Copper-Catalyzed Reaction of C60 with Tertiary Amines for the Preparation of Spiro-Linked Methanofullerenes and Fullerenoalkanals

Article abstract of DOI:10.1021/acs.joc.9b00335

CuI-catalyzed reaction of C₆₀ with tertiary amines by using air as the sole oxidant has been developed. Spiro-linked methanofullerenes bearing cyclic amides and fullerenoalkanals can be obtained selectively using the cyclic and acyclic amines a

Full text of DOI:10.1021/acs.joc.9b00335

Article
pubs.acs.org/joc
Cite This: J. Org. Chem. XXXX, XXX, XXX−XXX
Copper-Catalyzed Reaction of C60 with Tertiary Amines for the
Preparation of Spiro-Linked Methanofullerenes and
Fullerenoalkanals
Yong-Jian Liu, Jie Ge, Chun-Bao Miao, and Hai-Tao Yang*
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Advanced Catalysis and Green Manufacturing
Collaborative Innovation Center, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China
S
* Supporting Information
ABSTRACT: CuI-catalyzed reaction of C60 with tertiary amines by
using air as the sole oxidant has been developed. Spiro-linked
methanofullerenes bearing cyclic amides and fullerenoalkanals can be
obtained selectively using the cyclic and acyclic amines as starting
materials, respectively. The reactions show a wide functional group
tolerance. In addition, four ([6,6]-phenyl-C61-butyric acid methyl ester)
analogues can be easily prepared through the developed method.
of fullerenes receive more attention.9,10 In this respect, the
INTRODUCTION
■
transition metal-promoted or -catalyzed reaction has repre-
Tertiary amine derivatives are ubiquitous in nature. The direct
sented a powerful tool to functionalize fullerenes including
functionalization of C(sp3)−H bonds of tertiary amines
radical reactions,11 C−H activation,12 and asymmetric
represents an attractive protocol for the synthesis of complex
reactions.13 Over the past few years, Cu(I/II)-promoted
N-containing moieties as it avoids the introduction of an active
transformation of C60 has gradually attracted increasing
group and thus shortens the number of reaction steps. Among
attention.9a,14 We have been interested in this field and have
them, direct α-functionalization of tertiary amines has been
developed several new methods for the functionalization of
well explored as an efficient and conventional way to
C60.15 Most recently, we reported an interesting CuI-catalyzed
synthesize tertiary amine derivatives through either capture
reaction of C60 with aminoalcohols.15e 4-/5-Aminoalcohols
of the in situ generated iminium intermediates1 under
displayed an entirely different reactivity from 2-/3-amino-
alcohols, providing the surprising spiro-linked methanofuller-
enes bearing cyclic amides through cyclic enamine inter-
mediates. Unfortunately, most of the cyclic enamines are
unstable and the 4-/5-aminoalcohols are not easily available,
which limits the application of this method. In contrast, the
tertiary amines are either commercially available or can be
easily prepared from the reactions of secondary amines with
oxidative conditions or trap of α-aminoalkyl radical inter-
mediates under photo-redox catalytic conditions,2 as well
based on direct α-metalation.3 In contrast to the flourishing α-
functionalizations, β-functionalization of tertiary amines is
significantly limited owing to the relatively inert C−H bonds.
As far as we know, most of the developed β-functionalization
relies on the in situ generated nucleophilic enamines as key
intermediates followed by reactions with appropriate electro-
halide compounds. Inspired by the aformentioned β-
functionalization of tertiary amines, in which the enamines
philes4 or coupling with nucleophiles.5 Recently, a copper-
catalyzed β-functionalization of tertiary amines with thiophe-
nols has been reported via an enamine radical cation process.6
Although the promising chemistry of tertiary amines has been
exploited, further improvement for application is still in
demand such as development of novel transformation, use of
ubiquitous metals instead of precious metals, and extension of
the limited substrate scope. In addition, compared to the
specific functionalization of α- or β-tertiary amines, α,β-
difunctionalization of tertiary amines is extremely rare, which
needs to be further explored.7 The preparation of spiro
compounds at the β-position of tertiary amines is still blank.
On the other hand, the remarkable potential of organo-
fullerenes in materials and biomedical science, electronic
devices, and nanotechnology8 has made organic modification
were generated as the key intermediates catalyzed by Pt, Ru,
Pd, Cu, or Fe,4−6 we herein reported the CuI-catalyzed
functionalization of C60 with tertiary amines (Scheme 1).
RESULTS AND DISCUSSION
■
We began our study by investigating the reactions of C60 with
N-benzylpyrrolidine 1a in the presence of various copper
catalysts and ligands (Table 1). In a preliminary attempt, the
reaction of C60 with 2 equiv of 1a was carried out in the
presence of 0.2 equiv of CuI in chlorobenzene at 120 °C. No
Received: February 1, 2019
© XXXX American Chemical Society
A
DOI: 10.1021/acs.joc.9b00335
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The Journal of Organic Chemistry
Article
reaction to assess the generality of the CuI-catalyzed reaction
(Table 2). Either an electron-donating or an electron-
Scheme 1. Functionalization of Tertiary Amines
Table 2. CuI-Catalyzed Reaction of Cyclic Tertiary Amines
a
with C60
a
Table 1. Survey of the Reaction Conditions
b
c
entry
additive
molar ratio
time (h)
yield
1
2
3
4
5
6
7
8[
9
10
11
12
13
14
CuI
CuI, Phen
CuI, Bpy
CuI, pyridine
CuI, lutidine
CuI, DMAP
CuI, TMDEA
CuI, DMAP
CuCl, DMAP
CuBr, DMAP
Cu2O, DMAP
Cu(CH3CN)4PF6, DMAP
Cu(OAc)2, DMAP
CuCl2, DMAP
1:2:0.2
24
24
24
24
24
24
24
24
24
24
24
24
24
24
0
1:2:0.2:0.2
1:2:0.2:0.2
1:2:0.2:0.2
1:2:0.2:0.4
1:2:0.2:0.4
1:2:0.2:0.2
1:2:0.2:0.4
1:2:0.2:0.4
1:2:0.2:0.4
1:2:0.2:0.4
1:2:0.2:0.4
1:2:0.2:0.4
1:2:0.2:0.4
12 (74)
37 (63)
0
0
64 (79)
trace
6 (88)
27 (84)
52 (74)
0
d
]
0
trace
11 (69)
a
C60 (36 mg), other reactants and reagents, 10 mL of chlorobenzene,
b
c
120 °C, and air. C60/1a/[Cu]/additives. Isolated yield; the values in
parentheses are based on consumed C60. Operated under a N2
d
a
b
atmosphere.
The yield refers to an isolated yield. Under an O2 atmosphere.
reaction occurred by even prolonging the reaction time to 20
h, indicating that CuI alone could not trigger the reaction
(Table 1, entry 1). Next, the combination of CuI with different
ligands was tried because the catalytic system varied greatly
with the substrate structure, as has been observed in our
previous research.15 Using Phen (1,10-phenanthroline) or Bpy
(2,2′-bipyridine) as ligands afforded the anticipated product 2a
in 12 and 37% yield, respectively (Table 1, entries 2 and 3). A
further ligand screening revealed that DMAP was the most
effective, giving 64% yield of 2a (Table 1, entry 6); however,
the combination of CuI with pyridine, lutidine, or TMEDA
displayed no catalytic activity (Table 1, entries 4, 5, and 7). It
should be noted that O2 played a crucial role in this reaction
because the yield decreased significantly to 6% when the
reaction was carried out under a N2 atmosphere (Table 1,
entry 8). With the DMAP as the ligand, other copper salts were
also examined. CuCl and CuBr were inferior to CuI, giving 27
and 52% yield of 2a, respectively (Table 1, entries 9 and 10).
Cu2O, Cu(CH3CN)4PF6, and Cu(OAc)2 showed no catalytic
activity (Table 1, entries 11−13), and CuCl2 only furnished
11% production of 2a (Table 1, entry 14). The DMAP was
identified as a ligand rather than a base because no reaction
occurred when K2CO3 or Cs2CO3 was used instead of DMAP.
Under the optimized reaction conditions (Table 1, entry 6),
various N-substituted pyrrolidines were subjected to the
withdrawing group on the phenyl ring of the benzyl group
had little influence on the reaction (2b−d). Heteroaryl groups
such as 2-thienyl, 2-furyl, and 3-pyridyl were also examined.
Only N-(2-thienyl)pyrrolidine gave product 2l in 11% yield.
Various functional groups such as cyano, ester, vinyl, or
phenoxy group were well tolerated, giving 2f−i in satisfactory
yields. A terminal hydroxyl or amino group (−CH2CH2OH,
−CH2CH2NH2) on the nitrogen atom of pyrrolidine would
result in no formation of the desired product. When they were
pre-transformed to the OTBS or NHBoc group, the
anticipated products 2j and 2k could be obtained in 18 and
16% yield, respectively. Next, various N-substituted piperidines
1m−p were tested. N-Benzyl and N-butyl piperidines gave
good yields of 2m or 2n. When an ester group was connected
at the 4-position of the piperidine ring, product 2o was
obtained in a very low yield. Changing the ester group to the
hydroxyl group led to a complete failure of the reaction (2p,
0%). Changing the 4-hydroxyl group to the 4-hydroxymethyl
group led to the formation of a single product; however, the
NMR analysis showed that it was the spiro compound 2s
(Scheme 2). N-Benzylmorpholine could also react with C60 to
provide 2q in 12% yield. When the cyclic amine was further
extended to a seven-membered ring, that is, N-benzylazepane
1r, no analogous reaction occurred (2r, 0%).
B
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It was noteworthy that the reaction of C60 with methyl 5-
(dimethylamino)pentanoate 3i gave 37% yield of 4i. The
compound 4i had a structural similarity to PCBM ([6,6]-
phenyl-C61-butyric acid methyl ester), which had been
identified as the most representative electron acceptor material
frequently used in organic photovoltaic devices (OPVs).19 In
addition, the existence of a formyl group made it easily
transformable to various PCBM analogues. The reaction of 4i
with tosylhydrazide gave 5a in 90% yield. Also, the BF3·Et2O-
catalyzed reaction of 4i with indole or 5-chloroindole furnished
5b or 5c in 85 or 69% yield, respectively. These PCBM
analogues might show potential use in OPVs (Scheme 3).
