Copper-Catalyzed Functionalizations of C60 with Amino Alcohols

Article abstract of DOI:10.1021/acs.joc.7b00741

CuI-catalyzed diverse functionalizations of C₆₀ with amino alcohols with aerobic oxygen as the sole oxidant have been explored. For 2-/3-amino alcohols, an aminooxygenation reaction occurs to generate fulleromorpholine and fullerooxazepane derivatives. When a tethered furan ring exists, a further intramolecular [4 + 2] reaction with the neighboring double bond occurs to furnish the cis-1 products. In the case of 4-/5-amino alcohols, methanofullerenes linking with cyclic amides are obtained through cyclic enamine intermediates.

Full text of DOI:10.1021/acs.joc.7b00741

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Article
Copper-Catalyzed Functionalizations of C60 with Aminoalcohols
Hai-Tao Yang, Jie Ge, Xin-Wei Lu, Xiao-Qiang Sun, and Chun-Bao Miao
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 11 May 2017
Downloaded from http://pubs.acs.org on May 11, 2017
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Copper-Catalyzed Functionalizations of C60 with Aminoalcohols
HaiꢀTao Yang,* Jie Ge, XinꢀWei Lu, XiaoꢀQiang Sun, ChunꢀBao Miao
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of
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Petrochemical Engineering, Changzhou University, Changzhou 213164, China.
O
HO
R
n = 3, 4
N
+
( )m
( )
n
HN
R
CuI (cat.)
m = 1, 2
R
air
R'
O
=
O
R'
N
N
O
O
R'
O
O
2
CH -
hv
( )
n
N
R
Abstract
CuIꢀcatalyzed diverse functionalizations of C60 with aminoalcohols with aerobic oxygen as the
sole oxidant have been explored. For 2ꢀ/3ꢀaminoalcohols, an aminooxygenation reaction occurs to
generate fulleromorpholine and fullerooxazepane derivatives. When a tethered furan ring exists, a
further intramolecular [4+2] reaction with the neighbouring double bond occurs to furnish the
cisꢀ1 products. In the case of 4ꢀ/5ꢀaminoalcohols, methanofullerenes linking with cyclic amides
are obtained through cyclic enamine intermediates.
Introduction
The abundant availability of organofullerenes has provided the opportunity for extensive
1
investigation of their potential utilities in medicinal and material science. Development of new
synthetic methods towards organofullerenes with sophisticated and unprecedented architectures is
1
,2
still demanded intensively. Free radical reactions have become one of the most powerful tools
for the modification of C60. To date, the addition of different kinds of radicals generated under
3
photo/thermal conditions or by transition metals to fullerenes has been well documented. In
contrast to the widely investigated Cꢀ and Oꢀ centered radicals, the addition of Nꢀcentered radicals
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6
4
to fullerenes has received less attention. We have been interested in exploring the
functionalization of C60 through the addition of Nꢀcentered radical and have developed the
5
6
2
hypervalent iodine reagent/I systemꢀmediated or Cu(I/II)ꢀcatalyzed/promoted reactions of C60
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with amine compounds. A strategy for the annulation of C60 through an Nꢀcentered radical addition
has been proposed. Addition of Nꢀcentered radical to C60 produces the fullerenyl radical, which is
oxidized to form the diradicals or fullerenyl cation followed by an intramolecular radical coupling
or attack by the tethered nucleophilic atom to afford different kinds of heterocycleꢀfused fullerene
5,6
derivatives. Based on these results, we envision that an aminooxygenation of fullerene may
occur using aminoalcohols as the reactants. Currently, only a handful of reports describe the cyclic
aminooxygenation reaction to access heterocycles containing both oxygen and nitrogen atoms. The
reported cyclization is largely limits to the intermolecular oxidative cyclization of amide with
5
a,6a,7
8
olefines,
carbamates with olefins (Scheme 1).
nitrogen and oxygen atoms are in a conjugated system. Besides, the Nꢀsulfonyl oxaziridines have
intramolecular aminooxygenation of ureas tethered alkenes, or the reaction of
4d,9
The substrates have a common feature that both the
1
0
also been used in the aminooxgenation of olefins catalyzed by copper or iron. Aminoalcohols as
easily availible chemical reagents, which have an alkyl chain between the oxygen and nitrogen
11a
atom, have rarely been investigated in the oxidative cyclization with alkenes to form morpholine
11b
derivatives, which constitute an important scaffolds in drug design/therapeutic medicine. Herein,
we reported the copperꢀcatalyzed its reaction with C60 to realize aminooxygenation and a novel
cyclopropanation reaction (Scheme 1).
Scheme 1
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a. reported cyclic aminooxygenation of alkenes to form heterocycles
O
SO
N
O
2
R1
O
1
N
O
R
2
SO R
N
N
H
X
N
O
X
2
H N
R2
R
R2
X = NHR, OR
O
X = O, NR
b. this work
HO
O
Cu(I) (cat.), air
( )
n
or
N
HN
R
N
R
R
O
alkyl chain
n = 1, 2
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We initiated our study by investigating the reaction of C60 with 2ꢀ(methylamino)ethanol 1a
Table 1). In a preliminary attempt, the reaction of C60 with 2 equiv of 1a using 2 equiv of
(
Cu(OAc) as the oxidant at 120 ºC for 6 h afforded trace amount of the desired product 2a (entry
2
1). When 2 equiv of DMAP (4ꢀdimethylaminopyridine) was added, the desired aminooxygenation
product fulleromopholine 2a was obtained in 10% yield (entry 2). Increasing the amount of 1a to 4
equiv improved the yield of 2a to 21% (entry 3). An extensive copper salts screening showed that
II
other Cu sources such as Cu(NO
3
)
2
•3H
2
O, Cu(ClO
4
)
2
•6H
2
O, and CuSO
4
were ineffective and
CuCl gave a comparable yield of 2a (entries 4ꢀ7). When Cu(OAc) was replaced by CuCl, the
2
2
yield could be improved to 28% (entry 8). Using CuI gave the highest yield of 2a (35%, entry 9).
It was worth noting that in our previous work CuI could not initiate the reaction of primary alkyl
6
c
amines with C60. Gratifyingly, further optimizing the molar ratio of reactants revealed that only a
catalytic amount of CuI was required in the reaction. In view of the atomic economy, the molar
ratio of C :1a:CuI:DMAP as 1:2:0.2:0.4 and a reaction temperature of 120 °C were selected as the
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optimized conditions (entry 12). When the reaction was performed under a N
2
atmosphere, the
yield decreased notably to 6%, which indicated that O played a crucial rule in the reaction (entry
2
3
13). In the absence of DMAP or replacing DMAP by other commonly used base such as Et N,
pyridine, or K
2
3
CO , the yield of 2a was very low (entries 14ꢀ17).
a
Table 1 Screening of the Reaction Conditions
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HO
HN
O
N
conditions
+
Me
1a
Me
2a
ent
ry
1
time
b
additive
molar ratio
yield
(h)
6
0
1
2
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0
1
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1
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9
0
1
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8
9
0
Cu(OAc)
Cu(OAc)
2
2
1:2:2
trace
10
21
18
9
2
/DMAP
1:2:2:2
1:4:2:2
1:4:2:2
1:4:2:2
6
3
Cu(OAc) /DMAP
4
2
4
CuCl
CuSO
Cu(ClO
MAP
Cu(NO ) ꢁ3H O/D
2
/DMAP
/DMAP
ꢁ6H
2
5
4
2
4
)
2
2
O/D
6
7
1:4:2:2
1:4:2:2
2
2
trace
8
3
2
2
MAP
8
9
CuCl/DMAP
CuI/DMAP
CuI/DMAP
CuI/DMAP
1:4:2:2
1:4:2:2
2
2
2
2
2
2
6
2
2
3
28
38
33
22
35
6
1
1
0
1
1:4:0.2:0.2
1:2:0.2:0.2
1:2:0.2:0.4
1:2:0.2:0.4
1:2:0.2
12 CuI/DMAP
c
1
3
CuI/DMAP
CuI
1
4
5
5
1
CuI/Et
3
N
1:2:0.2:0.4
1:2:0.2:0.4
1:2:0.2:0.4
5
16 CuI/pyridine
CuI/K CO
5
1
7
2
3
8
a
C
60 (36 mg), other reactants and reagents,10 mL of
b
c
chlorobenzene, 120 ºC.
undedr N atmosphere.
C60/1a/[Cu]/additive. Operated
2
Under the optimized reaction conditions, the generality of the CuIꢀcatalyzed annulation
reaction of C with aminoalcohols was examined (Table 2). The yield decreased with an
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increase of the steric hindrance of alkyl group on the nitrogen atom (1a
ꢀe). In the case of
2
ꢀ(tertꢀbutylamino)ethanol 1e, no reaction occurred. The Ts ꢀtoluene sulfonyl) group
(p
substituted aminoethanol (1m) could also react with C60 to afford 2m, albeit in low yield.
An aryl group on the nitrogen atom (1p) resulted in the failure of the reaction. Next, the
influence of the substituents at the αꢀC of the oxygen/nitrogen atom was investigated (1fꢀi
and 1s). Both acyclic and cyclic substrates reacted well with C60 to give the desired
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products in good yields except 1s, which decomposed to benzophenone via CꢀC bond
cleavage. The alkenyl, acetal, ester groups and heterocyclic substituents were all tolerated
to the reaction conditions (1jꢀl). 3ꢀAminoꢀ1ꢀpropanols (1q and 1r) could also react with C60
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to provide the sevenꢀmembered ringꢀfused fullerooxazepanes 2q and 2r, however, in low
yield.
