sarcosine (26.7 mg, 0.30 mmol) and o-methylbenzyl chloride
(3d, 423.0 mg, 3.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C
for 24 h by the same procedure as above gave unreacted [60]fuller-
ene (16.3 mg, 45%) and 4d (18.5 mg, 43% yield, 78% based on
consumed [60]fullerene).
Synthesis of N-Methyl-2-(m-methylphenyl)fulleropyrrolidine (4e) in 145.63, 145.61, 145.57, 145.48, 145.44, 145.38, 145.29, 145.26,
PhCl and DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol)
with sarcosine (26.7 mg, 0.30 mmol) and m-methylbenzyl chloride
144.79, 144.72, 144.48, 144.45, 143.23, 143.11, 142.77, 142.75,
142.67, 142.36, 142.27, 142.24, 142.18, 142.14, 142.12 (2 C), 142.05,
6258
www.eurjoc.org
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2014, 6252–6262

Fulleropyrrolidines from [60]Fullerene, Halides, and Amino Acids
141.83, 141.74, 140.35, 140.27, 140.19, 139.72, 137.38, 136.50 (3 C),
Compound 5e: 1H NMR (300 MHz, CS2/CDCl3): δ = 6.58–6.45 (m,
136.03, 135.72, 121.48, 82.73, 76.00, 69.84, 69.43, 40.08 ppm. FTIR 1 H), 5.77 (d, J = 17.0 Hz, 1 H), 5.56 (d, J = 10.3 Hz, 1 H), 5.26
(KBr): ν = 3079, 2922, 2850, 2775, 1510, 1461, 1422, 1333, 1178, (d, J = 7.4 Hz, 1 H), 4.87 (q, J = 6.5 Hz, 1 H), 2.09 (d, J = 6.5 Hz,
˜
1229, 1178, 1160, 1122, 1036, 988, 929, 881, 803, 767, 739, 598,
3 H) ppm. 13C NMR (75 MHz, CS2/CDCl3): δ = 153.87, 153.43,
574, 554, 526, 478 cm–1. UV/Vis (CHCl3): λmax = 257, 308, 431 nm. 152.64, 152.58, 146.85 (2 C), 146.32 (2 C), 146.12, 146.09, 146.07
MS (APCI): m/z = 804 [M + 1]+, 720 [C60]+. HRMS (MALDI FT-
(2 C), 145.97, 145.96, 145.84, 145.81, 145.69, 145.44, 145.18 (2 C),
145.15 (2 C), 145.13 (2 C), 144.93, 144.35, 144.30, 144.07, 143.00,
142.82, 142.49 (2 C), 142.41 (2 C), 142.31, 142.02 (2 C), 141.98 (2
C), 141.94, 141.83, 141.79, 141.74, 141.54, 141.48, 140.02, 139.97,
139.70. 139.51, 136.52, 136.35, 136.25, 135.60, 135.49, 134.80,
130.46, 128.59, 119.14, 78.74, 75.22, 73.47, 67.82, 17.77 ppm. FTIR
ICR): calcd for C65H9N [M]+ 803.0735; found 803.0742.
Synthesis of N-Ethyl-2-vinylfulleropyrrolidine (5c) in PhCl and
DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with N-
ethylglycine (1c, 30.3 mg, 0.30 mmol) and allyl chloride (300.0 mg,
4.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C for 15.5 h by
the same procedure as above gave unreacted [60]fullerene (18.1 mg,
50%) and 5c (15.2 mg, 37% yield, 75% based on consumed
[60]fullerene). 1H NMR (400 MHz, CS2/CDCl3): δ = 6.41–6.31 (m,
1 H), 5.75 (d, J = 17.2 Hz, 1 H), 5.60 (d, J = 10.0 Hz, 1 H), 4.95
(d, J = 9.2 Hz, 1 H), 4.45 (d, J = 8.8 Hz, 1 H), 4.02 (d, J = 9.2 Hz,
1 H), 3.50–3.41 (m, 1 H), 2.77–2.68 (m, 1 H), 1.55 (t, J = 7.2 Hz,
3 H) ppm. 13C NMR (150 MHz, CS2/CDCl3): δ = 155.82, 154.10,
153.30, 152.35, 147.07, 147.05, 146.89, 146.63, 146.13 (2 C), 146.10,
146.02, 145.99, 145.94, 145.88, 145.77, 145.75, 145.65, 145.37,
145.34 (3 C), 145.21, 145.18, 145.11 (2 C), 145.01, 144.97, 144.54,
144.48, 144.23, 144.18, 142.97, 142.84, 142.50, 142.47, 142.40 (2 C),
142.10, 142.03, 141.98 (2 C), 141.93, 141.87, 141.85 (3 C), 141.79,
141.56, 141.46, 140.09, 140.01, 139.94, 139.41, 137.23, 136.67 (2 C),
136.36, 135.75, 135.46, 120.79, 81.21, 75.33, 68.90, 66.02, 47.25,
(KBr): ν = 3070, 3002, 2965, 2920, 2848, 2800, 1634, 1455, 1424,
˜
1376, 1275, 1184, 1072, 1033, 991, 926, 705, 702, 600, 575, 554,
526, 475 cm–1. UV/Vis (CHCl3): λmax = 258, 306, 431 nm. MS
(APCI): m/z = 804 [M + 1]+, 720 [C60]+. HRMS (MALDI FT-
ICR): calcd for C65H9N [M]+ 803.0735; found 803.0743.