Scheme 2. Reaction of N-Methyl-4-piperidinemethanol with
C60
Encouraged by the exciting results, we next turned our
attention to acyclic tertiary amines (Table 3). First, the tri(n-
Table 3. CuI-Catalyzed Reaction of Acyclic Tertiary Amines
with C60
Scheme 3. Transformation of 4i to PCBM Analogues
In a previously reported copper-catalyzed regioselective β-
functionalization of tertiary amines with thiophenols by Pan’s
group, a radical cation mechanism was proposed based on the
radical-trapping experiments.6 We speculated that the for-
mation of 2 and 4 underwent a similar reaction pathway.
However, when 3 equiv of TEMPO (2,2,6,6-tetramethyl-1-
piperidinyloxy) or BHT (2,6-ditertbutyl-4-methylphenol) as a
radical inhibitor was added to the standard reaction of C60 with
1a, no obvious inhibition effect was observed, which was
opposed to the radical mechanism (Scheme 4). The TEMPO
propyl)amine 3a and tri(n-butyl)amine 3b were tested.
Surprisingly, no methanofullerne product bearing an amide
group was formed. Instead, fullerenoalkanals 4a and 4b were
obtained in 47 and 44% yield, respectively. Other tertiary
amines 3c−e with different lengths of alkyl chains could also
provide corresponding fullerenoalkanals 4c−e in acceptable
yields. Vinyl, alkoxyl, OTBS, and ester groups were well
tolerated in the reaction, albeit the 4g was isolated in a very
low yield (9%).
Scheme 4. Free Radical Capture Experiments
Although the Bingel reaction and the reaction of C60 with
diazo compounds were the most widely used methods to
access methanofullerenes, the substrates of the Bingel reaction
were restricted to active methylene compounds bearing two
electron-withdrawing groups and the latter always yielded
fulleroides as byproducts.16 Fullerenoalkanals have been
prepared from the reaction of C60 with stabilized dimethylsul-
fonium α-formylalkylide or 2-bromoenol silyl ethers.17
However, the starting materials were not easily available and
needed to be synthesized from aldehydes through 2−3 steps of
the reaction. The BF3·Et2O-promoted conversion of C60-fused
dihydrofurans was an alternative method, but C60-fused
dihydrofurans needed to be synthesized from C60 and a large
excess amount of BF3·Et2O (200 equiv) was required.18
had no influence on the reaction and the addition of BHT
resulted in a longer reaction time and a slightly lower yield. At
present, the exact mechanism is still unclear. A similar reaction
mechanism as reported in our previous work involving
enamines as the key intermediate also could not be ruled
out.15e However, surely an imine cation intermediate 6 or 9
must be involved in the reaction. For the cyclic tertiary amine,
the generated intermediate 6 underwent addition with H2O
and subsequent oxidation with Cu(II) to afford 3. In the case
C
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Article
combined organic layers were dried with anhydrous sodium sulfate,
filtered, and evaporated in vacuo. The residue was purified by column
chromatography with ethyl acetate/petroleum ether (1:6) as the
eluent to give the product 4-OTBS-benzaldehyde. Step 2: A mixture
of 4-OTBS-benzaldehyde (1.89 g, 8 mmol), pyrrolidine (1.32 mL, 16
mmol), and sodium triacetoxyborohydride (2.54 g, 12 mmol) in 1,2-
dichloroethane (15 mL) was stirred at room temperature under a
nitrogen atmosphere for 4 h. Water (40 mL) was added, and the
mixture was extracted with methylene dichloride (3 × 25 mL). The
combined organic layers were dried with anhydrous sodium sulfate,
filtered, and evaporated in vacuo. The residue was purified by column
chromatography with CH2Cl2/MeOH (30:1) as the eluent to give the
1d (0.82 g, 35%, pale yellow liquid).
of acyclic tertiary amines, hydrolysis of the intermediate 9
furnished fullerenoalkanal 4 (Scheme 5). The formation of 2s
also proved the existence of 6.
Scheme 5. Plausible Intermediate
1d: 1H NMR (300 MHz, CDCl3): δ 7.17 (d, J = 8.4 Hz, 2H), 6.77
(d, J = 8.4 Hz, 2H), 3.53 (s, 2H), 2.44−2.53 (m, 4H), 1.72−1.82 (m,
4H), 0.98 (s, 9H), 0.18 (s, 6H); 13C NMR (75 MHz, CDCl3): δ
154.7, 132.1, 130.2, 119.9, 60.3, 54.2, 25.8, 23.5, 18.3, −4.3; HRMS
(ESI) m/z: [M + H]+ calcd for C17H30NOSi, 292.2097; found,
292.2088.
Preparation of 1j (Scheme S1b). Step 1: A mixture of 2-
bromoethanol (0.71 mL, 10 mmol), tert-butyldimethylsilyl chloride
(1.50 g, 10 mmol), and imidazole (884 mg, 13 mmol) in methylene
dichloride (15 mL) was stirred under a N2 atmosphere at room
temperature for 12 h. Water (50 mL) was added, and the mixture was
extracted with methylene dichloride (3 × 25 mL). The combined
organic layers were dried with anhydrous sodium sulfate, filtered, and
evaporated in vacuo. The residue was purified by column
chromatography with ethyl acetate/petroleum ether (1:3) as the
eluent to give the product 2-bromoethoxy(tert-butyl)dimethylsilane.
Step 2: A mixture of 2-bromoethoxy(tert-butyl)dimethylsilane (1.90 g,
8 mmol), pyrrolidine (0.99 mL, 12 mmol), and K2CO3 (1.1 g, 8
mmol) in acetonitrile (15 mL) was stirred at room temperature for 4
h; water (50 mL) was added and the mixture was extracted with
methylene dichloride (3 × 25 mL). The combined organic layers were
dried with anhydrous sodium sulfate, filtered, and evaporated in
vacuo. The residue was purified by column chromatography with
CH2Cl2/MeOH (15:1) as the eluent to give the 1j (1.21 g, 66%, pale
yellow liquid).
CONCLUSIONS
■
In summary, a unique α,β-difunctionalization of tertiary amines
via CuI-catalyzed reaction with C60 is disclosed. Aerobic
oxygen is used as the only external oxidant and DMAP ligand
addition is found to be crucial to the reaction. The cyclic and
acyclic tertiary amines show different reactivities and afford
selectively the spiro-linked methanofullerenes bearing cyclic
amides and fullerenoalkanals, respectively. To the best of our
knowledge, this is perhaps the simplest and most convenient
method to access these two kinds of organofullerenes. It is in
sharp contrast to the previously reported photoreactions or
thermal reactions of C60, which afford the fulleropyrrolidines or
cyclopentane-fused fullerene derivatives.20 The abundance of
commercially available tertiary amines further shows the
practical synthetic value of this approach. Furthermore, four
potential PCBM types of OPV candidates were prepared
through the developed method.
1
1j: H NMR (300 MHz, CDCl3): δ 3.75 (t, J = 6.8 Hz, 2H), 2.61
(t, J = 6.8 Hz, 2H), 2.52−2.57 (m, 4H), 1.73−1.78 (m, 4H), 0.89 (s,
9H), 0.05 (s, 6H); 13C NMR (75 MHz, CDCl3): δ 62.7, 58.5, 55.0,
26.1, 25.8, 23.6, 18.446, −5.2; HRMS (ESI) m/z: [M + H]+ calcd for
C12H28NOSi, 230.1940; found, 230.1934.
Preparation of 1k26 (Scheme S1c). A mixture of N-(2-
aminoethyl)pyrrolidine (0.48 mL, 4 mmol) and (Boc)2O (0.92 mL,
4 mmol) in tetrahydrofuran (15 mL) was stirred at room temperature
for 10 h. Water (40 mL) was added and the mixture was extracted
with methylene dichloride (3 × 25 mL). The combined organic layers
were dried with anhydrous sodium sulfate, filtered, and evaporated in
vacuo. The residue was purified by column chromatography with
ethyl acetate/petroleum ether (1:2) with CH2Cl2/MeOH (15:1) as
the eluent to give the product 1k (0.67 g, 78%, pale yellow liquid).
1k: 1H NMR (300 MHz, CDCl3): δ 5.08 (s, 1H), 3.23 (dd, J = 5.8,
11.5 Hz, 2H), 2.56 (t, J = 7.0 Hz, 2H), 2.48−2.52 (m, 4H), 2.07 (s,
2H), 1.74−1.78 (m, 4H), 1.43 (s, 9H).
EXPERIMENTAL SECTION
■
General Information. 1H and 13C NMR (proton broadband
decoupling) spectra were recorded on a 400/500 MHz (100/125
MHz for 13C NMR) spectrometer at ambient temperature, using
tetramethylsilane as an internal standard. Flash column chromatog-
raphy was performed over silica gel (200−300 mesh). High-resolution
mass spectrometry (HRMS) for those non-fullerene products was
performed on a Thermo Scientific LTQ Orbitrap XL equipped with
an ESI source (positive mode). Matrix-assisted laser desorption
ionization time-of-flight mass spectrometry (MALDI-TOF MS) for
organofullerenes was performed in a positive ion mode using DCTB
E-(2-[3-(4-tertbutylphenyl)-2-methyl-2-propenylidene]malononitrile)
as the matrix. UV−vis spectra were recorded on a Shimadzu UV-2401
spectrometer with CHCl3 as the solvent.
Preparation of 3g (Scheme S1d). Step 1: A mixture of 6-chloro-
1-hexanol (1.3 mL, 10 mmol), tert-butyldimethylsilyl chloride (1.5 g,
10 mmol), and imidazole (884 mg, 13 mmol) in methylene
dichloride(15 mL) was stirred at room temperature for 12 h. Water
(40 mL) was added, and the mixture was extracted with methylene
dichloride (3 × 25 mL). The combined organic layers were dried with
anhydrous sodium sulfate, filtered, and evaporated in vacuo. The
residue was purified by column chromatography with ethyl acetate/
petroleum ether = 1/6 as the eluent to give the TBS protected 6-
chloro-1-hexanol. Step 2: A mixture of the TBS protected 6-chloro-1-
hexanol (2.00 g, 8 mmol), aqueous solution of dimethylamine (40%,
2.75 mL, 16 mmol), and potassium carbonate (1.10 g, 8 mmol) in
acetonitrile (15 mL) was stirred at room temperature for 4 h; water
(50 mL) was added, and the mixture was extracted with methylene
dichloride (3 × 25 mL). The combined organic layers were dried with
Starting materials 1a, 1e, 1n, 1q, 3b, 3h, 3i,21 1b, 1c, 1i, 1l, 3f,22 1f,
1g,23 1h,24 and 1m25 were prepared according to the reported
procedures.