Table 2 Substrate Scope for the Aminooxygenation Reactions
CuI (0.2 equiv)
DMAP (0.4 equiv)
PhCl, 120 oC, air
HO R1
( )
O
R1
( )n
n
+
R2
HN
R3
R
2
N
R3
1
2
O
O
N
O
O
N
N
Me
N
Bn
2a (2 h, 35%)
2b (3 h, 30%)
2c (2.5 h, 26%)
2d (3 h, 17%)
O
N
O
Me
O
O
N
Me
N
Me
Me
N
2e (0%)
2f (2.5 h, 26%)
2g (3 h, 24%)
2h (2 h, 30%)
O
N
O
N
O
N
O
N
OMe
2
i (2 h, 29%)
2j (3 h, 34%)
2k (6 h, 7%)
OMe MeO
2l (6 h, 15%)
O
O
O
N
O
N
N
Ts
S
N
2
m (5.5 h, 11%)
2n (3 h, 33%)
2o (5 h, 10%)
O
O
N
O
Ph
O
Ph
Bn
N
Ph
N
N
2s (0%)
Me
Me
2
p (0%)
2q (3 h, 10%)
2r (3 h, 11%)
When 2ꢀ(2ꢀfurylmethylamino)ethanol 3a was introduced to the CuIꢀcatalyzed reaction
(Scheme 2), the cisꢀ1 product 4a was formed in 16% yield through a further intramolecular
4+2] reaction of the furan ring with a neighbouring double bond. However, the very poor
[
13
solubility did not enable the C NMR characterization. This problem was solved by
introducing a long alkyl chain on the furan ring (substrate 3b) and the cisꢀ1 product 4b was
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4
4
4
4
4
4
4
5
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5
5
5
5
5
5
6
obtained in 21% yield. No observation of the intermolecular reaction between C60 and
2ꢀpentylfuran indicated that the intramolecular fashion facilitated the [4+2] reaction. To the
best of our knowledge, only a few examples of the [4+2] cycloaddition of isobenzofuran
0
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5
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9
0
1
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9
0
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9
0
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with C60 have been reported up to now. This is the first example of a [4+2] reaction of
fullerene with simple furans. The cisꢀ1 product 4b was very sensitive to light. Upon
photoirradiation with a 125 W fluorescent highꢀpressure mercury lamp, it was transformed
to cisꢀ1 product 5b quickly via a retro [4+2] reaction and further intramolecular [2+2]
1
13
reaction. The structrure of 5b was fully characterized by its H NMR, C NMR, HꢀH Cosy,
HSQC, HMBC, and NOESY spectral analysis (see Supporting Information). In contrast to
4
b,
4a was more stable under photoirradiation, which meaned that the alkyl group on the
α
ꢀposition of the furan ring had great influence on the retro [4+2] reaction. The formtion of
cisꢀ1 fullerene derivatives through intramolecular [2+2] cyclization has only been reported
1
3
by Martín’s group from a fullerꢀ1,6ꢀenynes precursor under thermal conditions. In the
formation of 4b or its conversion to 5b, the key intermediate 4b' could not be detected. To
exactly prove the reaction pathway, 3t was prepared and reacted with C60 under the same
conditions. The aminooxygenation product 2t was obtained because the fusedꢀphenyl ring
prevented the intramolecular [4+2] reaction. As anticipated, 2t underwent intramolecular
[
2+2] reaction under photoirradiation to furnish the product 5t in 67% yield.
Scheme 2 Reaction of C60 with Aminoethanols Connecting a Furyl Group
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O
N
O
R
CuI (0.2 equiv)
DMAP (0.4 equiv)
PhCl, 120 oC, air
O
R
N
H
+
OH
4
equiv
3
a, R = H
3b, R = n-C H
4a (6 h, 16%)
4b (3 h, 21%)
5
11
5 11
C H
O
O
O
5 11
C H
10
11
12
13
14
15
16
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N
N
O
N
O
O
5 11
C H
hv, 1 h
4
b
4b'
5b (52%)
O
N
O
CuI (0.2 equiv)
DMAP (0.4 equiv)
PhCl, 120 oC, air
O
hv
N
2 h
+
O
N
H
2t (19%)
OH
O
5t (67%)
3t (4 equiv)
The success of the reaction between 3ꢀaminoꢀ1ꢀpropanols (1q and 1r) and C inspired
60
us to construct the more challenging eight/nineꢀmembered ring fused C60 derivatives using
aminoalchols with longer carbon chains (Scheme 3). Treatment of C60 with
4ꢀmethyaminoꢀ1ꢀbutanol 6a under the standard conditions delivered a single product.
Surprisingly, the NMR analysis revealed that it was not the anticipated eight membered
ring fused C60 but the methanofullerene 7a. 4ꢀBenzylaminoꢀ1ꢀbutanol 6b and
4
ꢀhexylaminoꢀ1ꢀbutanol 6c both reacted with C60 to give similar methanofullerenes 7b and
7c, respectively. During the course of the reaction of C60 with 6b, an intermediate 7b'
with greater polarity was formed at first. With the progress of the reaction, 7b' was
gradually transformed to 7b. Changing the substrate from 4ꢀbenzylaminoꢀ1ꢀbutanol to
5
ꢀbenzylaminoꢀ1ꢀpentanol gave the analogous product 7d in 24% yield. No reaction
occurred by further extending the carbon chain to 6ꢀmethylaminoꢀ1ꢀhexanol.
Scheme 3 Reaction of C60 with 4-/5-Aminoalcohols
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1
1
2
2
2
2
2
2
2
2
2
2
3
3
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3
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3
3
3
3
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4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
O
R
N
HO
NHR
6a, R = Me
6b, R = Bn
6c, R = n-C
7a (8 h, 15%)
7b (12 h, 50%)
7c (3 h, 29%)
6
H
11
CuI (0.2 equiv)
DMAP (0.4 equiv)
PhCl, 120 oC, air
Bun
O
HO
HO
NHBun
N
6
d
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
7
d (3 h, 24%)
Bn
N
7b'
As for the formation of methanofullerens 7aꢀd, undoubtedly a new CꢀN bond formed
between nitrogen atom and the carbon atom of hydroxyl group. The reasonable reaction
intermediate might be the cyclic enamines or the cyclic amides which could be formed
through oxidation of primary alcohols to aldehydes followed by intramolecular
condensation or further oxidation. To gain an insight into this interesting transformation,
two control experiments were conducted (Scheme 4). When
treated with C60 under standard conditions, no reaction occurred. However, the reaction of
cyclic enamine with C60 afforded the methanofullerene 7e in 21% yield, which
Nꢀmethylꢀ2ꢀpyrrolidinone was
8
unambiguously certified that cyclic enamines were the key intermediates. We also tried to
isolate the key intermediate cyclic enamine from the reaction of C60 with 6b, but failed, probably
because the formation of cyclic enamine is rather slower than it’s further oxidation by Cu(II). The
reaction of enamines derived from ketones with C60 has ever been investigated by the
Oshima and Wu groups. Whereas, the [2+2] cycloaddition products were obtained via
a
1
4
SET (single electron transfer) process.
Scheme 4 Control Experiments
CuI (0.2 equiv)
DMAP (0.4 equiv)
O
Me
Bn
N
N
+
× o
O
N
PhCl, 120 C, air
Me
7
a (0%)
CuI (0.2 equiv)
DMAP (0.4 equiv)
PhCl, 120 oC, air
O
+
Me
N
Me
Bn
8
7
e (6 h, 21%)
CuI (0.2 equiv)
DMAP (0.4 equiv)
HO
HO
O
O
+
×
PhCl, 120 oC, air
9 (0%)
To gain more information about the reaction mechanism, the CuIꢀcatalyzed reaction of C60 with
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1a
or
6b
in
the
presence
of
radical
scavengers
such
as
or
TEMPO
BHT
(2,2,6,6ꢀtetramethylpiperidineꢀ1ꢀoxy),
AIBN
(azoisobutyronitrile),
(2,6ꢀditertbutylꢀ4ꢀmethylphenol) was carried out (Scheme 5). For the reaction of C60 with 1a, the
radical scavengers has no significant influence on the reaction. The addition of BHT or AIBN only
resulted in lower yield. In terms of the reaction of C60 with 6b, the addition of TEMPO severely
prohibited the cyclopropanation reaction and only afforded trace of 7b after 22 h, however, a new
unidentified product with slightly less polarity was generated. In the presence of AIBN, the
reaction of C60 with 6b was inhibited completely. In the presence of BHT, within a short time, no
reaction occurred between C60 and 6b and only the oxidation of BHT was observed. Further
extending the reaction time, the formation of 7b was observed and was obtained in 39% yield
finally. Although the radical trapping experiment between C60 and 1a did not support a radical
process, this could not exclude the possibility of a radical pathway because TEMPO has generally
been used to capture Cꢀcentered radicals but not Nꢀcentered radicals. Moreover, many
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54
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57
58
59
60
1
5
TEMPOꢀmediated reactions have been reported to undergo a radical pathway. Recently,
oxidative conversion of tertiary amines to α,αꢀdisulfenylated aldehydes through enamine
1
6
intermediates was also reported involving a radical process.