Compound 5g: 1H NMR (400 MHz, CS2/CDCl3): δ = 6.40–6.20 (m,
2 H), 5.78 (dd, J = 1.2, 17.2 Hz, 1 H), 5.62 (dd, J = 1.6, 10.0 Hz,
1 H), 5.56 (dd, J = 1.6, 17.2 Hz, 1 H), 5.49 (dd, J = 0.8, 10.4 Hz,
1 H), 4.79 (d, J = 9.2 Hz, 1 H), 4.37 (q, J = 6.4 Hz, 1 H), 3.96 (dd,
J = 6.8, 15.2 Hz, 1 H), 3.88 (dd, J = 6.8, 15.2 Hz, 1 H), 2.02 (d, J
= 6.4 Hz, 3 H) ppm. 13C NMR (150 MHz, CS2/CDCl3): δ = 154.26,
153.77, 153.40, 153.12, 147.34, 147.32, 147.11, 146.92, 146.77,
146.54, 146.44, 146.42, 146.28, 146.26, 146.19, 146.16, 146.01,
145.84, 145.61, 145.58, 145.49, 145.44, 145.39 (2 C), 145.22, 145.20,
144.81, 144.75, 144.48, 144.44, 143.24, 143.10, 142.77, 142.75,
142.69, 142.67, 142.30, 142.28, 142.23 (2 C), 142.15, 142.13, 142.05,
142.01, 141.77, 141.71, 140.16, 139.85, 139.66, 137.51, 137.34,
136.61 (2 C), 135.93, 135.82, 131.37 (2 C), 121.34, 119.89, 78.42,
13.42 ppm. FTIR (KBr): ν = 3080, 2962, 2923, 2851, 2778, 1655,
˜
1509, 1460, 1422, 1384, 1280, 1181, 1122, 989, 929, 766, 597, 574,
553, 526 cm–1. UV/Vis (CHCl3): λmax = 256, 309, 430 nm. MS
(APCI): m/z = 818 [M + 1]+, 720 [C60]+. HRMS (MALDI FT-
ICR): calcd for C66H11N [M]+ 817.0891; found 817.0887.