Preparation of 1d (Scheme S1a). Step 1: A mixture of 4-
hydroxybenzaldehyde (1.22 g, 10 mmol), tert-butyldimethylsilyl
chloride (1.50 g, 10 mmol), and imidazole (884 mg, 13 mmol) in
methylene dichloride (15 mL) was stirred at room temperature for 12
h. After completion of the reaction, an aqueous solution of sodium
hydroxide (10 mL × 2 mol/L) and water (30 mL) was added, and the
mixture was extracted with methylene dichloride (3 × 25 mL). The
D
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The Journal of Organic Chemistry
Article
anhydrous sodium sulfate, filtered, and evaporated in vacuo. The
residue was purified by column chromatography with CH2Cl2/MeOH
(15:1) as the eluent to give the 3g (1.41 g, 68%, pale yellow liquid).
3g: 1H NMR (300 MHz, CDCl3): δ 3.76 (t, J = 6.2 Hz, 2H), 2.84
(t, J = 8.1 Hz, 2H), 2.24 (t, J = 7.4 Hz, 2H), 2.21 (s, 6H), 1.40−1.59
(m, 4H), 1.22−1.40 (m, 4H), 0.89 (s, 9H), 0.05 (s, 6H); 13C NMR
(75 MHz, CDCl3): δ 63.3, 59.9, 45.5, 32.9, 27.8, 27.4, 26.0, 25.9, 18.4,
−5.2; HRMS (ESI) m/z: [M + H]+ calcd for C14H34NOSi, 260.2410;
found, 260.2402.
44.43, 43.84, 43.66, 29.69, 25.19, 20.61, 14.07; UV−vis (CHCl3):
λmax/nm 260, 328, 429, 493, 687; HRMS (MALDI-TOFMS) m/z:
M+ calcd for C68H13NO, 859.0997; found, 859.0979.
1
2f (brown solid, 24.0 mg, 54%, mp > 300 °C): H NMR (300
MHz, CS2−CDCl3): δ 3.99 (t, J = 7.1 Hz, 2H), 3.88 (t, J = 6.6 Hz,
2H), 3.77 (s, 3H), 3.28 (t, J = 7.1 Hz, 2H), 2.84 (t, J = 6.5 Hz, 2H);
13C NMR (100 MHz, CS2−CDCl3): δ 171.75, 168.54, 146.56,
145.37, 145.30, 145.24, 145.11, 145.01, 144.97, 144.91, 144.65,
144.46, 144.42, 144.00, 143.95, 143.53, 143.48, 143.05, 142.97,
142.91, 142.67, 142.22, 142.05, 141.89, 141.12, 140.95, 140.83,
137.16, 76.11 (sp3-C of C60), 51.81, 44.73, 43.94, 39.87, 32.51, 25.27;
HRMS (MALDI-TOFMS) m/z: M+ calcd for C68H11NO3, 889.0739;
found, 889.0727.
General Procedure for the CuI-Catalyzed Reaction of C60
with Tertiary Amines. A mixture of C60 (36.0 mg, 0.05 mmol),
tertiary amines (0.1 mmol), CuI (1.9 mg, 0.01 mmol), and DMAP
(2.5 mg, 0.02 mmol) was stirred vigorously in 10 mL of
chlorobenzene in a tube (Φ18 × 150 mm) at 120 °C for a given
time (for 1a−n, 1p, and 1s, under open air; for 1o and 1q, under an
O2 atmosphere). The solvent was removed in vacuo and the residue
was purified on a silica gel column with CS2−CS2/toluene−toluene/
EA as the eluent (gradient elution) to give unreacted C60 and
products 2a−o, 2q, 2s, and 4a−i.
2g (brown solid, 24.0 mg, 56%, mp > 300 °C; the pure 2g has a
1
very poor solubility in CS2 or 1,2-dichlorobenzene. The H NMR
spectrum was obtained from the reaction mixture without
1
purification): H NMR (300 MHz, CS2−CDCl3): δ 4.13 (t, J = 7.1
Hz, 2H), 3.90 (t, J = 6.4 Hz, 2H), 3.31 (t, J = 7.1 Hz, 2H), 2.90 (t, J =
6.3 Hz, 2H); HRMS (MALDI-TOFMS) m/z: M+ calcd for
C67H8N2O, 856.0637; found, 856.0628.
2a15e (brown solid, 28.6 mg, 64%): H NMR (400 MHz, CS2−
1
CDCl3): δ 7.32−7.46 (m, 5H), 4.74 (s, 2H), 3.76 (t, J = 7.1 Hz, 2H),
3.23 (t, J = 7.1 Hz, 2H); 13C NMR (100 MHz, CS2−CDCl3): δ
168.21, 146.63, 145.46, 145.34, 145.31, 145.15, 145.08, 145.04,
145.02, 144.94, 144.69, 144.51, 144.49, 144.45, 144.05, 143.99,
143.56, 143.52, 143.09, 143.00, 142.94, 142.70, 142.27, 142.12,
142.08, 141.97, 141.91, 141.14, 141.00, 140.94, 137.18, 135.77,
129.04, 128.67, 128.13, 76.22 (sp3-C of C60), 47.82, 44.19, 43.24,
24.99.
1
2h (brown solid, 23.4 mg, 50%, mp > 300 °C): H NMR (300
MHz, CS2−CDCl3): δ 7.26 (t, J = 8.0 Hz, 2H), 6.87−6.97 (m, 3H),
4.17 (t, J = 5.9 Hz, 2H), 3.96 (t, J = 7.0 Hz, 2H), 3.82 (t, J = 7.0 Hz,
2H), 3.28 (t, J = 7.0 Hz, 2H), 2.30 (quint, J = 6.5 Hz, 2H); 13C NMR
(100 MHz, CS2−C6D6): δ 168.58, 158.57, 146.66, 145.49, 145.36,
145.32, 145.14, 145.06, 145.03, 144.99, 144.92, 144.67, 144.50,
144.47, 144.43, 144.01, 143.98, 143.56, 143.49, 143.07, 142.99,
142.93, 142.68, 142.25, 142.08, 141.92, 141.09, 140.92, 140.89,
140.85, 137.17, 129.58, 121.03, 114.44, 76.23 (sp3-C of C60), 65.45,
44.28, 44.23, 41.46, 27.51, 25.18; UV−vis (CHCl3): λmax/nm 261,
328, 429, 495, 688; HRMS (MALDI-TOFMS) m/z: M+ calcd for
C73H15NO2, 937.1103; found, 937.1099.
1
2b (Brown solid, 21.2 mg, 46%, mp > 300 °C): H NMR (300
MHz, CS2−CDCl3): δ 7.37 (d, J = 7.9 Hz, 2H), 6.93 (d, J = 8.0 Hz,
2H), 4.69 (s, 2H), 3.84 (s, 3H), 3.77 (t, J = 7.1 Hz, 2H), 3.24 (t, J =
7.1 Hz, 2H); 13C NMR (100 MHz, CS2−CDCl3): δ 168.05, 159.40,
146.66, 145.51, 145.33, 145.31, 145.13, 145.07, 145.02, 144.99,
144.92, 144.67, 144.49, 144.46, 144.45, 144.43, 144.03, 143.97,
143.55, 143.50, 143.08, 142.98, 142.93, 142.69, 142.25, 142.07,
141.96, 141.90, 141.11, 140.97, 140.91, 137.16, 130.02, 127.77,
114.35, 76.27 (sp3-C of C60), 55.10, 47.21, 44.33, 43.09, 24.96; UV−
vis (CHCl3): λmax/nm 260, 328, 429, 496, 687; HRMS (MALDI-
TOFMS) m/z: M+ calcd for C72H13NO2, 923.0946; found, 923.0935.
1
2i (brown solid, 19.1 mg, 40%, mp > 300 °C): H NMR (400
MHz, CS2−CDCl3): δ 5.79 (ddt, J = 17.0, 10.3, 6.7 Hz, 1H), 4.99
(dq, J = 17.0, 1.4 Hz, 1H), 4.93 (d, J = 10.3 Hz, 1H), 3.90 (t, J = 7.0
Hz, 2H), 3.59 (t, J = 7.5 Hz, 2H), 3.29 (t, J = 7.0 Hz, 2H), 2.05 (q, J =
7.0 Hz, 2H), 1.78 (quint, J = 7.4 Hz, 2H), 1.28−1.54 (m, 12H); 13C
NMR (100 MHz, CS2−CDCl3): δ 168.19, 146.75, 145.58, 145.37,
145.32, 145.14, 145.09, 145.03, 145.00, 144.93, 144.69, 144.51,
144.48, 144.44, 144.01, 143.99, 143.57, 143.53, 143.08, 142.99,
142.94, 142.69, 142.27, 142.08, 141.96, 141.93, 141.13, 140.96,
140.93, 138.93, 137.15, 114.32, 76.32 (sp3-C of C60), 44.41, 43.89,
43.80, 34.02, 29.78, 29.69, 29.58, 29.36, 29.16, 27.60, 27.27, 25.12;
UV−vis (CHCl3): λmax/nm 259, 331, 429, 494, 687; HRMS
(MALDI-TOFMS) m/z: M+ calcd for C75H25NO, 955.1936; found,
955.1922.
1
2c (brown solid, 28.1 mg, 59%, mp > 300 °C): H NMR (300
MHz, CS2−CDCl3): δ 8.10 (d, J = 8.2 Hz, 2H), 7.54 (d, J = 8.2 Hz,
2H), 4.81 (s, 2H), 3.94 (s, 3H), 3.80 (t, J = 7.1 Hz, 2H), 3.28 (t, J =
7.1 Hz, 2H); 13C NMR (100 MHz, CS2−CDCl3): δ 168.70, 166.40,
146.55, 145.39, 145.34, 145.20, 145.10, 145.07, 145.00, 144.74,
144.57, 144.55, 144.52, 144.49, 144.13, 144.03, 143.61, 143.55,
143.14, 143.06, 143.00, 142.76, 142.30, 142.13, 142.01, 141.95,
141.19, 141.06, 140.91, 140.89, 137.26, 130.39, 130.03, 128.53, 76.10
(sp3-C of C60), 52.13, 47.57, 43.97, 43.43, 24.99; UV−vis (CHCl3):
λmax/nm 259, 327, 429, 495, 688; HRMS (MALDI-TOFMS) m/z:
M+ calcd for C73H13NO3, 951.0895; found, 951.0891.