Scheme 5 Free Radicals Capture Experiments
CuI (0.2 equiv)
HO
O
DMAP (0.4 equiv)
PhCl, 120 oC, air
+
HN
N
CH
3
CH3
1a
additive
2a
TEMPO (3 equiv), 3 h
AIBN (3 equiv), 5 h
BHT (3 equiv), 5 h
33%
27%
23%
CuI (0.2 equiv)
DMAP (0.4 equiv)
PhCl, 120 oC, air
O
HO
Bn
N
+
HN
Bn 6b
7b
additive
TEMPO (3 equiv), 22 h
AIBN (3 equiv), 12 h
trace
0%
39%
BHT (3 equiv),16 h
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2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
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3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
The exact reaction process is still unclear now.
A
plausible mechanism for the formation
of
2
and
7
is outlined in Shceme 6. The reaction of CuI with aerobic O in the presence of
2
1
7
DMAP may generate a Cu(II) complex. For 2ꢀ/3ꢀaminoalcohol
oxidation by Cu(II) followed by release of proton from the generated radical cation
results in the formation of the nitrogen radical , which adds to C60 to furnish the fullerenyl
radical . Further oxidation of by Cu(II) may afford fullernyl cation
consequent intramolecular attack by hydroxyl group provides the aminooxygenation
product . A radical coupling pathway to through an oxygen radical was excluded
because the reaction of C60 with ethylene glycol under standard conditions did not produce
the C60ꢀfused dioxane (Scheme 4), which implied the oxygen radical could not be
1, single electron
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
A
B
18
C
C
D
and the
2
2
9
generated. In terms of 4ꢀ/5ꢀaminoalcohol
5
, an oxidation of primary alcohol to aldehyde
E
1
7b,19
may occur in the presence of Cu(I) and O2
followed by an intramolecular condensation
to afford cyclic enamine
another resonance form . Additon of
generates fullerenyl radical . Three possible pathways may exist for its further
transformation. In path a, similar SET process occurs to furnish biradical , which
undergoes coupling reaction to generate . In path b, addition of a fullerenyl radical to the
double bond of enamine generates radical , which undergoes single electron oxidation to
furnish . In path c, oxidation of the fullerenyl radical to the fullerenyl cation followed
by intramolecular attack with the enamine would also deliver . Nucleophilic addition of
O to generates the ꢀacetal and the subsequent oxidation affords the
methanofullerene
Scheme 6 Plausible mechanism
G
. SET from
G to Cu(II) gives radical cation H, which has
I
I
to C60 followed by concurrent release of a proton
K
M
P
N
P
O
P
H
2
P
O
,
N
Q
7
.
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HO
HO
HO
H+
HO
[CuII]
O
-
C
-H+
60
(
)
n
( )
n
HN
R
N
R
( )
n
( )
n
( )
n
N
R
N
R
N
R
A
-[CuI]
B
n = 1,2
CuI]
C
D
2
[
O
2
CuI + DMAP
O
[
CuII]
HO
II
[CuII]
[CuI]
[
Cu ], O
2
2
-H O
(
)
m
( )m
HO
( )
m
( )
m
(
)
n
( )n
N
R
F
N
n = 3, 4
N
R
N
HN
R
HN
m = 1,2
R
H
R
R
E
I
G
1
or 5
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41
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45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
( )
m
H
( )m
( )m
N
-H+
N
[CuII]
R
C
60
N
R
R
path a
L
J
b
K
th
a
p
( )
m
[CuII]
( )
m
(
)
m
N
R
N
N
R
R
P
N
M
2
H O
(
)
m
N
( )
m
CuII]
[
( )
m
R
N
N
R
R
HO
O
O
Q
7
Conclusion
In summary, the CuIꢀcatalyzed reaction of C60 with aminoalcohols using the aerobic
oxygen as the oxidant has been extensively investigated. The aminooxygenation reaction
occurs for 2ꢀ/3ꢀaminoalcohols. When a furylmethyl group bonds to the nitrogen atom,
further intramolecular [4+2] reaction with the neighbouring double bond occurs to generate
cisꢀ1 product, which undergoes retro [4+2] reaction and a further [2+2] reaction under
photoirradiation. In the case of the 4ꢀ/5ꢀaminoalcohols, an entirely different reaction
process is triggered through cyclic enamines intermediates to provide the
methanofullerenes linking with cyclic amides.
Experimental Section
1
13
General Information. All reactions were conducted under an air atmosphere. H and C NMR
(broadband decoupling) spectra were recorded on 300, 400, and 500 MHz (75, 100, and 125 MHz
13
for C NMR) spectrometer at ambient temperature, using TMS as an internal standard. HꢀH Cosy,
HSQC, HMBC, and NOESY spectra were recorded on 500 MHz spectrometer at ambient
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4
4
4
4
4
4
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4
5
5
5
5
5
5
5
5
5
5
6
temperature. Flash column chromatography was performed over silica gel (200−300 mesh). The
MALDIꢀTOF
Eꢀ(2ꢀ[3ꢀ(4ꢀtertbutylphenyl)ꢀ2ꢀmethylꢀ2ꢀpropenylidene]malononitrile) as the matrix. UVꢀvis spectra
were conducted on Shimadzu UVꢀ2401 spectrometer with CHCl as the solvent.
MS
were
measured
in
positive
ion
mode
using
DCTB
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
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9
0
1
2
3
4
5
6
7
8
9
0
3
2
0
21
22
23
24
Starting materials 1j, 1k, 1n, 1o, 3a, 6c, and 8 were prepared according to the reported
procedures.
Preparation of 1l and 3t. A mixture of ethanolamine (183 mg, 3 mmol) and corresponding
aldehydes (methyl 4ꢀformylbenzoate or benzofuranꢀ2ꢀcarbaldehyde, 2 mmol) in methanol (2 mL)
o
o
4
was stirred at 60 C for overnight. After cooling to 0 C, NaBH (114 mg, 3 mmol) was added
portionꢀwise. The mixture was stirred at room temperature for 1 h until completion of the
reduction as determined by TLC. 0.5 mL of water was added to quench the reaction and the
solvent was removed in vacuo. The residue was extracted with methylene dichloride (2 × 20 mL).
The combined organic layers was dried with anhydrous sodium sulfate, filtered, and evaporated in
vacuo. The residue was purified by column chromatography with CH
2
Cl
2
/MeOH (1:15) as a eluent
1
to give the 1l (pale yellow oil, 188 mg, 45%) or 3t (pale yellow oil, 267.5 mg, 70%). 1l: H NMR
3
(300 MHz, CDCl ) δ 8.01 (d, J = 8.3 Hz, 2H), 7.40 (d, J = 8.4 Hz, 2H), 3.92 (s, 3H), 3.88 (s, 2H),
13
3
.68 (t, J = 5.1 Hz, 2H), 2.81 (t, J = 5.1 Hz, 2H), 1.91 (br, 2H); C NMR (75 MHz, CDCl ) δ
3
+
1
67.1, 145.4, 129.9, 129.1, 128.1, 61.1, 53.3, 52.2, 50.7; HRMS (ESIꢀQꢀTOF) m/z [M+H] Calcd
1
for C11
H
16NO
3
210.1130, found 210.1126. 3t: H NMR (300 MHz, CDCl
3
) δ 7.49ꢀ7.54 (m, 1H),
7.41ꢀ7.46 (m, 1H), 7.16ꢀ7.28 (m, 2H), 6.56 (q, J = 0.7 Hz, 1H), 3.94 (d, J = 0.6 Hz, 2H), 3.67 (t, J
13
=
5.2 Hz, 2H), 2.82 (t, J = 5.2 Hz, 2H), 2.44 (br, 2H); C NMR (75 MHz, CDCl
3
) δ 156.3, 155.0,
+
1
28.4, 124.0, 122.8, 120.8, 111.1, 104.0, 60.9, 50.5, 46.2; HRMS (ESIꢀQꢀTOF) m/z [M+H] Calcd
2
for C11H14NO 192.1025, found 192.1016.
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Preparation of 1r. Step 1: Amixture of diethyl benzylmalonate (500 mg, 2 mmol) and
methylamine (25% aqueous solution, 372 mg, 3 mmol,) in 3 mL of tetrahydrofuran was stirred at
room temperature for overnight. Water (20 mL) was added and the mixture was extracted with
methylene dichloride (2 × 20 mL). The combined organic layers was 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 a eluent to give the product ethyl
2ꢀbenzylꢀ3ꢀ(methylamino)ꢀ3ꢀoxopropanoate (350 mg, 74%). Step 2: To a solution of lithium
aluminum hydride (114 mg, 3 mmol) in dry tetrahydrofuran (15 mL) was added dropꢀwise a
solution of ethyl 2ꢀbenzylꢀ3ꢀ(methylamino)ꢀ3ꢀoxopropanoate (300 mg, 1.3 mmol) in dry
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49
50
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54
55
56
57
58
59
60
o
tetrahydrofuran (10 mL) at 0 C. After addition, the mixture was heated at reflux for overnight.