74.43, 74.33, 68.60, 50.60, 17.08 ppm. FTIR (KBr): ν = 3075, 2958,
˜
Synthesis of N-Benzyl-2-vinylfulleropyrrolidine (5d) in PhCl and
DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with N-
benzylglycine (1d, 49.5 mg, 0.30 mmol) and allyl chloride
(300.0 mg, 4.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C for
15.5 h by the same procedure as above gave unreacted [60]fullerene
(17.5 mg, 49%) and 5d (15.8 mg, 36% yield, 70% based on con-
sumed [60]fullerene). 1H NMR (400 MHz, CS2/CDCl3): δ = 7.66
(d, J = 7.6 Hz, 2 H), 7.45 (t, J = 7.6 Hz, 2 H), 7.35 (t, J = 7.6 Hz,
2 H), 6.53–6.43 (m, 1 H), 5.84 (d, J = 17.2 Hz, 1 H), 5.69 (d, J =
10.4 Hz, 1 H), 4.71 (d, J = 9.6 Hz, 1 H), 4.67 (d, J = 13.2 Hz, 1
H), 4.60 (d, J = 9.2 Hz, 1 H), 4.02 (d, J = 9.2 Hz, 1 H), 3.75 (d, J =
13.2 Hz, 1 H) ppm. 13C NMR (100 MHz, CS2/CDCl3): δ = 155.98,
154.19, 153.42, 152.57, 147.36 (2 C), 147.15, 146.90, 146.44, 146.40,
146.33 (2 C), 146.27, 146.23, 146.17, 146.07, 146.04, 145.92, 145.68,
145.61 (3 C), 145.54, 145.48, 145.39 (2 C), 145.31, 145.27, 144.82,
144.76, 144.48 (2 C), 143.25, 143.12, 142.78, 142.76, 142.70, 142.68,
142.44, 142.30, 142.26 (2 C), 142.22, 142.13 (3 C), 142.07, 141.81,
141.77, 140.39, 140.31, 140.21, 139.71, 137.91 (2 C), 137.49, 136.78
(3 C), 136.52, 136.16, 135.75, 129.00, 128.83, 127.70, 80.72, 75.56,
2922, 2852, 1534, 1451, 1424, 1378, 1270, 1183, 1127, 1074, 1026,
983, 924, 871, 843, 819, 751, 666, 603, 573, 553, 526, 479 cm–1. UV/
Vis (CHCl3): λmax = 254, 307, 429 nm. MS (APCI): m/z = 844 [M
+ 1]+, 720 [C60]+. HRMS (MALDI FT-ICR): calcd for C68H13N
[M]+ 843.1048; found 843.1043.
Synthesis of N-Methyl-2-(1-methylvinyl)fulleropyrrolidine (6b) in
PhCl and DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol)
with sarcosine (1b, 26.7 mg, 0.30 mmol) and methylallyl chloride
(364.0 mg, 4.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C for
20 h by the same procedure as above gave unreacted [60]fullerene
(22.9 mg, 64%) and 6b (11.1 mg, 27% yield, 75% based on con-
sumed [60]fullerene). 1H NMR (400 MHz, CS2/CDCl3): δ = 5.55
(s, 1 H), 5.44 (s, 1 H), 4.89 (d, J = 9.6 Hz, 1 H), 4.42 (s 1 H), 4.13
(d, J = 9.2 Hz, 1 H), 2.83 (s, 3 H), 2.19 (s, 3 H) ppm. 13C NMR
(150 MHz, CS2/CDCl3): δ = 155.69, 154.31, 153.70, 153.44, 147.07,
147.05, 146.85, 146.11 (2 C), 146.08, 145.98 (2 C), 145.95, 145.89,
145.85, 145.78, 145.76, 145.58, 145.36, 145.34, 145.32, 145.31,
145.17, 145.07 (2 C), 145.05 (2 C), 144.95, 144.53, 144.49, 144.19,
144.18, 143.02, 142.84, 142.50, 142.46, 142.44, 142.41, 142.00 (2
C), 141.97, 141.96, 141.94, 141.88, 141.87, 141.83, 141.80, 141.73,
141.54, 141.50, 141.40, 140.05, 139.97, 139.70, 139.57, 136.43,
136.39, 135.49, 135.22, 118.75, 85.04, 75.63, 69.76, 69.17, 40.03,
69.11, 66.49, 57.19 ppm. FTIR (KBr): ν = 3083, 3060, 3025, 2956,
˜
2918, 2849, 1655, 1611, 1508, 1461, 1450, 1421, 1384, 1174, 987,
928, 732, 694, 598, 572, 552, 525 cm–1. UV/Vis: λmax = 257, 308,
429 nm. MS (APCI): m/z = 880 [M + 1]+, 796 [C64H6N]+, 720
[C60]+. HRMS (MALDI FT-ICR): calcd for C71H13N [M]+
879.1048; found 879.1053.
29.90 ppm. FTIR (KBr): ν = 3085, 2939, 2918, 2845, 2778, 1618,
˜
1539, 1461, 1425, 1400, 1259, 1217, 1176, 1102, 1036, 904, 803,
766, 726, 600, 574, 524, 478 cm–1. UV/Vis (CHCl3): λmax = 257,
306, 431 nm. MS (APCI): m/z = 818 [M + 1]+, 720 [C60]+. HRMS
(MALDI FT-ICR): calcd for C66H11N [M]+ 817.0891; found
817.0885.