2j (brown solid, 8.7 mg, 18%, mp > 300 °C): 1H NMR (300 MHz,
CS2−CDCl3): δ 4.06 (t, J = 7.1 Hz, 2H), 3.99 (t, J = 5.2 Hz, 2H),
3.71 (t, J = 5.2 Hz, 2H), 3.28 (t, J = 7.1 Hz, 2H), 0.98 (s, 9H), 0.18 (s,
6H); 13C NMR (100 MHz, CS2−CDCl3): δ 168.62, 146.79, 145.65,
145.39, 145.16, 145.09, 145.05, 145.01, 144.95, 144.69, 144.54,
144.49, 144.46, 144.03, 144.00, 143.59, 143.52, 143.09, 143.00,
142.96, 142.72, 142.27, 142.10, 141.99, 141.96, 141.15, 140.97,
140.83, 137.21, 76.33 (sp3-C of C60), 61.74, 46.51, 45.79, 44.31,
25.98, 25.35, 18.24, −5.18; UV−vis (CHCl3): λmax/nm 258, 328, 429,
493, 689; HRMS (MALDI-TOFMS) m/z: M+ calcd for
C72H23NO2Si, 961.1498; found, 961.1487.
1
2d (brown solid, 31.2 mg, 61%, mp > 300 °C): H NMR (500
MHz, CS2−CDCl3): δ 7.27 (d, J = 8.3 Hz, 2H), 6.82 (d, J = 8.4 Hz,
2H), 4.64 (s, 2H), 3.73 (t, J = 7.2 Hz, 2H), 3.20 (t, J = 7.1 Hz, 2H),
0.98 (s, 9H), 0.21 (s, 6H); 13C NMR (100 MHz, CS2−CDCl3): δ
167.92, 155.45, 146.65, 145.49, 145.31, 145.28, 145.09, 145.04,
144.98, 144.96, 144.88, 144.63, 144.45, 144.43, 144.39, 143.99,
143.94, 143.52, 143.47, 143.04, 142.95, 142.89, 142.65, 142.22,
142.04, 141.91, 141.87, 141.08, 140.92, 137.13, 129.91, 128.38,
120.45, 76.27 (sp3-C of C60), 47.22, 44.30, 43.10, 25.68, 24.95, 18.13,
−4.31; UV−vis (CHCl3): λmax/nm 260, 328, 429, 497, 688; HRMS
(MALDI-TOFMS) m/z: M+ calcd for C77H25NO2Si, 1023.1655;
found, 1023.1655.
2k (brown solid, 7.6 mg, 16%, mp > 300 °C): 1H NMR (300 MHz,
CS2−CDCl3−DMSO-d6): δ 6.31 (t, J = 5.3 Hz, 1H), 3.93 (t, J = 7.0
Hz, 2H), 3.60 (t, J = 6.8 Hz, 2H), 3.39 (q, J = 5.7 Hz, 2H), 3.22 (t, J =
7.0 Hz, 2H), 1.43 (s, 9H); 13C NMR (125 MHz, CS2−CDCl3−
DMSO-d6): δ 167.32, 155.12, 146.22, 145.09, 144.54, 144.50, 144.15,
144.08, 144.01, 143.99, 143.69, 143.67, 143.59, 143.47, 143.46,
143.04, 143.02, 142.66, 142.52, 142.14, 142.06, 142.01, 141.98,
141.79, 141.31, 141.20, 141.11, 140.82, 140.18, 140.02, 139.89,
136.27, 75.85 (sp3-C of C60), 43.89, 43.12, 43.07, 37.22, 27.68, 24.41;
UV−vis (CHCl3): λmax/nm 260, 328, 429, 493, 687; HRMS
(MALDI-TOFMS) m/z: M+ calcd for C71H18N2O3, 946.1317;
found, 946.1311.
1
2e (brown solid, 24.5 mg, 57%, mp > 300 °C): H NMR (300
MHz, CS2−CDCl3): δ 3.88 (t, J = 7.1 Hz, 2H), 3.58 (t, J = 7.5 Hz,
2H), 3.27 (t, J = 7.1 Hz, 2H), 1.75 (quint, J = 7.1 Hz, 2H), 1.51 (sext,
J = 7.5 Hz, 2H), 1.05 (t, J = 7.3 Hz, 3H); 13C NMR (125 MHz, CS2−
CDCl3): δ 168.19, 146.79, 145.61, 145.41, 145.36, 145.18, 145.14,
145.07, 145.04, 144.96, 144.73, 144.54, 144.51, 144.48, 144.05,
144.03, 143.60, 143.57, 143.11, 143.03, 142.98, 142.72, 142.31,
142.12, 142.01, 141.97, 141.17, 141.00, 137.18, 76.38 (sp3-C of C60),
E
DOI: 10.1021/acs.joc.9b00335
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
2l (brown solid, 4.9 mg, 11%, mp > 300 °C): 1H NMR (300 MHz,
CS2−CDCl3): δ 7.33 (dd, J = 5.1, 1.2 Hz, 1H), 7.16 (dd, J = 3.5, 1.2
Hz, 1H), 7.05 (dd, J = 5.1, 3.5 Hz, 1H), 4.94 (s, 2H), 3.88 (t, J = 7.1
Hz, 2H), 3.27 (t, J = 7.1 Hz, 2H); 13C NMR (100 MHz, CS2−
CDCl3): δ 167.91, 146.55, 145.38, 145.33, 145.28, 145.14, 145.06,
145.03, 145.01, 144.93, 144.68, 144.49, 144.45, 144.05, 143.98,
143.55, 143.51, 143.08, 142.99, 142.93, 142.69, 142.26, 142.07,
141.95, 141.90, 141.13, 140.99, 140.91, 137.84, 137.18, 127.61,
127.26, 126.14, 76.10 (sp3-C of C60), 44.06, 43.13, 41.97, 24.97; UV−
vis (CHCl3): λmax/nm 260, 328, 429, 495, 689; HRMS (MALDI-
TOFMS) m/z: M+ calcd for C69H9NOS, 899.0405; found, 899.0405.
4a16 (brown solid, 18.2 mg, 47%): H NMR (300 MHz, CS2−
CDCl3): δ 10.60 (s, 1H), 2.36 (s, 3H).
1
4b15b (brown solid, 17.4 mg, 44%): H NMR (300 MHz, CS2−
1
CDCl3): δ 10.59 (s, 1H), 2.88 (q, J = 7.2 Hz, 2H), 1.55 (t, J = 7.3 Hz,
3H); 13C NMR (125 MHz, CS2−CDCl3): δ 193.80, 146.81, 145.85,
145.36, 145.34, 145.27, 145.25, 145.08, 144.81, 144.75, 144.74,
144.72, 144.69, 144.52, 143.86, 143.80, 143.30, 143.19, 143.13,
143.06, 143.05, 142.17, 142.09, 142.07, 141.66, 141.24, 141.16,
138.12, 137.93, 75.31 (sp3-C of C60), 51.09, 19.51, 12.29.
1
4c (brown solid, 12.3 mg, 29%, mp > 300 °C): H NMR (300
MHz, CS2−CDCl3): δ 10.58 (s, 1H), 2.81 (t, J = 8.2 Hz, 2H), 1.88−
2.03 (m, 2H), 1.61 (quint, J = 7.3 Hz, 2H), 1.37−1.52 (m, 4H), 0.97
(t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CS2−CDCl3): δ 194.20,
146.97, 145.94, 145.39, 145.38, 145.30, 145.28, 145.11, 144.84,
144.79, 144.76, 144.75, 144.72, 144.55, 143.91, 143.84, 143.33,
143.22, 143.16, 143.09, 143.07, 142.20, 142.12, 141.71, 141.25,
141.19, 138.11, 137.97, 75.33 (sp3-C of C60), 50.39, 31.90, 29.93,
27.85, 26.06, 22.98, 14.35; UV−vis (CHCl3): λmax/nm 260, 327, 429,
493, 689; HRMS (MALDI-TOFMS) m/z: M+ calcd for C68H14O,
846.1045; found, 846.1040.
1
2m (brown solid, 27.7 mg, 61%, mp > 300 °C): H NMR (300
MHz, CS2−CDCl3): δ 7.24−7.40 (m, 5H), 4.81 (s, 2H), 3.68 (t, J =
6.3 Hz, 2H), 2.99−3.07 (m, 2H), 2.30−2.41 (m, 2H); 13C NMR (100
MHz, CS2−CDCl3): δ 164.88, 147.20, 146.41, 145.43, 145.21,
145.08, 145.04, 144.99, 144.88, 144.68, 144.50, 144.47, 144.44,
143.98, 143.51, 143.37, 143.06, 142.96, 142.93, 142.84, 142.52,
142.22, 142.00, 141.72, 141.62, 141.16, 140.88, 140.58, 137.78,
136.69, 128.82, 128.35, 127.75, 76.56 (sp3-C of C60), 50.98, 47.32,
44.94, 25.26, 22.39; UV−vis (CHCl3): λmax/nm 259, 328, 429, 495,
688; HRMS (MALDI-TOFMS) m/z: M+ calcd for C72H13NO,
907.0997; found, 907.0989.
1
4d (brown solid, 11.8 mg, 27%, mp > 300 °C): H NMR (300
MHz, CS2−CDCl3): δ 10.57 (s, 1H), 2.81 (t, J = 8.0 Hz, 2H), 1.83−
2.07 (m, 2H), 1.54−1.72 (m, 2H), 1.19−1.43 (m, 8H), 0.93 (t, J =
7.1 Hz, 3H); 13C NMR (100 MHz, CS2−CDCl3): δ 193.85, 146.91,
145.87, 145.33, 145.24, 145.23, 145.06, 144.78, 144.73, 144.70,
144.66, 144.50, 143.85, 143.78, 143.28, 143.17, 143.11, 143.03,
143.01, 142.15, 142.06, 141.65, 141.21, 141.14, 138.04, 137.91, 75.28
(sp3-C of C60), 50.32, 32.13, 30.25, 29.71, 29.56, 27.85, 26.01, 23.07,
14.42; UV−vis (CHCl3): λmax/nm 259, 328, 429, 498, 691; HRMS
(MALDI-TOFMS) m/z: M+ calcd for C70H18O, 874.1358; found,
874.1344.