Under iceꢀcooling, the reaction was quenched with water (1 mL) and the insoluble substance was
filtered off. The filtrate was dried with anhydrous sodium sulfate and concentrated. The crude
product was purified by column chromatography with CH
2
Cl
2
/MeOH (1:30) as a eluent to give the
) δ 7.10ꢀ7.32 (m, 5H), 3.72 (ddd, J
1
1
r (143 mg, 63%, pale yellow oil). H NMR (300 MHz, CDCl
3
=
10.8, 3.8, 1.7 Hz, 1H), 3.66 (br, 2H), 3.56 (dd, J = 10.6, 8.3 Hz, 1H), 2.78 (ddd, J = 11.8, 3.4, 1.6
Hz, 1H), 2.59 (dd, J = 11.8, 9.5 Hz, 1H), 2.53 (dd, J = 13.7, 7.3 Hz, 1H), 2.43 (dd, J = 13.5, 7.4 Hz,
13
1
H), 2.35 (s, 3H), 1.97ꢀ2.13 (m, 1H); C NMR (75 MHz, CDCl ) δ 139.9, 128.9, 128.4, 126.1,
3
+
6
7.8, 56.58, 40.8, 36.4, 36.2; HRMS (ESIꢀQꢀTOF) m/z [M+H] Calcd for C11
H
18NO 180.1388,
found 180.1390.
Preparation of 3b. Step 1: Phosphorus oxychloride (670 mg, 4.5 mmol) was added dropwise to
o
dry N,Nꢀdimethylformamide (2 mL) while keeping the temperature below 20 C. The solution was
o
stirred for 1 h at 40 C. 2ꢀPentylfuran (415 mg, 3 mmol) was added slowly with a syringe at such a
rate to maintain the temperature below 25 ºC. The mixture was stirred for 3 h at the room
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6
temperature. An aqueous sodium carbonate solution (20 mL) was added slowly to quench the
reaction and the mixture was extracted with ethyl acetate (2 × 20 mL). The combined organic
layers was dried with anhydrous sodium sulfate, filtered, and evaporated in vacuo. The residue was
purified by column chromatography with ethyl acetate/petroleum ether = 1/20 as the eluent to give
the product 5ꢀpentylfuranꢀ2ꢀcarbaldehyde. Step 2: A mixture of 5ꢀpentylfuranꢀ2ꢀcarbaldehyde
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(332 mg, 2 mmol) and ethanolamine (183 mg, 3mmol) of in methanol (2 mL) was stirred for
overnight at 60 ºC. After cooling to 0 ºC, sodium borohydride (114mg, 3mmol) was added
portionꢀwise, and then the resulting solution was stirred at room temperature for 1 h. 20 mL of
water was added and the mixture was extracted with methylene dichloride (2 x 20 mL). The
combined organics were dried with anhydrous sodium sulfate, filtered, and evaporated in vacuo.
2 2
The crude product was purified by column chromatography with CH Cl /MeOH (1:20) as eluent
1
to give the 3b (240 mg, 57%, pale yellow oil). H NMR (300 MHz, CDCl ) δ 6.05 (d, J = 3.0 Hz,
3
1H), 5.88 (d, J = 3.0 Hz, 1H), 3.74 (s, 2H), 3.64 (t, J = 5.2 Hz, 2H), 2.78 (t, J = 5.2 Hz, 2H), 2.58
(t, J = 7.6 Hz, 2H), 2.03 (br, 2H), 1.62 (quint, J = 7.4 Hz, 2H), 1.27ꢀ1.42 (m, 4H), 0.90 (t, J = 6.8
1
3
Hz, 3H); C NMR (75 MHz, CDCl
3
) δ 156.2, 151.5, 107.8, 105.2, 60.9, 50.4, 45.9, 31.5, 28.1;
212.1651, found 212.1644.
+
HRMS (ESIꢀQꢀTOF) m/z [M+H] Calcd for C12
H
22NO
2
Preparation of 6d. A mixture of δꢀvalerolactone (500 mg, 5 mmol) and nꢀbutylamine (1.1 g, 15
mmol) in water (2 mL) was stirred at room temperature for 2 h. Water and excess amine were
removed under reduced pressure by adding ethanol. The obtained crude
4
Nꢀbutylꢀ5ꢀhydroxypentanamide in 20 ml THF was slowly added to LiAlH (380 mg, 10 mmol) at 0
o
C. The mixture was refluxed for overnight, cooled to room temperature, and quenched with water.
The suspension was filtered and concentrated to dryness with anhydrous sodium sulfate to give the
1
crude compound as pale yellow oil (536 mg, 67%) without further purification. H NMR (300
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2
5
MHz, CDCl
3
)
δ 3.64 (t, J = 6.3 Hz, 2H), 2.61 (t, J = 7.2 Hz, 2H), 2.59 (t, J = 7.3 Hz, 2H),
+
1
.26ꢀ1.65 (m, 10H), 0.92 (t, J = 7.2 Hz, 3H); HRMS (ESIꢀQꢀTOF) m/z [M+H] Calcd for
C
9
H
22NO 160.1701, found 160.1696.
General Procedure for the CuI-Catalyzed Reaction of C60 with Aminoalcohols 1, 6, 3a, 3b,
or 3t. A mixture of C60 (36.0 mg,0.05mmol), aminoalcohols (1aꢀl, 1n-s and 6aꢀd, 0.1 mmol; 1m,
.25 mmol; 3a, 3b, and 3t, 0.2 mmol), CuI (1.9 mg, 0.01 mmol), and DMAP (2.5 mg, 0.02 mmol)
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13
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21
22
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31
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40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
0
was stirred vigorously in 10 mL of chlorobenzene in a tube (Φ18 × 150 mm) under open air at 120
ºC for given time. The solvent was removed in vacuo and the residue was purified on a silica gel
column with CS
products 2aꢀd, 2f-o, 2q, 2s, 6a-d, 4a, 4b, and 2t.
a (brown solid, 13.9 mg, 35%, mp > 300 °C): H NMR (400 MHz, CS
2
/toluene (100:0ꢀ0:100, gradient elution) as the eluent to give unreacted C60 and
1
2
2
ꢀCDCl
3
) δ 4.97 (t, J =
13
7
1
1
1
λ
.8 Hz, 2H), 4.07 (t, J = 7.7 Hz, 2H), 3.54 (s, 3H); C NMR (100 MHz, CS ꢀCDCl ) δ 150.23,
2
3
48.58, 148.35, 146.70, 146.62, 146.33, 146.22, 145.90, 145.80, 145.60, 145.57, 145.44, 145.40,
44.91, 144.87, 142.81, 142.80, 142.47, 142.41, 141.98, 141.69, 141.63, 141.42, 139.75, 139.31,
3
3
37.81, 137.30, 89.20 (sp ꢀC of C60), 78.67 (sp ꢀC of C60), 61.50, 48.20, 43.77; UV−vis (CHCl
3
)
+
max/nm 257, 316, 690; HRMS (MALDIꢀTOFMS) m/z [M+H] calcd for C63
H
8
NO 794.0606,
found 794.0603.
b (brown solid, 12.5 mg, 30%, mp > 300 °C): H NMR (500 MHz, CS
.6 Hz, 2H), 4.20 (t, J = 7.6 Hz, 2H), 4.03 (t, J = 7.2 Hz, 2H), 1.89 (quint, J = 7.4 Hz, 2H), 1.59
1
2
2 3
ꢀCDCl ) δ 4.89 (t, J =
7
13
(
sextet, J = 7.4 Hz, 2H), 1.05 (t, J = 7.4 Hz, 3H); C NMR (100 MHz, CS
2
ꢀCDCl
50.54, 148.55, 148.32, 146.64, 146.57, 146.28, 146.27, 146.19, 145.83, 145.73, 145.53, 145.49,
45.44, 145.36, 144.91, 144.86, 142.78, 142.72, 142.44, 142.40, 141.93, 141.69, 141.52, 141.50,
3
) δ 151.54,
1
1
1
3
3
39.68, 139.58, 137.84, 136.99, 87.69 (sp ꢀC of C60), 79.78 (sp ꢀC of C60), 61.18, 54.16, 43.75,
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1
1
1
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1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
32.48, 20.92, 14.45; UVꢀVis (CHCl
3
) λmax/nm 258, 316, 693; HRMS (MALDIꢀTOFMS) m/z
+
[
M+H] calcd for C H NO 836.1075, found 836.1074.
6
6
14
1
2c (brown solid, 11.2 mg, 26%, mp > 300 °C): H NMR (400 MHz, CS
2
ꢀCDCl
3
) δ 7.69 (d, J =
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
7.4 Hz, 2H), 7.42 (t, J = 7.3 Hz, 2H), 7.33 (t, J = 7.2 Hz, 1H), 5.25 (s, 2H), 4.90 (t, J = 7.5 Hz, 2H),
1
3
4.06 (t, J = 7.5 Hz, 2H); C NMR (100 MHz, CS
46.70, 146.62, 146.34, 146.32, 146.25, 145.85, 145.80, 145.56, 145.52, 145.49, 145.42, 144.94,
144.91, 142.82, 142.78, 142.49, 142.44, 142.01, 141.76, 141.56, 141.52, 139.80, 139.67, 139.52,
2 3
ꢀCDCl ) δ 151.26, 150.52, 148.60, 148.37,
1
3
3
137.90, 137.17, 128.89, 128.67, 127.57, 88.04 (sp ꢀC of C60), 79.57 (sp ꢀC of C60), 61.29, 58.71,
+
42.62; UVꢀVis (CHCl
12NO 870.0919, found 870.0911.
d (brown solid, 7.0 mg, 17%, mp > 300 °C): H NMR (500 MHz, CS
Hz, 2H), 4.60 (hept, J = 6.5 Hz, 1H), 4.14 (t, J = 7.7 Hz, 2H), 1.60 (d, J = 6.5 Hz, 6H); C NMR
125 MHz, CS ꢀCDCl ) δ 151.49, 150.67, 148.49, 148.35, 146.57, 146.55, 146.26, 146.10,
45.74, 145.63, 145.59, 145.42, 145.32, 144.90, 144.89, 142.82, 142.75, 142.72, 142.44, 142.39,
3
) λmax/nm 258, 317, 691; HRMS (MALDIꢀTOFMS) m/z [M+H] calcd for
69
C H
1
2
2 3
ꢀCDCl ) δ 4.80 (t, J = 7.7
13
(
2
3
1
1
6
3
3
41.93, 141.67, 141.41, 139.62, 139.42, 137.89, 136.62, 87.81 (sp ꢀC of C60), 79.46 (sp ꢀC of C60),
3
2.37, 52.86, 38.31, 23.09; UVꢀVis (CHCl ) λmax/nm 258, 319, 691; HRMS (MALDIꢀTOFMS)
+
m/z [M+H] calcd for C H NO 822.0919, found 822.0911.