Synthesis of 2-Vinyl-4-methylfulleropyrrolidine (5e) and N-Allyl-2-
vinyl-4-methylfulleropyrrolidine (5g) in PhCl and DMSO: Treatment
of [60]fullerene (36.0 mg, 0.05 mmol) with alanine (1e, 26.7 mg,
0.30 mmol) and allyl chloride (300.0 mg, 4.0 mmol) in PhCl/DMSO
(20 mL/10 mL) at 80 °C for 17 h by the same procedure as above Synthesis of N-Ethyl-2-(1-methylvinyl)fulleropyrrolidine (6c) in PhCl
gave unreacted [60]fullerene (20.5 mg, 57%), 5g (5.2 mg, 12% yield, and DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with
29% based on consumed [60]fullerene), and 5e (8.3 mg, 21% yield,
N-ethylglycine (1c, 30.3 mg, 0.30 mmol) and methylallyl chloride
48% based on consumed [60]fullerene).
(364.0 mg, 4.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C for
Eur. J. Org. Chem. 2014, 6252–6262
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6259

B. Jin, J. Shen, R. Peng, C. Chen, S. Chu
FULL PAPER
16 h by the same procedure as above gave unreacted [60]fullerene
(22.7 mg, 63%) and 6c (12.4 mg, 30% yield, 74% based on con-
sumed [60]fullerene). 1H NMR (300 MHz, CS2/CDCl3): δ = 5.53
(s, 1 H), 5.42 (s, 1 H), 5.04 (d, J = 9.3 Hz, 1 H), 4.56 (s 1 H), 4.01
FTIR (KBr): ν = 3026, 2930, 2846, 2774, 1540, 1512, 1495, 1462,
˜
1400, 1329, 1223, 1180, 1121, 965, 746, 689, 598, 568, 527,
476 cm–1. UV/Vis: λmax = 256, 310, 431 nm. MS (APCI): m/z = 880
[M + 1]+, 720 [C60]+. HRMS (MALDI FT-ICR): calcd for
(d, J = 9.3 Hz, 1 H), 3.40–3.33 (m, 1 H), 2.63–2.55 (m, 1 H), 2.17 C71H13N [M]+ 879.1048; found 879.1042.
(s, 3 H), 1.56 (t, J = 7.2 Hz, 3 H) ppm. 13C NMR (75 MHz, CS2/
Synthesis of N-Methyl-2-ethynylfulleropyrrolidine (8b) in PhCl and
CDCl3): δ = 155.69, 154.38, 153.70, 153.65, 153.33, 146.91, 146.88,
146.73, 146.05, 145.96, 145.92, 145.82 (2 C), 145.78, 145.73, 145.69,
145.62, 145.60, 145.44, 145.20, 145.19, 145.16 (2 C), 145.04, 144.92
(2 C), 144.89 (2 C), 144.78, 144.39, 144.35, 144.05, 144.03, 142.87,
142.35, 142.30, 142.28, 142.26, 141.86, 141.82, 141.81, 141.79,
141.71, 141.69, 141.64, 141.58, 141.55 (3 C), 141.40, 141.34, 139.92,
139.82, 139.57, 139.39, 136.34, 136.31, 135.28, 135.03, 118.59,
DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with
sarcosine (1b, 22.7 mg, 0.30 mmol) and propargyl bromide (7b,
357.0 mg, 3.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 90 °C for
1 h by the same procedure as above gave unreacted [60]fullerene
(17.9 mg, 50%) and 8b (13.8 mg, 35% yield, 69% based on con-
sumed [60]fullerene). 1H NMR (300 MHz, CS2/CDCl3): δ = 4.96
(s, 1 H), 4.73 (d, J = 9.5 Hz, 1 H), 4.22 (d, J = 9.4 Hz, 1 H), 3.05
(s, 3 H), 2.86 (s, 1 H) ppm. 13C NMR (75 MHz, CS2/CDCl3): δ =
154.51, 153.55, 152.62, 152.52, 147.08, 147.04, 146.53, 146.12,
146.07, 146.05, 145.98 (2 C), 145.85, 145.80, 145.74 (2 C), 145.71
(2 C), 145.45, 145.40, 145.28 (2 C), 145.24 (2 C), 145.17, 145.02 (2
C), 144.97 (2 C), 144.38, 144.31, 144.19, 144.16, 142.83, 142.75 (2
C), 142.41 (2 C), 142.36 (2 C), 142.00, 141.91 (2 C), 141.81, 141.79,
141.75, 141.72 (2 C), 141.51, 141.47, 139.99, 139.93, 139.87, 139.45,
137.04, 136.40, 136.02, 135.62, 135.27, 79.63, 79.01, 74.20, 69.06,
83.82, 74.95, 68.78, 66.18, 47.55, 29.83, 13.65 ppm. FTIR (KBr): ν
˜
= 3078, 2961, 2920, 2851, 2786, 1506, 1455, 1424, 1375, 1341, 1261,
1184, 1153, 1094, 1024, 902, 802, 756, 700, 662, 600, 573, 550, 526,
478 cm–1. UV/Vis (CHCl3): λmax = 257, 307, 432 nm. MS (APCI):
m/z = 832 [M + 1]+, 720 [C60]+. HRMS (MALDI FT-ICR): calcd
for C67H13N [M]+ 831.1048; found 831.1044.