2n15e (brown solid, 16.2 mg, 37%): H NMR (300 MHz, CS2−
1
CDCl3): δ 3.80 (t, J = 6.3 Hz, 2H), 3.61 (t, J = 7.6 Hz, 2H), 2.94−
3.10 (m, 2H), 2.33−2.50 (m, 2H), 1.65−1.82 (m, 2H), 1.35−1.54
(m, 2H), 1.03 (t, J = 7.4 Hz, 3H); 13C NMR (100 MHz, CS2−
CDCl3): δ 164.61, 147.36, 146.55, 145.48, 145.27, 145.11, 145.06,
144.99, 144.90, 144.71, 144.55, 144.47, 144.46, 144.00, 143.95,
143.54, 143.40, 143.08, 142.99, 142.95, 142.86, 142.54, 142.25,
142.03, 141.78, 141.66, 141.08, 140.89, 140.58, 137.78, 76.66 (sp3-C
of C60), 48.16, 48.03, 44.98, 29.58, 25.28, 22.54, 20.62, 14.20.
2o (brown solid, 3.6 mg, 8%, mp > 300 °C): 1H NMR (300 MHz,
CS2−CDCl3): δ 4.36 (q, J = 7.1 Hz, 2H), 4.25 (t, J = 4.0 Hz, 1H),
3.62−3.84 (m, 2H), 3.18 (s, 3H), 2.62−2.82 (m, 2H), 1.36 (t, J = 7.0
Hz, 3H); 13C NMR (100 MHz, CS2−CDCl3): δ 170.62, 163.86,
148.63, 147.73, 145.35, 145.28, 145.26, 145.24, 145.18, 145.16,
145.14, 145.11, 145.07, 145.02, 144.90, 144.86, 144.83, 144.71,
144.65, 144.58, 144.52, 144.45, 144.40, 144.24, 144.16, 143.96,
143.67, 143.52, 143.44, 143.39, 143.10, 143.04, 143.00, 142.97,
142.91, 142.85, 142.56, 142.44, 142.32, 142.21, 142.17, 141.93,
141.88, 141.69, 141.65, 141.58, 141.03, 140.96, 140.92, 140.70,
140.62, 138.06, 136.83, 75.81 (sp3-C of C60), 75.10 (sp3-C of C60),
61.88, 47.24, 44.71, 41.02, 35.40, 24.59, 14.53; UV−vis (CHCl3):
λmax/nm 259, 328, 428, 492, 688; HRMS (MALDI-TOFMS) m/z:
M+ calcd for C69H13NO3, 903.0895; found, 903.0887.
1
4e (brown solid, 11.7 mg, 26%, mp > 300 °C): H NMR (300
MHz, CS2−CDCl3): δ 10.57 (s, 1H), 2.81 (t, J = 8.0 Hz, 2H), 1.95
(quint, J = 7.7 Hz, 2H), 1.61 (quint, J = 7.2 Hz, 2H), 1.22−1.53 (m,
12H), 0.92 (t, J = 6.6 Hz, 3H); 13C NMR (125 MHz, CS2−CDCl3): δ
193.95, 146.95, 145.91, 145.37, 145.28, 145.26, 145.09, 144.82,
144.79, 144.77, 144.74, 144.69, 144.53, 143.89, 143.82, 143.32,
143.20, 143.15, 143.08, 143.07, 143.05, 142.19, 142.10, 141.69,
141.24, 141.17, 138.08, 137.95, 75.33 (sp3-C of C60), 50.38, 32.17,
30.24, 29.90, 29.89, 29.75, 29.65, 27.86, 26.04, 23.06, 14.41; UV−vis
(CHCl3): λmax/nm 260, 327, 429, 492, 689; HRMS (MALDI-
TOFMS) m/z: M+ calcd for C72H22O, 902.1671; found, 902.1665.
1
4f (brown solid, 15.1 mg, 34%, mp > 300 °C): H NMR (300
MHz, CS2−CDCl3): δ 10.58 (s, 1H), 5.82 (ddt, J = 17.0, 10.3, 6.6 Hz,
1H), 5.01 (J = 17.1, 1.7 Hz, 1H), 4.94 (ddt, J = 10.2, 2.2, 1.2 Hz, 1H),
2.81 (t, J = 8.1 Hz, 2H), 2.08 (t, J = 6.6 Hz, 2H), 1.88−2.02 (m, 2H),
1.54−1.67 (m, 2H), 1.33−1.50 (m, 6H); 13C NMR (100 MHz, CS2−
CDCl3): δ 194.35, 146.99, 145.96, 145.42, 145.33, 145.31, 145.13,
144.87, 144.82, 144.79, 144.77, 144.73, 144.57, 143.93, 143.86,
143.36, 143.25, 143.19, 143.11, 143.10, 143.09, 142.22, 142.15,
141.74, 141.27, 141.21, 138.98, 138.13, 138.00, 114.43, 75.35 (sp3-C
of C60), 50.40, 34.00, 30.15, 29.55, 29.30, 29.14, 27.83, 26.04; UV−vis
(CHCl3): λmax/nm 259, 327, 429, 489, 689; HRMS (MALDI-
TOFMS) m/z: M+ calcd for C71H18O, 886.1358; found, 886.1355.
4g (brown solid, 4.3 mg, 9%, mp > 300 °C): 1H NMR (300 MHz,
CS2−CDCl3): δ 10.59 (s, 1H), 3.76 (t, J = 6.2 Hz, 2H), 2.84 (t, J =
8.1 Hz, 2H), 1.96−2.10 (m, 2H), 1.75−1.88 (m, 2H), 0.90 (s, 9H),
0.10 (s, 6H); 13C NMR (100 MHz, CS2−CDCl3): δ 194.52, 147.02,
145.99, 145.47, 145.38, 145.36, 145.18, 144.92, 144.86, 144.82,
144.78, 144.63, 143.98, 143.92, 143.40, 143.30, 143.23, 143.16,
143.14, 142.27, 142.22, 142.19, 141.78, 141.31, 141.26, 138.20,
138.06, 75.35 (sp3-C of C60), 62.75, 50.44, 33.29, 26.07, 25.95, 24.35,
18.39, −5.08; UV−vis (CHCl3): λmax/nm 259, 327, 429, 485, 688;
HRMS (MALDI-TOFMS) m/z: M+ calcd for C72H24O2Si, 948.1546;
found, 948.1538.
2q (brown solid, 5.5 mg, 12%, mp > 300 °C): 1H NMR (300 MHz,
CS2−CDCl3): δ 7.37−7.48 (m, 5H), 4.91 (s, 2H), 4.50 (t, J = 5.3 Hz,
2H), 3.80 (t, J = 5.3 Hz, 2H); 13C NMR (100 MHz, CS2−CDCl3): δ
162.71, 145.49, 145.37, 145.16, 145.13, 145.00, 144.99, 144.68,
144.58, 144.56, 144.23, 144.13, 144.01, 143.74, 143.41, 143.05,
143.03, 142.91, 142.89, 142.33, 142.17, 142.15, 141.84, 141.16,
141.10, 140.78, 140.75, 138.71, 135.69, 129.11, 128.72, 128.24, 77.07
(sp3-C of C60), 72.35, 64.66, 50.46, 46.36; UV−vis (CHCl3): λmax/nm
259, 328, 430, 491, 684; HRMS (MALDI-TOFMS) m/z: M+ calcd
for C71H11NO2, 909.0790; found, 909.0790.
2s (brown solid, 9.7 mg, 23%, mp > 300 °C): 1H NMR (300 MHz,
CS2−CDCl3): δ 5.31 (s, 1H), 4.58 (ddd, J = 8.1, 4.5, 2.0 Hz, 1H),
4.32 (d, J = 8.1 Hz, 1H), 3.36 (td, J = 4.2, 2.0 Hz, 1H), 3.10 (dd, J =
11.4, 5.7 Hz, 1H), 2.93 (td, J = 11.9, 4.9 Hz, 1H), 2.59−2.71 (m, 1H),
2.60 (s, 3H), 2.06 (dt, J = 13.4, 4.1 Hz, 1H); 13C NMR (100 MHz,
CS2−CDCl3): δ 148.87, 147.72, 146.14, 145.71, 145.66, 145.55,
145.46, 145.35, 145.04, 144.97, 144.91, 144.72, 144.68, 144.62,
144.59, 144.57, 144.22, 144.12, 144.08, 144.04, 143.52, 143.44,
143.22, 143.18, 143.05, 142.98, 142.91, 142.54, 142.26, 142.23,
142.19, 142.13, 141.17, 141.08, 141.06, 141.01, 137.50, 137.27,
136.90, 136.29, 92.17, 80.70 (sp3-C of C60), 78.21 (sp3-C of C60),
70.54, 55.17, 46.82, 42.87, 36.38, 28.04; UV−vis (CHCl3): λmax/nm
261, 327, 429, 494, 686; HRMS (MALDI-TOFMS) m/z: M+ calcd
for C67H11NO, 845.0841; found, 845.0841.
4h (brown solid, 8.6 mg, 21%, mp > 300 °C): 1H NMR (300 MHz,
CS2−CDCl3): δ 10.49 (s, 1H), 3.99 (t, J = 6.2 Hz, 2H), 3.51 (s, 3H),
3.17 (t, J = 6.1 Hz, 2H); 13C NMR (100 MHz, CS2−CDCl3): δ
193.68, 146.71, 146.00, 145.42, 145.32, 145.20, 144.89, 144.87,
144.81, 144.76, 144.74, 144.57, 143.97, 143.84, 143.36, 143.28,
F
DOI: 10.1021/acs.joc.9b00335
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
143.25, 143.14, 143.06, 142.28, 142.19, 142.17, 141.81, 141.27,
141.24, 138.22, 138.08, 75.00 (sp3-C of C60), 70.32, 59.21, 48.93,
27.33; UV−vis (CHCl3): λmax/nm 259, 327, 429, 486, 687; HRMS
(MALDI-TOFMS) m/z: M+ calcd for C65H8O2, 820.0524; found,
820.0520.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.joc.9b00335.