65
12
1
2
f (brown solid, 10.5 mg, 26%, mp > 300 °C): H NMR (500 MHz, CS
H), 4.27 (dd, J = 12.9, 7.7 Hz, 1H), 3.48ꢀ3.53 (m, 1H), 3.49 (s, 3H), 1.90 (d, J = 6.3 Hz, 3H); C
NMR (100 MHz, CS ꢀCDCl ) δ 150.67, 150.62, 149.96, 148.52, 148.29, 146.68, 146.64, 146.59,
46.56, 146.30, 146.27, 146.20, 146.08, 145.91, 145.89, 145.84, 145.73, 145.69, 145.51, 145.40,
2 3
ꢀCDCl ) δ 5.14ꢀ5.24 (m,
13
1
2
3
1
1
1
45.37, 145.36, 145.35, 144.92, 144.89, 144.88, 144.78, 142.81, 142.79, 142.76, 142.73, 142.47,
42.41, 142.38, 141.97, 141.93, 141.85, 141.68, 141.58, 141.56, 141.50, 141.07, 139.79, 139.64,
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139.29, 139.02, 138.11, 137.75, 137.11, 136.98, 89.93 (sp ꢀC of C60), 77.84 (sp ꢀC of C60), 68.39,
5
6.14, 44.15, 23.93; UVꢀVis (CHCl ) λmax/nm 258, 316, 690; HRMS (MALDIꢀTOFMS) m/z
3
+
[M+H] calcd for C64
H10NO 808.0762, found 808.0753.
10
11
12
13
14
15
16
17
18
19
20
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48
49
50
51
52
53
54
55
56
57
58
59
60
1
2
g (brown solid, 9.8 mg, 24%, mp > 300 °C): H NMR (500 MHz, CS
2
ꢀCDCl
3
) δ 4.98 (dd, J =
10.7, 8.7 Hz, 1H), 4.84 (sextet, J = 7.3 Hz, 1H), 4.42 (t, J = 10.0 Hz, 1H), 3.56 (s, 3H), 1.71 (d, J =
13
6
.7 Hz, 3H); C NMR (125 MHz, CS
2
ꢀCDCl
3
) δ 152.31, 150.98, 150.92, 150.76, 148.52, 148.30,
146.63, 146.58, 146.54, 146.28, 146.24, 146.19, 146.15, 146.09, 145.93, 145.60, 145.53, 145.47,
45.40, 145.39, 145.36, 145.30, 145.09, 144.99, 144.75, 144.69, 143.08, 142.79, 142.77, 142.76,
142.74, 142.66, 142.45, 142.44, 142.40, 142.36, 142.10, 141.75, 141.68, 141.65, 141.50, 141.46,
1
3
3
1
41.25, 139.74, 139.69, 139.50, 138.64, 137.33, 136.81, 136.71, 86.98 (sp ꢀC of C60), 80.01 (sp ꢀC
3
of C60), 68.13, 49.82, 36.54, 18.86; UVꢀVis (CHCl ) λmax/nm 257, 316, 690; HRMS
+
(
MALDIꢀTOFMS) m/z [M+H] calcd for C H NO 808.0762, found 808.0752.
64
10
1
2
h (brown solid, 12.3 mg, 30%, mp > 300 °C): H NMR (500 MHz, CS
2 3
ꢀCDCl ) δ 5.18 (dd, J =
1
3
1.5, 7.4 Hz, 1H), 4.50 (dd, J = 11.6, 5.3 Hz, 1H), 4.25ꢀ4.32 (m, 1H), 4.21 (td, J = 8.7, 3.5 Hz, 1H),
1
3
.63 (q, J = 7.9 Hz, 1H), 2.55ꢀ2.65 (m, 1H), 2.45ꢀ2.55 (m, 1H), 2.18ꢀ2.29 (m, 2H); C NMR (125
ꢀC ) δ 152.66, 152.46, 150.86, 150.78, 149.08, 148.82, 147.23, 147.17, 147.13,
46.92, 146.86, 146.83, 146.82, 146.77, 146.70, 146.57, 146.39, 146.35, 146.30, 146.25, 146.03,
MHz, CS
2
6 6
D
1
1
1
1
46.01, 145.98, 145.94, 145.88, 145.56, 145.44, 145.41, 143.37, 143.34, 143.32, 143.07, 142.96,
42.95, 142.57, 142.45, 142.31, 142.22, 141.72, 140.34, 140.29, 140.25, 140.05, 139.14, 137.93,
3
3
37.42, 137.15, 88.41 (sp ꢀC of C60), 77.03 (sp ꢀC of C60), 69.66, 56.00, 53.15, 35.19, 24.20;
+
UVꢀVis (CHCl
3
) λmax/nm 257, 317, 691; HRMS (MALDIꢀTOFMS) m/z [MꢀH] calcd for
C H NO 818.0606, found 818.0603.
65
8
1
2
2 3
i (brown solid, 12.1 mg, 29%, mp > 300 °C): H NMR (500 MHz, CS ꢀCDCl ) δ 5.08 (dd, J =
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11.4, 8.1 Hz, 1H), 4.47 (dd, J = 11.4, 6.8 Hz, 1H), 4.22ꢀ4.30 (m, 2H), 3.52ꢀ3.60 (m, 1H), 2.16ꢀ2.25
13
(
m, 1H), 1.92ꢀ2.13 (m, 4H), 1.69ꢀ1.78 (m, 1H); C NMR (125 MHz, CS ꢀCDCl ) δ 150.48,
2
3
150.38, 150.35, 148.25, 148.06, 146.43, 146.38, 146.33, 146.07, 146.05, 146.03, 146.02, 145.97,
45.93, 145.88, 145.69, 145.60, 145.56, 145.48, 145.34, 145.20, 145.14, 145.11, 145.08, 144.74,
144.73, 144.65, 144.56, 142.90, 142.60, 142.58, 142.56, 142.54, 142.52, 142.27, 142.22, 142.20,
41.77, 141.69, 141.60, 141.42, 141.39, 141.33, 141.29, 140.89, 139.58, 139.39, 139.12, 138.69,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
1
3
3
138.36, 137.05, 136.87, 136.84, 88.58 (sp ꢀC of C ), 78.94 (sp ꢀC of C ), 66.28, 51.49, 32.12,
60
60
+
2
6.89, 21.61; UVꢀVis (CHCl
calcd for C66 12NO 834.0919, found 834.0915.
j (brown solid, 13.9 mg, 34%, mp > 300 °C): H NMR (500 MHz, CS ꢀCDCl ) δ 6.25 (ddt, J =
3
) λmax/nm 258, 316, 688; HRMS (MALDIꢀTOFMS) m/z [M+H]
H
1
2
2
3
17.0, 10.1, 6.3 Hz, 1H), 5.60 (dq, J = 17.1, 1.2 Hz, 1H), 5.38 (dq, J = 10.1, 1.1 Hz, 1H), 4.89 (t, J
1
3
=
7.6 Hz, 2H), 4.66 (dt, J = 6.3, 1.3 Hz, 2H), 4.16 (t, J = 7.6 Hz, 2H); C NMR (125 MHz,
CS ꢀCDCl ) δ 150.95, 150.49, 148.57, 148.35, 146.67, 146.61, 146.31, 146.21, 145.83, 145.79,
45.55, 145.53, 145.46, 145.40, 144.90, 142.80, 142.77, 142.47, 142.43, 141.97, 141.71, 141.56,
2
3
1
1
6
3
3
41.48, 139.67, 139.60, 137.80, 137.16, 136.69, 118.20, 88.19 (sp ꢀC of C60), 79.25 (sp ꢀC of C60),
3
1.35, 57.85, 42.89; UVꢀVis (CHCl ) λmax/nm 258, 317, 690; HRMS (MALDIꢀTOFMS) m/z
+
[
M+H] calcd for C H NO 820.0762, found 820.0752.
6
5
10
1
2
k (brown solid, 3.1 mg, 7%, mp > 300 °C): H NMR (500 MHz, CS
2 3
ꢀCDCl ) δ 4.91 (t, J = 7.6
Hz, 2H), 4.75 (t, J = 5.2 Hz, 1H), 4.35 (t, J = 7.6 Hz, 2H), 4.24 (d, J = 5.3 Hz, 2H), 3.51 (s, 6H);
1
3
2 3
C NMR (125 MHz, CS ꢀCDCl ) δ 151.46, 150.34, 148.63, 148.42, 146.71, 146.66, 146.37,
1
1
1
46.35, 146.28, 145.82, 145.74, 145.55, 145.52, 145.47, 144.94, 144.91, 143.15, 142.85, 142.83,
42.79, 142.50, 142.46, 142.00, 141.81, 141.60, 141.50, 139.91, 139.65, 137.82, 137.20, 130.75,
3
3
28.84, 105.59, 87.43 (sp ꢀC of C60), 80.02 (sp ꢀC of C60), 60.95, 56.20, 54.30, 45.66; UVꢀVis
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+
(CHCl
68.0974, found 868.0961.