Synthesis of N-Benzyl-2-(1-methylvinyl)fulleropyrrolidine (6d) in
PhCl and DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol)
with N-benzylglycine (1d, 49.5 mg, 0.30 mmol) and methylallyl
chloride (364.0 mg, 4.0 mmol) in PhCl/DMSO (20 mL/10 mL) at
80 °C for 16 h by the same procedure as above gave unreacted [60]-
fullerene (24.5 mg, 68%) and 6d (10.8 mg, 24% yield, 76% based
68.99, 67.62, 39.09 ppm. FTIR (KBr): ν = 3292, 2929, 2841, 2774,
˜
2190, 1539, 1510, 1462, 1428, 1327, 1264, 1215, 1180, 1163,
1106, 1028, 884, 803, 766, 706, 660, 636, 600, 572, 526, 477 cm–1.
UV/Vis (CHCl3): λmax = 254, 307, 429 nm. MS (APCI): m/z = 802
[M + 1]+, 720 [C60]+. HRMS (MALDI FT-ICR): calcd for C65H7N
[M]+ 801.0578; found 801.0577.
1
on consumed [60]fullerene). H NMR (300 MHz, CS2/CDCl3): δ =
7.69 (d, J = 7.4 Hz, 2 H), 7.49–7.43 (m, 2 H), 7.39–7.33 (m, 1 H),
5.68 (s, 1 H), 5.53 (s, 1 H), 4.76 (d, J = 9.5 Hz, 1 H), 4.71 (s 1 H),
4.62 (d, J = 13.5 Hz, 1 H), 4.02 (d, J = 9.5 Hz, 1 H), 3.60 (d, J =
13.5 Hz, 1 H), 2.30 (s, 3 H) ppm. 13C NMR (75 MHz, CS2/CDCl3):
δ = 155.91, 154.49, 153.76, 153.60, 147.15 (2 C), 146.98, 146.24,
146.16 (2 C), 146.05 (2 C), 145.99, 145.97, 145.92, 145.86, 145.83,
145.66, 145.44 (2 C), 145.42, 145.33, 145.22, 145.17, 145.15, 145.13
(2 C), 145.02, 144.61, 144.56, 144.26 (2 C), 143.09, 142.89, 142.56,
142.49, 142.13, 142.06, 142.03, 141.98, 141.95, 141.91, 141.87,
141.79, 141.57 (2 C), 141.55 (3 C), 140.08, 139.98, 139.76, 139.61,
137.92 (2 C), 136.58, 136.39, 135.63, 135.25, 128.66 (2 C), 128.56
(2 C), 127.46, 119.21, 83.22, 75.17, 68.96, 66.59, 57.22 ppm. FTIR
Synthesis of N-Methyl-2-ethoxycarbonylfulleropyrrolidine (8c) in
PhCl and DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol)
with sarcosine (1b, 22.7 mg, 0.30 mmol) and ethyl bromoacetate
(7c, 418.0 mg, 2.5 mmol) in PhCl/DMSO (20 mL/10 mL) at 90 °C
for 1 h by the same procedure as above gave unreacted [60]fullerene
(15.6 mg, 43%) and 8c[11b] (14.0 mg, 33% yield, 58% based on con-
sumed [60]fullerene). 1H NMR (300 MHz, CDCl3/CS2): δ = 4.95
(d, J = 9.3 Hz, 1 H), 4.78 (s, 1 H), 4.41–4.27 (m, 2 H), 4.26 (d, J
= 9.3 Hz, 1 H), 3.01 (s, 3 H), 1.28 (t, J = 7.1 Hz, 3 H) ppm. MS
(APCI): m/z = 850 [M + 1]+, 776 [M – COOCH2CH3]+, 720
[C60]+.