■
S
1
4i (brown solid, 15.9 mg, 37%, mp > 300 °C): H NMR (300
Spectral data; UV−vis spectra of 2a, 2m, 2q, 2s, 4i, 5a,
5b, and 5c; and NMR spectra of 1d, 1j, 3g, 2a−o, 2q,
2s, 4a−i, and 5a−c (PDF)
MHz, CS2−CDCl3): δ 10.60 (s, 1H), 3.73 (s, 3H), 2.80−2.92 (m,
2H), 2.64 (t, J = 7.4 Hz, 2H), 2.22−2.36 (m, 2H); 13C NMR (100
MHz, CDCl3): δ 194.88, 173.52, 146.85, 145.87, 145.57, 145.54,
145.49, 145.47, 145.46, 145.20, 145.00, 144.94, 144.90, 144.81,
144.73, 144.05, 143.99, 143.48, 143.36, 143.30, 143.23, 143.21,
142.32, 142.24, 141.82, 141.40, 141.33, 138.30, 138.15, 75.06 (sp3-C
of C60), 51.93, 49.58, 34.18, 25.40, 23.02; UV−vis (CHCl3): λmax/nm
260, 328, 429, 496, 692; HRMS (MALDI-TOFMS) m/z: M+ calcd
for C67H10O3, 862.0630; found, 862.0630.
AUTHOR INFORMATION
Corresponding Author
*E-mail: yht898@yahoo.com.
ORCID
■
Reaction of 4i with 4-Methylbenzenesulfonhydrazide for
the Synthesis of 5a. A mixture of 4i (10 mg, 0.0125 mmol) and 4-
methylbenzenesulfonhydrazide (37.2 mg, 0.2 mmol) in chloroform
(10 mL) was stirred at room temperature for 4 h. Upon completion of
the reaction determined by TLC, the solvent was evaporated under
reduced pressure and the residue was purified by column
chromatography with toluene/ethyl acetate (5:1) as the eluent to
give the product 5a (11.6 mg, 90%).
Chun-Bao Miao: 0000-0003-4666-2619
Hai-Tao Yang: 0000-0001-9803-5452
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful for the financial support from the Natural
Science Foundation of Jiangsu Province (BK20181462), the
Jiangsu Key Laboratory of Advanced Catalytic Materials and
Technology (BM2012110), and the Advanced Catalysis and
Green Manufacturing Collaborative Innovation Center.
1
5a (brown solid, 11.6 mg, 90%, mp > 300 °C): H NMR (300
MHz, CS2-DMSO-d6): δ 11.52 (s, 1H), 8.16 (s, 1H), 7.77 (d, J = 7.6
Hz, 2H), 7.54 (s, 1H), 3.69 (s, 3H), 2.40−2.54 (m, 6H), 2.11−2.13
(m, 3H); 13C NMR (125 MHz, CS2−CDCl3−DMSO-d6); δ 171.76,
146.68, 146.35, 144.63, 144.52, 144.30, 144.12, 143.87, 143.80,
143.63, 143.57, 143.55, 143.16, 142.83, 142.18, 142.10, 142.03,
141.60 (br), 141.21, 140.96, 140.12, 139.91, 137.07, 136.23, 135.50,
128.74, 127.02 (br), 76.70 (sp3-C of C60), 50.51, 44.53, 32.94, 27.47,
21.66, 20.86; UV−vis (CHCl3): λmax/nm 259, 328, 431; HRMS
(MALDI-TOFMS) m/z: M+ calcd for C74H18N2O4S, 1030.0987;
found, 1030.0985.
REFERENCES
■
(1) For selected reviews, see: (a) Li, C.-J. Cross-Dehydrogenative
Coupling (CDC): Exploring C−C Bond Formations beyond
Functional Group Transformations. Acc. Chem. Res. 2009, 42, 335−
344. (b) Girard, S. A.; Knauber, T.; Li, C.-J. The Cross-
Dehydrogenative Coupling of Csp3-H Bonds: A Versatile Strategy
for C-C Bond Formations. Angew. Chem., Int. Ed. 2014, 53, 74−100.
(c) Yeung, C. S.; Dong, V. M. Catalytic Dehydrogenative Cross-
Coupling: Forming Carbon−Carbon Bonds by Oxidizing Two
General Procedure for the Reaction of 4i with Indole and 5-
Chloroindole. A mixture of 4i (10 mg, 0.0125 mmol), indole (0.1
mmol), and BF3·Et2O (15 μL, 0.125 mmol) in chloroform (10 mL)
was stirred at room temperature for 4 h. Upon completion of the
reaction determined by TLC, diethyl amine (0.5 mL) was added
slowly under stirring, and then the solvent was evaporated under
reduced pressure and the residue was purified by column
chromatography with toluene/ethyl acetate (5:1) as the eluent to
give the products 5b (11.5 mg, 85%) or 5c (9.9 mg, 69%).
Carbon−Hydrogen Bonds. Chem. Rev. 2011, 111, 1215−1292.
.
For selected recent papers, see: (d) Griffiths, R. J.; Burley, G. A.;
Talbot, E. P. A. Transition-Metal-Free Amine Oxidation: A
Chemoselective Strategy for the Late-Stage Formation of Lactams.
Org. Lett. 2017, 19, 870−873. (e) Jo, H.; Hassan, A. H. E.; Jung, S. Y.;
Lee, J. K.; Cho, Y. S.; Min, S.-J. Construction of 8-Azabicyclo[3.2.1]-
octanes via Sequential DDQ-Mediated Oxidative Mannich Reactions
of N-Aryl Pyrrolidines. Org. Lett. 2018, 20, 1175−1178.
(2) (a) Miyake, Y.; Nakajima, K.; Nishibayashi, Y. Visible-Light-
Mediated Utilization of α-Aminoalkyl Radicals: Addition to Electron-
Deficient Alkenes Using Photoredox Catalysts. J. Am. Chem. Soc.
2012, 134, 3338−3341. (b) Le, C.; Liang, Y.; Evans, R. W.; Li, X.;
MacMillan, D. W. C. Selective sp3 C−H alkylation via polarity-match-
based cross-coupling. Nature 2017, 547, 79−83. (c) Thullen, S. M.;
Rovis, T. A Mild Hydroaminoalkylation of Conjugated Dienes Using
a Unified Cobalt and Photoredox Catalytic System. J. Am. Chem. Soc.
2017, 139, 15504−15508. (d) Nakajima, K.; Miyake, Y.;
Nishibayashi, Y. Synthetic Utilization of α-Aminoalkyl Radicals and
Related Species in Visible Light Photoredox Catalysis. Acc. Chem. Res.
2016, 49, 1946−1956s.
(3) (a) Klapars, A.; Campos, K. R.; Waldman, J. H.; Zewge, D.;
Dormer, P. G.; Chen, C.-Y. Enantioselective Pd-Catalyzed α-Arylation
ofN-Boc-Pyrrolidine: The Key to an Efficient and Practical Synthesis
of a Glucokinase Activator. J. Org. Chem. 2008, 73, 4986−4993.
(b) Cordier, C. J.; Lundgren, R. J.; Fu, G. C. Enantioconvergent
Cross-Couplings of Racemic Alkylmetal Reagents with Unactivated
Secondary Alkyl Electrophiles: Catalytic Asymmetric Negishi α-
Alkylations of N-Boc-pyrrolidine. J. Am. Chem. Soc. 2013, 135,
10946−10949. (c) Jain, P.; Verma, P.; Xia, G.; Yu, J.-Q.
Enantioselective amine α-functionalization via palladium-catalysed
C-H arylation of thioamides. Nat. Chem. 2017, 9, 140−144.
1
5b (brown solid, 11.5 mg, 85%, mp > 300 °C): H NMR (300
MHz, CS2−CDCl3−DMSO-d6): δ 9.94 (s, 2H), 7.35 (s, 2H), 7.22−
7.31 (m, 4H), 6.97 (t, J = 7.4 Hz, 2H), 6.77 (t, J = 7.2 Hz, 2H), 6.05
(s, 1H), 3.45 (s, 3H), 2.88 (t, J = 7.8 Hz, 2H), 1.92 (t, J = 6.9 Hz,
2H), 1.36−1.52 (m, 2H); 13C NMR (100 MHz, CS2−CDCl3−
DMSO-d6): δ 172.17, 148.93, 148.19, 145.12, 145.01, 144.69, 144.59,
144.55, 144.17, 143.95, 143.74, 143.62, 143.28, 143.19, 142.60,
142.48, 142.45, 142.37, 142.34, 141.84, 141.70, 141.57, 140.41,
140.34, 136.88, 136.26, 126.97, 123.39, 121.23, 119.69, 118.63,
115.59, 111.12, 80.56 (sp3-C of C60), 50.60, 49.64, 35.98, 34.01,
29.31, 23.86; UV−vis (CHCl3): λmax/nm 260, 327, 431, 689; HRMS
(MALDI-TOFMS) m/z: M+ calcd for C83H22N2O2, 1078.1681;
found, 1078.1677.
5c (brown solid, 9.9 mg, 69%, mp > 300 °C): 1H NMR (400 MHz,
CS2−CDCl3): δ 8.34 (s, 2H), 7.54 (d, J = 1.9 Hz, 2H), 7.43 (d, J =
1.7 Hz, 2H), 7.34 (d, J = 8.6 Hz, 2H), 7.14 (dd, J = 8.6, 1.9 Hz, 2H),
6.07 (s, 1H), 3.59 (s, 3H), 2.93−3.01 (m, 2H), 2.09 (t, J = 7.1 Hz,
2H), 1.51−1.60 (m, 2H); 13C NMR (100 MHz, CS2−CDCl3): δ
173.04, 148.63, 148.11, 145.42, 145.33, 145.26, 145.23, 145.20,
145.18, 144.95, 144.78, 144.60, 144.41, 144.34, 143.82, 143.75,
143.21, 143.19, 143.10, 143.06, 142.97, 142.95, 142.36, 142.15,
142.13, 141.15, 141.01, 137.45, 137.43, 134.89, 128.41, 125.83,
124.86, 123.04, 119.81, 116.33, 112.45, 80.29 (sp3-C of C60), 51.37,
48.90, 36.27, 34.54, 29.70, 24.34; UV−vis (CHCl3): λmax/nm 258,
327, 432, 692; HRMS (MALDI-TOFMS) m/z: M+ calcd for
C83H20N2O2Cl2, 1146.0902; found, 1146.0894.