2l (brown solid, 6.9 mg, 15%, mp > 300 °C): H NMR (500 MHz, CS
Hz, 2H), 7.78 (d, J = 8.2 Hz, 2H), 5.32 (s, 2H), 4.90 (t, J = 7.6 Hz, 2H), 4.08 (t, J = 7.6 Hz, 2H),
3 3
) λmax/nm 257, 316, 690; HRMS (MALDIꢀTOFMS) m/z [M+H] calcd for C66H14NO
8
1
2
3
ꢀCDCl ) δ 8.06 (d, J = 8.2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
3
3.91 (s, 3H); C NMR (125 MHz, CS
46.63, 146.34, 146.33, 146.26, 145.87, 145.66, 145.50, 145.47, 145.43, 145.09, 144.90, 142.82,
142.79, 142.48, 142.42, 142.00, 141.77, 141.50, 139.83, 139.69, 137.80, 137.20, 130.00, 129.46,
2 3
ꢀCDCl ) δ 166.50, 150.98, 150.35, 148.60, 148.37, 146.69,
1
3
3
1
3
28.56, 88.07 (sp ꢀC of C60), 79.47 (sp ꢀC of C60), 61.15, 58.49, 51.84, 43.37; UVꢀVis (CHCl )
+
λ
max/nm 257, 317, 689; HRMS (MALDIꢀTOFMS) m/z [MꢀH] calcd for C71
H12NO
3
926.0817,
found 926.0808.
m (brown solid, 5.1 mg, 11%, mp > 300 °C): H NMR (500 MHz, CS
1
2
2
3
ꢀCDCl ) δ 7.99 (d, J =
8
3
1
1
.3 Hz, 2H), 7.26 (d, J = 8.2 Hz, 2H), 5.09 (t, J = 7.5 Hz, 2H), 4.88 (t, J = 7.5 Hz, 2H), 2.41 (s,
1
3
2 3
H); C NMR (125 MHz, CS ꢀCDCl ) δ 148.98, 148.46, 148.38, 148.04, 146.61, 146.60, 146.32,
46.27, 146.20, 145.88, 145.41, 144.80, 144.67, 144.66, 143.63, 142.77, 142.75, 142.37, 141.95,
3
41.63, 141.23, 140.93, 139.79, 139.03, 138.88, 137.63, 137.44, 129.49, 128.38, 87.99 (sp ꢀC of
3
C
60), 76.15 (sp ꢀC of C60), 61.74, 43.09, 21.74; UVꢀVis (CHCl
3
) λmax/nm 257, 318, 421, 688;
+
HRMS (MALDIꢀTOFMS) m/z M calcd for C H NO S 933.0460, found 933.0451.
69
11
3
1
2
n (brown solid, 14.5 mg, 33%, mp > 300 °C): H NMR (500 MHz, CS
2
ꢀCDCl
3
) δ 7.28 (dd, J =
5
.1, 1.2 Hz, 1H), 7.21 (dd, J = 3.5, 1.1 Hz, 1H), 7.02 (dd, J = 5.1, 3.5 Hz, 1H), 5.46 (s, 2H), 4.90 (t,
13
J = 7.6 Hz, 2H), 4.17 (t, J = 7.6 Hz, 2H); C NMR (125 MHz, CS
2
ꢀCDCl
48.56, 148.32, 146.66, 146.59, 146.30, 146.28, 146.22, 145.85, 145.79, 145.50, 145.46, 145.45,
45.39, 144.89, 144.86, 143.92, 142.78, 142.75, 142.42, 141.96, 141.75, 141.48, 141.45, 139.79,
3
) δ 151.00, 150.38,
1
1
1
3
3
39.63, 137.79, 137.11, 126.82, 125.80, 125.45, 87.89 (sp ꢀC of C60), 79.29 (sp ꢀC of C60), 61.20,
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5
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6
+
53.85, 42.87; UVꢀVis (CHCl
3
) λmax/nm 257, 318, 689; HRMS (MALDIꢀTOFMS) m/z [M+H]
calcd for C H NOS 876.0483, found 876.0465.
67
10
1
2o (brown solid, 4.4 mg, 10%, mp > 300 °C): H NMR (500 MHz, CS
2
ꢀCDCl
3
) δ 8.80ꢀ9.01 (m,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
H), 8.48ꢀ8.70 (m, 1H), 8.06 (d, J = 7.7 Hz, 1H), 7.32ꢀ7.42 (m, 1H), 5.30 (s, 2H), 4.92 (t, J = 7.6
13
Hz, 2H), 4.08 (t, J = 7.6 Hz, 2H); C NMR (100 MHz, CS
49.01, 148.94, 148.58, 148.36, 146.67, 146.62, 146.33, 146.31, 146.25, 145.86, 145.55, 145.46,
145.41, 144.88, 144.86, 142.81, 142.78, 142.46, 142.39, 141.99, 141.75, 141.47, 139.84, 139.69,
2 3
ꢀCDCl ) δ 150.82, 150.23, 150.20,
1
3
3
1
37.75, 137.20, 136.18, 88.09 (sp ꢀC of C60), 79.43 (sp ꢀC of C60), 61.08, 56.10, 43.04; UVꢀVis
+
(CHCl
3
) λmax/nm 257, 317, 689; HRMS (MALDIꢀTOFMS) m/z [M+H] calcd for C68
H
11
N
2
O
8
71.0871, found 871.0851.
q (brown solid, 4.0 mg, 10%, mp > 300 °C): H NMR (500 MHz, CS
H), 4.80ꢀ4.92 (m, 1H), 4.48ꢀ4.60 (m, 1H), 3.88ꢀ4.01 (m, 1H), 3.73 (s, 3H), 2.96ꢀ3.11 (m, 1H),
1
2
2 3
ꢀCDCl ) δ 5.07ꢀ5.22 (m,
1
2
1
3
2
3
.00ꢀ2.10 (m, 1H); C NMR (100 MHz, CS
2
ꢀCDCl
3
) δ 135ꢀ155 (sp ꢀC of C60), 95.69 (sp ꢀC of
) λmax/nm 258, 317, 689;
10NO 808.0762, found 808.0753.
ꢀCDCl ) δ 7.31ꢀ7.39 (m,
3
C
60), 82.21 (sp ꢀC of C60), 72.00, 53.84, 39.62, 27.77; UVꢀVis (CHCl
3
+
HRMS (MALDIꢀTOFMS) m/z [M+H] calcd for C64
H
1
2r (brown solid, 4.9 mg, 11%, mp > 300 °C): H NMR (500 MHz, CS
2
3
4
1
1
1
1
1
1
H), 7.23ꢀ7.27 (m, 1H), 4.88 (t, J = 12.2 Hz, 1H), 4.68 (dt, J = 12.7, 3.7 Hz, 1H), 4.26 (dd, J =
4.9, 11.7 Hz, 1H), 3.85 (dt, J = 15.1, 3.2 Hz, 1H), 3.71 (s, 3H), 3.23ꢀ3.36 (m, 1H), 2.82 (dd, J =
13
2 3
3.6, 6.5 Hz, 1H), 2.78 (dd, J = 13.7, 7.7 Hz, 1H); C NMR (125 MHz, CS ꢀCDCl ) δ 154.38,
54.34, 152.48, 150.82, 148.68, 148.38, 146.72, 146.66, 146.60, 146.59, 146.23, 146.20, 146.08,
45.96, 145.76, 145.56, 145.51, 145.47, 145.43, 145.41, 145.36, 145.18, 144.98, 144.91, 144.88,
44.84, 144.82, 144.53, 143.07, 142.80, 142.78, 142.76, 142.69, 142.67, 142.63, 142.50, 141.98,
41.87, 141.76, 141.55, 141.49, 141.46, 141.38, 140.84, 140.01, 139.56, 139.30, 139.27, 139.10,
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138.69, 136.77, 136.50, 136.31, 128.85, 128.75, 126.48, 95.08 (sp ꢀC of C60), 81.89 (sp ꢀC of C60),
7
6.30, 59.54, 40.33, 37.96, 36.12; UVꢀVis (CHCl ) λmax/nm 256, 316, 688; HRMS
3
+
(MALDIꢀTOFMS) m/z [M+H] calcd for C71
H
16NO 898.1232, found 898.1221.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
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45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2
t (brown solid, 8.8 mg, 19%, mp > 300 °C; Caution: After purification on silica gel column, the
1
solvent should be removed under dark using aluminum foil to wrap the roundꢀbottom flask): H
NMR (500 MHz, CS ꢀCDCl ) δ 7.54 (d, J = 7.4 Hz, 1H), 7.47 (d, J = 8.1 Hz, 1H), 7.25 (td, J = 7.2,
2
3
1.2 Hz), 7.20 (td, J = 7.5, 1.0 Hz), 6.92 (s, 1H), 5.44 (s, 2H), 4.96 (t, J = 7.6 Hz, 2H), 4.24 (t, J =
13
7
.6 Hz, 2H); C NMR (125 MHz, CS
2
ꢀCDCl
3
) δ 155.90, 155.27, 150.92, 150.29, 148.60, 148.37,
146.70, 146.63, 146.34, 146.26, 145.90, 145.79, 145.52, 145.48, 145.46, 145.44, 144.91, 144.88,
42.83, 142.80, 142.79, 142.47, 142.46, 142.00, 141.79, 141.51, 141.46, 139.84, 139.69, 137.82,
1
3
3
137.19, 128.50, 124.16, 122.90, 120.90, 111.36, 105.89, 87.95 (sp ꢀC of C60), 79.15 (sp ꢀC of C60),
6
1.12, 52.27, 43.71; UVꢀVis (CHCl ) λmax/nm 258, 317, 688; HRMS (MALDIꢀTOFMS) m/z
3
+
[
M+H] calcd for C71
H12NO
2
910.0868, found 910.0846.