(KBr): ν = 3077, 3024, 2953, 2918, 2847, 2787, 1539, 1512, 1494,
˜
Synthesis of N-Methyl-2-cyanofulleropyrrolidine (8d) in PhCl and
DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with
sarcosine (1b, 22.7 mg, 0.30 mmol) and bromoacetonitrile (7d,
360.0 mg, 3.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 90 °C for
2 h by the same procedure as above gave unreacted [60]fullerene
(17.7 mg, 49%) and 8d (8.7 mg, 22% yield, 43% based on con-
sumed [60]fullerene). 1H NMR (400 MHz, CS2/CDCl3): δ = 5.43
(s, 1 H), 4.59 (s, 2 H), 3.14 (s, 3 H) ppm. 13C NMR (100 MHz,
CS2/CDCl3): δ = 54.01, 152.67, 151.70, 149.90, 147.58, 147.47,
146.53, 146.49, 146.47, 146.42, 146.24 (3 C), 146.22, 146.04, 145.95,
145.83, 145.82, 145.73, 145.64, 145.60, 145.58, 145.55, 145.47 (2 C),
145.34, 145.23 (2 C), 144.73, 144.59, 144.55, 144.53, 143.19 (2 C),
142.85 (2 C), 142.83, 142.77, 142.35 (2 C), 142.29, 142.19 (2 C),
142.13, 142.10, 142.04 (2 C), 142.01, 141.92, 141.84, 140.50, 140.45,
140.28, 140.15, 138.11, 137.17, 136.62, 135.85, 114.75, 72.87, 69.42,
1462, 1451, 1427, 1372, 1340, 1235, 1163, 1139, 1119, 1098, 1070,
1028, 906, 803, 767, 734, 696, 598, 575, 553, 527, 477 cm–1. UV/Vis
(CHCl3): λmax = 257, 307, 431 nm. MS (APCI): m/z = 894
[M + 1]+, 720 [C60]+. HRMS (MALDI FT-ICR): calcd for
C72H15N [M]+ 893.1204; found 893.1206.
Synthesis of N-Methyl-2-styrylfulleropyrrolidine (8a) in PhCl and
DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with
sarcosine (1b, 22.7 mg, 0.30 mmol) and cinnamyl chloride (7a,
383.0 mg, 2.5 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C for
15 h by the same procedure as above gave unreacted [60]fullerene
(17.2 mg, 48%) and 8a (13.9 mg, 32% yield, 61% based on con-
sumed [60]fullerene). 1H NMR (300 MHz, CS2/CDCl3): δ = 7.44
(d, J = 7.8 Hz, 2 H), 7.34–7.29 (m, 2 H), 7.28–7.20 (m, 1 H), 7.06
(d, J = 15.6 Hz, 1 H), 6.68 (dd, J = 9.0, 15.6 Hz, 1 H), 4.89 (d, J
= 9.4 Hz, 1 H), 4.48 (d, J = 9.1 Hz, 1 H), 4.16 (d, J = 9.3 Hz, 1
H), 2.92 (s, 3 H) ppm. 13C NMR (100 MHz, CS2/CDCl3): δ =
155.65, 153.84, 153.23, 152.28, 147.07, 147.04, 146.58, 146.50,
146.12 (2 C), 146.00, 145.93, 145.88, 145.77, 145.75, 145.61, 145.39,
145.37, 145.32, 145.28, 145.24, 145.18, 145.12, 145.09, 145.01,
144.99, 144.53, 144.45, 144.22, 144.17, 142.96, 142.84, 142.50,
142.46, 142.40, 142.37, 142.11, 142.04, 141.98, 141.94, 141.90,
141.84 (2 C), 141.83, 141.80, 141.55, 141.49, 140.09, 139.93, 139.66,
137.15, 136.28, 135.92 (2 C), 135.86, 135.76, 135.50, 128.56 (2 C),
128.17, 127.12, 126.76 (2 C), 82.00, 76.32, 69.63, 69.14, 39.94 ppm.
68.66, 67.03, 38.79 ppm. FTIR (KBr): ν = 2921, 2851, 2790, 2330,
˜
1510, 1462, 1429, 1333, 1267, 1181, 1163, 1112, 1093, 1039, 885,
769, 600, 575, 554, 526, 479 cm–1. UV/Vis (CHCl3): λmax
=
260, 313, 428, 697 nm. MS (APCI): m/z = 803 [M + 1]+, 776 [M –
CN]+, 720 [C60]+. HRMS (MALDI FT-ICR): calcd for C64H6N2
[M]+ 802.0531; found 802.0527.