G
DOI: 10.1021/acs.joc.9b00335
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
(4) (a) Sundararaju, B.; Achard, M.; Sharma, G. V. M.; Bruneau, C.
sp3 C−H Bond Activation with Ruthenium(II) Catalysts and C(3)-
Alkylation of Cyclic Amines. J. Am. Chem. Soc. 2011, 133, 10340−
10343. (b) Xia, X.-F.; Shu, X.-Z.; Ji, K.-G.; Yang, Y.-F.; Shaukat, A.;
Liu, X.-Y.; Liang, Y.-M. Platinum-Catalyzed Michael Addition and
Cyclization of Tertiary Amines with Nitroolefins by Dehydrogenation
of α,β-sp3 C−H Bonds. J. Org. Chem. 2010, 75, 2893−2902.
(c) Zhou, M.-J.; Zhu, S.-F.; Zhou, Q.-L. Copper-catalyzed Mannich-
type oxidative β-functionalization of tertiary amines. Chem. Commun.
2017, 53, 8770−8773. (d) Takasu, N.; Oisaki, K.; Kanai, M. Iron-
Catalyzed Oxidative C(3)-H Functionalization of Amines. Org. Lett.
2013, 15, 1918−1921. (e) Xia, X.-F.; Shu, X.-Z.; Ji, K.-G.; Shaukat, A.;
Liu, X.-Y.; Liang, Y.-M. Platinum/Scandium-Cocatalyzed Cascade
Cyclization and Ring-Opening Reaction of Tertiary Amines with
Substituted Salicylaldehydes to Synthesize 3-(Aminoalkyl)coumarins.
J. Org. Chem. 2011, 76, 342−345. (f) He, Y.; Wang, F.; Zhang, X.;
Fan, X. C(sp3)−H dehydrogenation and C(sp2)−H alkoxy carbon-
ylation of inactivated cyclic amines towards functionalized N-
heterocycles. Chem. Commun. 2017, 53, 4002−4005. (g) Morigaki,
A.; Kawamura, M.; Arimitsu, S.; Ishihara, T.; Konno, T. Application of
Tertiary Amines Synthesized by Catalytic Dehydrogenation of
Enamines as Nucleophilic C2 Synthons for 1,4-Conjugate Addition
with Fluoroalkylated Olefins. Asian J. Org. Chem. 2013, 2, 239−243.
(5) Griffiths, R. J.; Kong, W. C.; Richards, S. A.; Burley, G. A.; Willis,
M. C.; Talbot, E. P. A. Oxidative β-C-H sulfonylation of cyclic amines.
Chem. Sci. 2018, 9, 2295−2300.
[60]fullerene-fused dihydrocarbolines. Chem. Commun. 2018, 54,
13331−13334. (c) Hu, B.; Liu, T.-X.; Zhang, P.; Liu, Q.; Bi, J.; Shi,
L.; Zhang, Z.; Zhang, G. N-Heterocyclic Carbene-Catalyzed α,β-
Unsaturated Aldehydes Umpolung in Fullerene Chemistry: Con-
struction of [60]Fullerene-Fused Cyclopentan-1-ones and Cyclohex-
2-en-1-ones. Org. Lett. 2018, 20, 4801−4805. (d) Li, Y.; Gan, L.
[60]Fullerene-Based Macrocycle Ligands. Chem. - Eur. J. 2017, 23,
10485−10490. (e) Peng, J.; Huang, G.; Wang, H.-J.; Li, F.-B.; Huang,
C.; Xiang, J.-J.; Huang, Y.; Liu, L.; Liu, C.-Y.; Asiri, A. M.; Alamry, K.
A. TEMPO-Mediated Synthesis of Tetrahydropyridinofullerenes:
Reaction of [60]Fullerene with α-Methyl-Substituted Arylmethan-
amines and Aldehydes in the Presence of 4-Dimethylaminopyridine. J.
Org. Chem. 2018, 83, 85−95.
(10) (a) Li, F.; Wang, L.; Wang, J.; Peng, D.; Zhao, Y.; Li, S.; Zhou,
H.; Wu, J.; Tian, X.; Tian, Y. KOtBu-Mediated, Three-Component
Coupling Reaction of Indoles, [60]Fullerene, and Haloalkanes: One-
Pot, Transition-Metal-Free Synthesis of Various 1,4-(3-Indole)-
(organo)[60]fullerenes. Org. Lett. 2017, 19, 1192−1195. (b) Li, S.-
H.; Li, Z.-J.; Yang, W.-W.; Gao, X. Controlled Synthesis of C70
Equatorial Multiadducts with Mixed Addends from an Equatorial
Diadduct: Evidence for an Electrophilic Carbanion. Org. Lett. 2018,
20, 2328−2332. (c) Lou, N.; Li, Y.; Gan, L. Synthesis of C70-Based
Fluorophores through Sequential Functionalization to Form Isomeri-
cally Pure Multiadducts. Angew. Chem., Int. Ed. 2017, 56, 2403−2407.
́
(d) Reboredo, S.; Giron, R. M.; Filippone, S.; Mikie, T.; Sakurai, T.;
Seki, S.; Martín, N. Cyclobuteno[60]fullerenes as Efficient n-Type
Organic Semiconductors. Chem.Eur. J. 2016, 22, 13627−13631.
(e) Zhou, Z.; Xin, N.; Gan, L. Synthesis of Metal Complexes with an
Open-Cage Fullerene as the Ligand. Chem.Eur. J. 2018, 24, 451−
457.
(6) Huang, X.; Wang, J.; Ni, Z.; Wang, S.; Pan, Y. Synthesis of α,α-
Disulfenylated Aldehydes via Oxidative Transformation of Tertiary
Amines. Org. Lett. 2015, 17, 5488−5491.
(7) (a) Shi, X.; He, Y.; Zhang, X.; Fan, X. FeCl3-Catalyzed Cascade
Reactions of Cyclic Amines with 2-Oxo-2-arylacetic Acids toward
Furan-2(5H)-one Fused N,O-Bicyclic Compounds. Adv. Synth. Catal.
2018, 360, 261−266. (b) Xu, G.-Q.; Xu, J.-T.; Feng, Z.-T.; Liang, H.;
Wang, Z.-Y.; Qin, Y.; Xu, P.-F. Dual C(sp3)-H Bond Functionalization
of N-Heterocycles through Sequential Visible-Light Photocatalyzed
Dehydrogenation/[2+2] Cycloaddition Reactions. Angew. Chem., Int.
Ed. 2018, 57, 5110−5114.
(8) (a) Cui, C.; Li, Y.; Li, Y. Fullerene Derivatives for the
Applications as Acceptor and Cathode Buffer Layer Materials for
Organic and Perovskite Solar Cells. Adv. Energy Mater. 2017, 7,
1601251. (b) Nierengarten, I.; Nierengarten, J.-F. Fullerene Sugar
Balls: A New Class of Biologically Active Fullerene Derivatives.
Chem.−Asian J. 2014, 9, 1436−1444. (c) Anilkumar, P.; Lu, F.; Cao,
L.; G. Luo, P.; Liu, J.-H.; Sahu, S.; N. Tackett II, K., II; Wang, Y.; Sun,
Y.-P. Fullerenes for Applications in Biology and Medicine. Curr. Med.
Chem. 2011, 18, 2045−2059. (d) Martín, N. Carbon Nanoforms for
Photovoltaics: Myth or Reality? Adv. Energy Mater. 2017, 7, 1601102.
(11) Tzirakis, M. D.; Orfanopoulos, M. Radical Reactions of
Fullerenes: From Synthetic Organic Chemistry to Materials Science
and Biology. Chem. Rev. 2013, 113, 5262.
(12) (a) Li, F.; Wang, J.-J.; Wang, G.-W. Palladium-catalyzed
synthesis of [60]fullerene-fused benzofurans via heteroannulation of
phenols. Chem. Commun. 2017, 53, 1852−1855. (b) Wang, G.-W.
Functionalization of [60]Fullerene via Palladium-Catalyzed C-H Bond
Activation. Topics in Organometallic Chemistry; Springer, 2015; Vol.
55, pp 119−136.
(13) Maroto, E. E.; Izquierdo, M.; Reboredo, S.; Marco-Martínez, J.;
Filippone, S.; Martín, N. Chiral Fullerenes from Asymmetric
Catalysis. Acc. Chem. Res. 2014, 47, 2660−2670.
(14) (a) Zhang, Y.; Matsuo, Y.; Li, C.-Z.; Tanaka, H.; Nakamura, E.
A Scalable Synthesis of Methano[60]fullerene and Congeners by the
Oxidative Cyclopropanation Reaction of Silylmethylfullerene. J. Am.
Chem. Soc. 2011, 133, 8086−8089. (b) Zhang, Y.; Matsuo, Y.;
Nakamura, E. Regiocontrolled Synthesis of 1,2-Di(organo)fullerenes
via Copper-Assisted 1,4-Aryl Migration from Silicon to Carbon. Org.
Lett. 2011, 13, 6058−6061. (c) Lu, S.; Jin, T.; Kwon, E.; Bao, M.;
Yamamoto, Y. Highly Efficient Cu(OAc)2-Catalyzed Dimerization of
Monofunctionalized Hydrofullerenes Leading to Single-Bonded
[60]Fullerene Dimers. Angew. Chem., Int. Ed. 2012, 51, 802−806.
(d) Si, W.; Lu, S.; Bao, M.; Asao, N.; Yamamoto, Y.; Jin, T. Cu-
Catalyzed C-H Amination of Hydrofullerenes Leading to 1,4-
Difunctionalized Fullerenes. Org. Lett. 2014, 16, 620−623. (e) Liu,
T.-X.; Zhang, Z.; Liu, Q.; Zhang, P.; Jia, P.; Zhang, Z.; Zhang, G.
Synthesis of [60]Fullerene-Fused Tetrahydroazepinones and Azepi-
nonimines via Cu(OAc)2-Promoted N-Heteroannulation Reaction.
Org. Lett. 2014, 16, 1020−1023. (f) Jiang, S.-P.; Su, Y.-T.; Liu, K.-Q.;
Wu, Q.-H.; Wang, G.-W. Copper(I)-catalyzed heteroannulation of
[60]fullerene with ketoxime acetates: preparation of novel 1-
fulleropyrrolines. Chem. Commun. 2015, 51, 6548−6551. (g) Jiang,
S.-P.; Zhang, M.; Wang, C.-Y.; Yang, S.; Wang, G.-W. Cascade Radical
Reaction of N-Sulfonyl-2-allylanilines with [60]Fullerene: Synthesis
and Functionalization of (2-Indolinyl)methylated Hydrofullerenes.