1
4a (brown solid, 6.8 mg, 16%, mp > 300 °C): H NMR (500 MHz, CS
2
ꢀCDCl
3
) δ 7.07 (dd, J =
5
.8, 1.8 Hz, 1H), 6.85 (d, J = 5.8 Hz, 1H), 6.23 (d, J = 1.5 Hz, 1H), 4.80ꢀ4.87 (m, 1H), 4.56ꢀ4.62
(
m, 1H), 4.23 (d, J = 12.5 Hz, 1H), 4.15 (d, J = 12.5 Hz, 1H), 4.02ꢀ4.08 (m, 1H), 3.92ꢀ3.97 (m, 1H);
+
UVꢀVis (CHCl ) λ /nm 257, 708; HRMS (MALDIꢀTOFMS) m/z M calcd for C H NO
3
max
67
9
2
8
59.0633, found 859.0626.
4b (brown solid, 9.7 mg, 21%, mp > 300 °C; Caution: it is very sensitive to sunlight. After
purification on silica gel column, the solvent should be removed under dark using aluminum foil to
1
wrap the roundꢀbottom flask): H NMR (500 MHz, CS
2
ꢀCDCl
3
) δ 6.87 (d, J = 5.6 Hz, 1H), 6.79 (d,
J = 5.8 Hz, 1H), 4.82 (ddd, J = 11.8, 9.9, 4.4 Hz, 1H), 4.58 (ddd, J = 11.6, 7.1, 2.5 Hz, 1H), 4.17 (d,
J = 12.4 Hz, 1H), 4.10 (d, J = 12.5 Hz, 1H), 4.01ꢀ4.08 (m, 1H), 3.88ꢀ3.94 (m, 1H), 2.59ꢀ2.73 (m,
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2H), 1.87ꢀ2.01 (m, 1H), 1.70ꢀ1.83 (m, 1H), 1.27ꢀ1.57 (m, 4H), 0.96 (t, J = 7.1 Hz, 3H); C NMR
(
125 MHz, CS ꢀCDCl ) δ 152.09, 149.29, 149.18, 149.06, 148.31, 148.14, 147.89, 147.00, 146.76,
2
3
146.32, 146.20, 146.18, 146.05, 145.90, 145.82, 145.62, 145.51, 145.36, 145.22, 144.95, 144.71,
44.59, 144.55, 144.20, 144.12, 143.98, 143.91, 143.85, 143.82, 143.68, 143.48, 143.05, 143.02,
142.96, 142.84, 142.36, 142.28, 142.20, 142.16, 141.99, 141.18, 141.04, 140.52, 139.85, 137.88,
0
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37.15, 136.83, 135.14, 133.68, 99.21, 98.03, 87.55 (sp ꢀC of C60), 84.07 (sp ꢀC of C60), 76.10
3
3
(sp ꢀC of C ), 74.39 (sp ꢀC of C ), 62.33, 54.62, 47.76, 32.59, 31.56, 25.91, 23.05, 14.35; UVꢀVis
6
0
60
+
(CHCl
3 2
) λmax/nm 257, 713; HRMS (MALDIꢀTOFMS) m/z M calcd for C72H19NO 929.1416,
found 929.1423.
1
7
a (brown solid, 6.3 mg, 15%, mp > 300 °C): H NMR (500 MHz, CS ꢀCDCl ) δ 3.88 (t, J = 7.1
2
3
13
Hz, 2H), 3.28 (t, J = 7.0 Hz, 2H), 3.04 (s, 3H); C NMR (125 MHz, CS
2
ꢀCDCl
3
, the low quality of
1
3
C NMR spectrum was due to its very poor solubility) δ 146.65, 145.43, 145.33, 145.22, 145.06,
1
1
λ
45.00, 144.90, 144.67, 144.47, 144.42, 143.97, 143.53, 142.92, 142.73, 142.66, 142.25, 142.06,
3
41.90, 141.03, 140.96, 137.13, 76.63 (sp ꢀC of C60), 45.90, 30.52, 25.11; UVꢀVis (CHCl
3
)
+
max/nm 260, 328, 430, 496, 689; HRMS (MALDIꢀTOFMS) m/z M calcd for C65
H
7
NO 817.0528,
found 817.0520.
b' (small amount of 7b' could be isolated within 2 h from the reaction of C60 with 6b): H
NMR (500 MHz, CS ꢀCDCl ) δ 7.46 (d, J = 7.5 Hz, 2H), 7.34 (t, J = 7.5 Hz, 2H), 7.27 (t, J = 7.3
Hz, 1H), 5.55 (s, 1H), 4.21 (d, J = 12.9 Hz, 1H), 4.17 (d, J = 12.9 Hz, 1H), 3.46ꢀ3.54 (m, 1H),
1
7
2
3
13
3
.34ꢀ3.41 (m, 1H), 3.09ꢀ3.16 (m, 1H), 3.01ꢀ3.08 (m, 1H), 2.37 (br, 1H); C NMR (125 MHz,
CS ꢀCDCl ) δ 145.36, 145.08, 144.97, 144.78, 144.72, 144.64, 144.24, 144.15, 144.09, 144.06,
2
3
1
43.59, 143.55, 143.17, 143.09, 143.06, 143.02, 142.99, 142.25, 142.21, 142.19, 141.11, 128.72,
3
1
28.65, 127.48, 88.01 (HOCHN), 72.96 (sp ꢀC of C60), 54.72, 54.05, 49.62, 28.63; UVꢀVis (CHCl
3
)
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+
λ
2 12
max/nm 259, 328, 429, 498, 691; HRMS (MALDIꢀTOFMS) m/z [M+HꢀH O] calcd for C71H N
8
78.0970, found 878.0952.
1
7b (brown solid, 22.3 mg, 50%, mp > 300 °C): H NMR (500 MHz, CS
2
ꢀCDCl
3
) δ 7.38ꢀ7.46 (m,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
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29
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59
60
13
4
H), 7.35 (t, J = 7.5 Hz, 1H), 4.74 (s, 2H), 3.77 (t, J = 7.1 Hz, 2H), 3.24 (t, J = 7.1 Hz, 2H); C
NMR (100 MHz, CS
2 3
ꢀCDCl ) δ 168.30, 146.68, 145.52, 145.38, 145.36, 145.19, 145.13, 145.09,
1
45.06, 144.99, 144.74, 144.56, 144.53, 144.50, 144.10, 144.04, 143.61, 143.57, 143.14, 143.05,
142.99, 142.75, 142.31, 142.13, 142.03, 141.96, 141.18, 141.04, 140.99, 137.22, 135.83, 129.07,
3
128.70, 128.15, 76.28 (sp ꢀC of C60), 47.87, 44.26, 43.27, 25.03; UVꢀVis (CHCl
3
) λmax/nm 259,
+
328, 429, 497, 690; HRMS (MALDIꢀTOFMS) m/z M calcd for C71
H
11NO 893.0841, found
8
93.0821.
c (brown solid, 12.9 mg, 29%, mp > 300 °C): H NMR (500 MHz, CS
.1 Hz, 2H), 3.57 (t, J = 7.3 Hz, 2H), 3.27 (t, J = 7.1 Hz, 2H), 1.76 (quint, J = 7.4 Hz, 2H),
1
7
2 3
ꢀCDCl ) δ 3.88 (t, J =
7
1
1
1
1
2
1
3
2 3
.33ꢀ1.51 (m, 6H), 0.93 (t, J = 7.0 Hz, 3H); C NMR (125 MHz, CS ꢀCDCl ) δ 168.12, 146.78,
45.60, 145.40, 145.34, 145.18, 145.13, 145.06, 145.03, 144.96, 144.73, 144.54, 144.51, 144.47,
44.04, 144.02, 143.60, 143.57, 143.11, 143.03, 142.97, 142.71, 142.30, 142.12, 141.99, 141.96,
3
41.16, 141.00, 137.17, 76.38 (sp ꢀC of C60), 44.44, 43.93, 43.83, 31.78, 27.61, 26.97, 25.20,
2.95, 14.28; UVꢀVis (CHCl ) λmax/nm 260, 328, 429, 497, 685; HRMS (MALDIꢀTOFMS) m/z
3
+
M calcd for C70
H
17NO 887.1310, found 887.1290.