Synthesis of N-Methyl-2-methylfulleropyrrolidine (10a) in PhCl and
DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with
sarcosine (1b, 22.7 mg, 0.30 mmol) and ethyl bromide (9a,
6260
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© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2014, 6252–6262

Fulleropyrrolidines from [60]Fullerene, Halides, and Amino Acids
327.0 mg, 3.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C for (75 MHz, CS2/CDCl3): δ = 156.36, 154.82, 154.65, 153.55, 147.03,
3 h by the same procedure as above gave unreacted [60]fullerene
(20.3 mg, 56%) and 10a[14] (10.7 mg, 27% yield, 62% based on con-
sumed [60]fullerene). 1H NMR (300 MHz, CS2/CDCl3): δ = 4.81
(d, J = 9.3 Hz, 1 H), 4.11 (d, J = 9.2 Hz, 1 H), 3.91 (q, J = 6.2 Hz,
1 H), 2.93 (s, 3 H), 2.00 (d, J = 6.3 Hz, 3 H) ppm.
147.00, 146.59, 146.30, 146.12, 146.08 (2 C), 146.02, 145.98, 145.90,
145.86, 145.81, 145.80, 145.60, 145.51, 145.41, 145.29, 145.21,
145.16, 145.11 (3 C), 145.08, 145.01, 144.58, 144.44, 144.27, 144.23,
143.06, 142.92, 142.50, 142.45, 142.10, 142.08, 142.05, 142.00,
141.96, 141.95, 141.91, 141.89, 141.69, 141.58 (2 C), 140.10, 140.03,
139.76, 139.55, 138.38 (2 C), 136.97, 136.08, 135.61, 135.28, 128.71
(2 C), 128.62 (2 C), 127.41, 77.63, 76.12, 70.39, 66.76, 56.44, 23.73,
Synthesis of N-Methyl-2-ethylfulleropyrrolidine (10b) in PhCl and
DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with
sarcosine (1b, 22.7 mg, 0.30 mmol) and n-bromopropane (9b,
369.0 mg, 3.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C for
3 h by the same procedure as above gave unreacted [60]fullerene
(21.9 mg, 61%) and 10b (11.9 mg, 30% yield, 75% based on con-
sumed [60]fullerene). 1H NMR (600 MHz, CS2/CDCl3): δ = 4.83
(d, J = 9.4 Hz, 1 H), 4.20 (d, J = 9.5 Hz, 1 H), 3.89 (t, J = 5.2 Hz,
1 H), 3.02 (s, 3 H), 2.74–2.67 (m, 1 H), 2.64–2.56 (m, 1 H), 1.50 (t, J
= 7.5 Hz, 3 H) ppm. 13C NMR (150 MHz, CS2/CDCl3): δ = 156.30,
154.37, 154.29, 153.32, 147.06, 147.03, 146.65, 146.32, 146.18,
146.14, 146.11, 146.03, 146.00, 145.93, 145.89, 145.82, 145.79,
145.65, 145.40, 145.33, 145.32, 145.30, 145.19, 145.12 (3 C), 145.08,
145.03, 144.61, 144.46, 144.26, 144.21, 143.06. 142.92, 142.55,
142.52 (2 C), 142.48, 142.06, 142.05 (2 C), 142.03, 142.02, 141.95,
141.93, 141.70, 141.59, 141.53, 140.17, 140.09, 139.70, 139.51,
137.09, 136.21, 135.71, 135.37, 79.35, 76.02, 70.32, 69.93, 39.75,
11.84 ppm. FTIR (KBr): ν = 3056, 3027, 2957, 2921, 2857, 1603,
˜
1540, 1494, 1458, 1428, 1335, 1280, 1184, 1120, 1097, 1028, 799,
766, 725, 576, 552, 526 cm–1. UV/Vis: λmax = 257, 310, 430 nm. MS
(APCI): m/z = 882 [M + 1]+, 720 [C60]+. HRMS (MALDI FT-
ICR): calcd for C71H15N [M]+ 881.1204; found 881.1206.