Org. Lett. 2017, 19, 5110−5113.
́
́
́
(e) Rodríguez-Perez, L.; Ramos-Soriano, J.; Perez-Sanchez, A.;
Illescas, B. M.; Munoz, A.; Luczkowiak, J.; Lasala, F.; Rojo, J.;
̃
Delgado, R.; Martín, N. Nanocarbon-Based Glycoconjugates as
Multivalent Inhibitors of Ebola Virus Infection. J. Am. Chem. Soc.
2018, 140, 9891−9898. (f) Munoz, A.; Sigwalt, D.; Illescas, B. M.;
̃
́
Luczkowiak, J.; Rodríguez-Perez, L.; Nierengarten, I.; Holler, M.;
Remy, J.-S.; Buffet, K.; Vincent, S. P.; Rojo, J.; Delgado, R.;
Nierengarten, J.-F.; Martín, N. Synthesis of giant globular multivalent
glycofullerenes as potent inhibitors in a model of Ebola virus
infection. Nat. Chem. 2016, 8, 50−57. (g) Li, Y.; Lou, N.; Xu, D.; Pan,
C.; Lu, X.; Gan, L. Oxygen-Delivery Materials: Synthesis of an Open-
Cage Fullerene Derivative Suitable for Encapsulation of H2O2 and O2.
Angew. Chem., Int. Ed. 2018, 57, 14144−14148. (h) Isobe, H.; Cho,
K.; Solin, N.; Werz, D. B.; Seeberger, P. H.; Nakamura, E. Synthesis of
Fullerene Glycoconjugates via a Copper-Catalyzed Huisgen Cyclo-
addition Reaction. Org. Lett. 2007, 9, 4611−4614.
(9) (a) Yang, X.-Y.; Lin, H.-S.; Jeon, I.; Matsuo, Y. Fullerene-Cation-
Mediated Noble-Metal-Free Direct Introduction of Functionalized
Aryl Groups onto [60]Fullerene. Org. Lett. 2018, 20, 3372−3376.
(b) Liu, T.-X.; Yue, S.; Wei, C.; Ma, N.; Zhang, P.; Liu, Q.; Zhang, G.
Solvent-promoted catalyst-free regioselective N-incorporation multi-
component domino reaction: rapid assembly of π-functionalized
(15) (a) Yang, H.-T.; Liang, X.-C.; Wang, Y.-H.; Yang, Y.; Sun, X.-
Q.; Miao, C.-B. CuI-Catalyzed Oxidative [3 + 2] Reaction of
Fullerene with Amidines or Amides Using Air as the Oxidant:
H
DOI: 10.1021/acs.joc.9b00335
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
Preparation of Fulleroimidazole or Fullerooxazole Derivatives. Org.
Lett. 2013, 15, 4650−4653. (b) Yang, H.-T.; Liang, X.-C.; Wang, Y.-
H.; Yang, Y.; Sun, X.-Q.; Miao, C.-B. CuCl2-Mediated Reaction of
[60]Fullerene with Amines in the Presence or Absence of Dimethyl
Acetylenedicarboxylate: Preparation of Fulleropyrroline or Aziridino-
fullerene Derivatives. J. Org. Chem. 2013, 78, 11992−11998. (c) Lu,
X.-W.; Xing, M.-L.; Miao, C.-B.; Li, J.-X.; Sun, X.-Q.; Yang, H.-T.
Cu(OAc)2-promoted reaction of [60]fullerene with primary amines
or diamines. Org. Biomol. Chem. 2015, 13, 8405−8410. (d) Yang, H.-
T.; Tan, Y.-C.; Yang, Y.; Sun, X.-Q.; Miao, C.-B. Cu(OAc)2-Mediated
Reaction of C60 with Ureas for the Preparation of Fulleroimidazo-
lidinones. J. Org. Chem. 2016, 81, 1157−1163. (e) Yang, H.-T.; Ge, J.;
Lu, X.-W.; Sun, X.-Q.; Miao, C.-B. Copper-Catalyzed Functionaliza-
tions of C60 with Amino Alcohols. J. Org. Chem. 2017, 82, 5873−
5880. (f) Teng, Q.; Tan, Y.-C.; Miao, C.-B.; Sun, X.-Q.; Yang, H.-T.
Tunable Copper-Catalyzed Reaction of C60 with 2-Ethoxycarbonyla-
cetamides and Subsequent BF3·Et2O-Mediated Isomerization of the
Generated Dihydrofuran-Fused Fullerenes to Fulleropyrrolidinones. J.
Org. Chem. 2018, 83, 15268−15276.
(23) Borah, K. J.; Phukan, M.; Borah, R. Aza-Michael Addition of
Amines to α,β-Unsaturated Compounds Using Molecular Iodine as
Catalyst. Synth. Commun. 2010, 40, 2830−2836.
(24) Wang, S.; Jin, G.; Wang, W.; Zhu, L.; Zhang, Y.; Dong, G.; Liu,
Y.; Zhuang, C.; Miao, Z.; Yao, J.; Zhang, W.; Sheng, C. Design,
synthesis and structure-activity relationships of new triazole
derivatives containing N-substituted phenoxypropylamino side chains.
Eur. J. Med. Chem. 2012, 53, 292−299.
(25) Holland, H. L.; Morris, T. A.; Nava, P. J.; Zabic, M. A new
paradigm for biohydroxylation by Beauveria bassiana ATCC 7159.
Tetrahedron 1999, 55, 7441−7460.
(26) Klenke, B.; Wiegand, I.; Schiffer, G.; Broetz-Oesterhelt, H.;
Maiti, S. N.; Khan, J.; Reddy, A.; Yang, Z.; Hena, M.; Jia, G.; Ligong,
O.; Liang, H.; Yip, J.; Gao, C.; Tajammul, S.; Mohammad, R.;
Biswajeet, G. Amidine Substituted Beta-Lactam Compounds, their
Preparation and use as Antibacterial Agents. U.S. Patent 9,556,165
B2, 2013.
(16) For books, see: (a) Hirsch, A.; Brettreich, M. Fullerenes:
Chemistry and Reactions; Wiley-VCH Verlag GmbH & Co. KGaA:
Weinheim, Germany, 2005. (b) Langa, F.; Nierengarten, J.-F.
Fullerenes: Principles and Applications; RSC Publishing: Cambridge,
U.K., 2007.
(17) (a) Hamada, M.; Hino, T.; Kinbara, K.; Saigo, K. Synthesis and
transformation of a novel methano[60]fullerene having a formyl
group. Tetrahedron Lett. 2001, 42, 5069−5071. (b) Saigo, K.; Ito, H.;
Kishi, Y.; Nishikawa, Y.; Tada, T.; Ishida, Y. A General Method for
the Synthesis of 2,2-[60]Fullerenoalkanals: The Reaction of [60]-
Fullerene with 2-Bromoenol Silyl Ethers. Synlett 2010, 2010, 1811−
1814.
(18) Wang, G.-W.; Lu, Y.-M.; Chen, Z.-X.; Wu, S.-H. An Alternative
Type of Fullerene Products from the Reaction of [60]Fullerene with
Alkoxides and Subsequent Derivatization. J. Org. Chem. 2009, 74,
4841−4848.
(19) (a) Brabec, C. J.; Gowrisanker, S.; Halls, J. J. M.; Laird, D.; Jia,
S.; Williams, S. P. Polymer-Fullerene Bulk-Heterojunction Solar Cells.
́
Adv. Mater. 2010, 22, 3839−3856. (b) Thompson, B. C.; Frechet, J.
M. J. Polymer-Fullerene Composite Solar Cells. Angew. Chem., Int. Ed.
2008, 47, 58−77. (c) Graham, K. R.; Cabanetos, C.; Jahnke, J. P.;
Idso, M. N.; El Labban, A.; Ngongang Ndjawa, G. O.; Heumueller, T.;
Vandewal, K.; Salleo, A.; Chmelka, B. F.; Amassian, A.; Beaujuge, P.
M.; McGehee, M. D. Importance of the Donor:Fullerene
Intermolecular Arrangement for High-Efficiency Organic Photo-
voltaics. J. Am. Chem. Soc. 2014, 136, 9608−9618.
(20) (a) Lawson, G. E.; Kitaygorodskiy, A.; Ma, B.; Bunker, C. E.;
Sun, Y.-P. Photoinduced inter- and intra-molecular electron transfer
reactions of [60]fullerene and a tertiary amine. Formation of the
cycloadduct N-ethyl-trans-2′,5′-dimethylpyrrolidino[3′,4′:1,2][60]-
fullerene. J. Chem. Soc., Chem. Commun. 1995, 2225−2226. (b) Law-
son, G. E.; Kitaygorodskiy, A.; Sun, Y.-P. Photoinduced Electron-
Transfer Reactions of [60]Fullerene with Triethylamine. J. Org. Chem.
1999, 64, 5913−5920. (c) Wang, G.-W.; Chen, X.-P.; Cheng, X.
Unexpected Reactions of [60]Fullerene Involving Tertiary Amines
and Insight into the Reaction Mechanisms. Chem. - Eur. J. 2006, 12,
7246−7253. (d) Chen, M.; Shen, W.; Bao, L.; Cai, W.; Xie, Y.;
Akasaka, T.; Lu, X. Regioselective Thermal Reaction between
Triethylamine and C60 Revisited: X-ray Confirmation of the
Pentane-Fused Adduct and in Situ Mechanism Study. Eur. J. Org.
Chem. 2015, 2015, 5742−5746.
(21) Han, J.; Chen, Y.; Yang, C.; Liu, T.; Wang, M.; Xu, H.; Zhang,
L.; Zheng, C.; Song, Y.; Zhu, J. Structure-based optimization leads to
the discovery of NSC765844, a highly potent, less toxic and orally
efficacious dual PI3K/mTOR inhibitor. Eur. J. Med. Chem. 2016, 122,
684−701.
(22) Banister, S. D.; Rendina, L. M.; Kassiou, M. 7-Azabicyclo-
[2.2.1]heptane as a scaffold for the development of selective sigma-2
(σ2) receptor ligands. Bioorg. Med. Chem. Lett. 2012, 22, 4059−4063.
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DOI: 10.1021/acs.joc.9b00335
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