1
7
d (brown solid, 10.5 mg, 24%, mp > 300 °C): H NMR (500 MHz, CS
2 3
ꢀCDCl ) δ 3.78 (t, J =
6
.3 Hz, 2H), 3.60 (t, J = 7.7 Hz, 2H), 3.04 (t, J = 6.2 Hz, 2H), 2.41 (quint, J = 6.3 Hz, 2H), 1.72
1
3
(
quint, J = 7.6 Hz, 2H), 1.44 (sextet, J = 7.5 Hz, 2H), 1.01 (t, J = 7.4 Hz, 3H); C NMR (125 MHz,
CS ꢀCDCl ) δ 164.64, 147.41, 146.59, 145.53, 145.30, 145.16, 145.11, 145.04, 144.95, 144.76,
2
3
1
44.59, 144.52, 144.50, 144.05, 144.00, 143.58, 143.45, 143.12, 143.00, 142.91, 142.59, 142.30,
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142.07, 141.84, 141.72, 141.12, 140.94, 140.63, 137.82, 76.73 (sp ꢀC of C60), 48.16, 48.03, 45.08,
2
9.64, 25.30, 22.58, 20.63, 14.18; UVꢀVis (CHCl ) λmax/nm 260, 328, 429, 496, 692; HRMS
3
+
(MALDIꢀTOFMS) m/z M calcd for C69
H
15NO 873.1154, found 873.1136.
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The Conversion of 4b or 2t to 5b or 5t under Photoirradiation. A solution of 4b or 2t
(0.015mmol) in CS (20 mL) in a big tube (Φ18 × 150 mm) was irradiated with a 125 W
2
fluorescent highꢀpressure mercury lamp under nitrogen atmosphere for 1 h. The solvent was
removed in vacuo and the residue was purified on a silica gel column with CS /toluene
2
(
100:0ꢀ0:100, gradient elution) as the eluent to give the product 5b (7.2 mg, 52%) or 5t (9.1 mg,
67%).
b (brown solid, mp > 300 °C): H NMR (500 MHz, CS ꢀCDCl ) δ 5.31 (d, J = 10.1 Hz, 1H),
1
5
2
3
5.02 (s, 2H), 4.76ꢀ4.88 (m, 2H), 4.32 (d, J = 10.0 Hz, 1H), 4.26 (dt, s = 15.0, 8.0 Hz, 1H), 3.73
(
ddd, J = 15.1, 8.9, 5.7 Hz, 1H), 2.34 (t, J = 7.5 Hz, 2H), 1.54ꢀ1.70 (m, 2H), 1.25ꢀ1.41 (m, 4H),
1
3
0
1
1
1
1
9
2 3
.86 (t, J = 7.1 Hz, 3H); C NMR (125 MHz, CS ꢀCDCl ) δ 164.06, 152.74, 149.55, 149.52,
49.07, 148.94, 148.52, 148.32, 148.07, 147.52, 147.11, 147.04, 146.73, 146.49, 146.46, 146.26,
46.21, 145.73, 145.66, 145.59, 145.42, 145.38, 145.29, 145.22, 145.11, 145.06, 144.94, 144.87,
44.74, 144.66, 144.57, 144.52, 144.46, 144.21, 144.18, 143.92, 143.79, 143.41, 143.02, 142.98,
42.80, 142.59, 142.50, 142.09, 141.81, 141.69, 140.49, 140.13, 139.73, 139.06, 138.98, 136.64,
3
3
3
3
7.60, 95.28, 83.09 (sp ꢀC of C60), 79.28 (sp ꢀC of C60), 78.82 (sp ꢀC of C60), 67.85, 64.09 (sp ꢀC
3
of C60), 61.44, 57.29, 40.05, 32.33, 28.97, 27.47, 23.44, 14.87; UVꢀVis (CHCl ) λmax/nm 258, 690;
+
HRMS (MALDIꢀTOFMS) m/z M calcd for C72
H
19NO
2
929.1416, found 929.1432.
ꢀCDCl ) δ 7.31 (d, J = 7.5 Hz, 1H),
1
5
t (brown solid, mp > 300 °C): H NMR (500 MHz, CS
2
3
7
.25 (d, J = 7.9 Hz, 1H), 6.92ꢀ6.99 (m, 2H), 5.52 (s, 1H), 5.40 (d, J = 10.0 Hz, 1H), 4.79ꢀ4.91 (m,
H), 4.46 (d, J = 10.1 Hz, 1H), 4.30 (dt, s = 15.0, 8.0 Hz, 1H), 3.78 (ddd, J = 15.1, 9.1, 5.9 Hz,
2
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1H), 2.34 (t, J = 7.5 Hz, 2H), 1.54ꢀ1.70 (m, 2H), 1.25ꢀ1.41 (m, 4H), 0.86 (t, J = 7.1 Hz, 3H); C
NMR (125 MHz, CS ꢀCDCl ) δ 161.25, 152.19, 149.26, 149.20, 148.78, 148.28, 148.25, 148.07,
2
3
147.53, 147.19, 146.83, 146.70, 146.44, 146.14, 145.94, 145.89, 145.29, 145.07, 144.97, 144.91,
44.84, 144.77, 144.59, 144.39, 144.23, 144.21, 144.10, 143.93, 143.90, 143.87, 143.58, 143.43,
143.08, 142.70, 142.65, 142.47, 142.22, 142.18, 142.14, 141.69, 141.55, 141.43, 141.20, 140.20,
39.86, 139.39, 138.68, 138.06, 136.31, 129.94, 127.17, 126.27, 121.92, 110.65, 96.29, 82.96
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59
60
1
1
3
3
3
3
(sp ꢀC of C ), 79.04 (sp ꢀC of C ), 77.90 (sp ꢀC of C ), 67.34, 62.93 (sp ꢀC of C ), 61.22, 55.42,
6
0
60
60
60
+
39.63, 0.09; UVꢀVis (CHCl
3
) λmax/nm 256, 691; HRMS (MALDIꢀTOFMS) m/z [M+H] calcd for
C
71 2
H12NO
910.0868, found 910.0851.
The Reaction of C60 with Cyclic Enamine 8 Catalyzed by CuI/DMAP System. A mixture of
60 (36.0 mg, 0.05 mmol), enamine 8 (0.1 mmol), CuI (1.9 mg, 0.01 mmol), and DMAP (2.5 mg,
C
0
.02 mmol) was stirred vigorously in 10 mL of chlorobenzene in a tube (Φ18 × 150 mm) under
open air at 120 ºC for 6 h. The solvent was removed in vacuo and the residue was purified on a
silica gel column with CS
2
as the eluent to give unreacted C60 and then with toluene as the eluent
1
to give product 7e (9.7 mg, 21%, brown solid, mp > 300 °C). H NMR (500 MHz, CS ꢀCDCl ) δ
2
3
7
3
1
.30ꢀ7.39 (m, 4H), 7.27 (t, J = 6.9 Hz, 1H), 5.51 (d, J = 15.1 Hz, 1H), 4.29 (d, J = 15.1 Hz, 1H),
.89 (sextet, J = 6.1 Hz, 1H), 3.13 (ddd, J = 14.2, 9.3, 4.0 Hz, 1H), 3.01 (ddd, J = 14.3, 7.8, 4.0 Hz,
1
3
H), 2.42ꢀ2.51 (m, 1H), 2.10ꢀ2.20 (m, 1H), 1.55 (d, J = 6.5 Hz, 3H); C NMR (125 MHz,
CS
2
ꢀCDCl ) δ 165.37, 147.48, 147.00, 146.64, 146.38, 145.51, 145.49, 145.28, 145.16, 145.14,
3
1
1
1
1
45.12, 145.01, 144.96, 144.94, 144.77, 144.75, 144.56, 144.53, 144.51, 144.08, 144.07, 144.05,
43.98, 143.62, 143.57, 143.46, 143.42, 143.13, 143.07, 143.04, 143.01, 142.92, 142.90, 142.59,
42.58, 142.31, 142.28, 142.09, 142.05, 141.81, 141.70, 141.68, 141.40, 141.29, 140.99, 140.90,
3
3
40.68, 140.63, 137.86, 137.84, 137.25, 128.82, 127.91, 127.55, 76.80 (sp ꢀC of C60), 76.76 (sp ꢀC
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of C60), 51.73, 48.05, 44.97, 29.77, 22.83, 20.63; λmax/nm 260, 328, 429, 496, 693; HRMS
+
(
MALDIꢀTOFMS) m/z M calcd for C H NO 921.1154, found 921.1133.
73
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Corresponding Author
Eꢀmail: yht898@yahoo.com
Acknowledgments
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We are grateful for financial support from the National Natural Science Foundation of China
(Nos. 21202011), Natural Science Foundation of Jiangsu Province (BK20141171), the Jiangsu
Key Laboratory of Advanced Catalytic Materials and Technology (BM2012110), and Advanced
Catalysis and Green Manufacturing Collaborative Innovation Center.
Supporting Information
This material is available free of charge via the Internet at http://pubs.acs.org.
UVꢀvis spectra of 2b, 4a, 5b, 5t, and 7b
1
13
H and C NMR spectra of the products
H−H Cosy, HSQC, HMBC, and NOESY spectra of 5b
References
1
(a) Li, C.ꢀZ.; Yip, H.ꢀL.; Jen, A. K.ꢀY. J. Mat. Chem. 2012, 22, 4161. (b) Chochos, C.;
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For recent papers, see: (a) Wu, A.ꢀJ.; Tseng, P.ꢀY.; Hsu, W.ꢀH.; Chuang, S.ꢀC. Org. Lett. 2016,
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For reviews, see: (a) Tzirakis, M. D.; Orfanopoulos, M. Chem. Rev. 2013, 113, 5262. For
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