Synthesis of N-Methyl-2-propylfulleropyrrolidine (10e) in PhCl and
DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with
sarcosine (1b, 22.7 mg, 0.30 mmol) and n-bromobutane (9c,
343.0 mg, 2.5 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C for
3 h by the same procedure as above gave unreacted [60]fullerene
(14.1 mg, 39%) and 10e[14] (15.4 mg, 38% yield, 62% based on con-
sumed [60]fullerene). 1H NMR (300 MHz, CS2/CDCl3): δ = 4.80
(d, J = 9.6 Hz, 1 H), 4.18 (d, J = 9.7 Hz, 1 H), 3.92 (t, J = 4.8 Hz,
1 H), 3.00 (s, 3 H), 2.57–2.46 (m, 1 H), 2.42–2.29 (m, 1 H), 2.04–
1.90 (m, 2 H), 1.13 (t, J = 7.3 Hz, 1 H) ppm.
23.93, 12.17 ppm. FTIR (KBr): ν = 2957, 2923, 2855, 1530, 1460,
˜
Supporting Information (see footnote on the first page of this arti-
1429, 1265, 1184, 1105, 1095, 577, 552, 526 cm–1. UV/Vis: λmax
=
1
cle): H NMR and 13C NMR spectra of products 2a–c, 4b–4e, 5a–
257, 310, 431 nm. MS (APCI): m/z = 806 [M + 1]+, 720 [C60]+.
HRMS (MALDI FT-ICR): calcd for C65H11N [M]+ 805.0891;
found 805.0887.
5g, 6b–6d, 8a–d and 10a–e.
Acknowledgments
Synthesis of N-Ethyl-2-ethylfulleropyrrolidine (10c) in PhCl and
DMSO: Treatment of [60]fullerene (36.0 mg, 0.05 mmol) with N-
ethylglycine (1c, 26.7 mg, 0.30 mmol) and n-bromopropane (9b,
369.0 mg, 3.0 mmol) in PhCl/DMSO (20 mL/10 mL) at 80 °C for
3 h by the same procedure as above gave unreacted [60]fullerene
(25.4 mg, 71%) and 10c (10.5 mg, 26% yield, 87% based on con-
sumed [60]fullerene). 1H NMR (300 MHz, CS2/CDCl3): δ = 4.94
(d, J = 9.8 Hz, 1 H), 4.13 (d, J = 9.7 Hz, 1 H), 4.10 (t, J = 5.4 Hz,
1 H), 3.72–3.58 (m, 1 H), 2.97–2.83 (m, 1 H), 2.64–2.45 (m, 2 H),
1.57 (t, J = 7.2 Hz, 3 H), 1.45 (t, J = 7.4 Hz, 3 H) ppm. 13C NMR
(100 MHz, CS2/CDCl3): δ = 156.24, 154.71, 154.60, 153.36, 146.90,
146.87, 146.42, 146.20, 146.00 (2 C), 145.99, 145.89, 145.86, 145.78,
145.74, 145.69, 145.67, 145.50, 145.33, 145.28, 145.17, 145.15,
145.04 (2 C), 144.98 (2 C), 144.96, 144.90, 144.47, 144.33, 144.15,
144.12, 142.95, 142.82, 142.42, 142.40, 142.39, 142.36, 141.97,
141.96, 141.93, 141.89 (2 C), 141.85, 141.83, 141.81 (2 C), 141.59,
141.51, 141.45, 140.04, 139.99, 139.67, 139.42, 136.92, 136.11,
135.44, 135.24, 77.85, 75.85, 70.15, 66.24, 46.61, 23.91, 13.74,
The authors are grateful for financial support from the National
Natural Science Foundation of China (NSFC) (project num-
bers 21301142, 21201142), the National Defense Fundamental Re-
search Projects (project numbers A3120133002 and A3120110005),
the Youth Innovation Research Team of Sichuan for Carbon
Nanomaterials (grant number 2011JTD0017), and the Southwest
University of Science and Technology Researching Project (grant
numbers 13zx9107, 13xnkf05).
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benzylglycine (1d, 49.5 mg, 0.30 mmol) and n-bromopropane (9b,
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(d, J = 7.3 Hz, 2 H),7.50–7.40 (m, 2 H), 7.40–7.30 (m, 1 H), 4.84
(d, J = 13.0 Hz, 1 H), 4.71 (d, J = 10.0 Hz, 1 H), 4.26 (t, J =
5.3 Hz, 1 H), 4.12 (d, J = 10.0 Hz, 1 H), 3.92 (d, J = 13.0 Hz, 1
H), 2.73–2.57 (m, 2 H), 1.51 (t, J = 7.4 Hz, 3 H) ppm. 13C NMR
Eur. J. Org. Chem. 2014, 6252–6262
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Received: May 28, 2014
Published Online: August 14, 2014
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