Ce(OTf)3-catalyzed multicomponent domino cyclization- aromatization of ferrocenylacetylene, aldehydes, and amines: A straightforward synthesis of ferrocene-containing quinolines

Article abstract of DOI:10.1016/j.tet.2013.05.026

A straightforward and economic method for the synthesis of ferrocene-containing quinolines by the Ce(OTf)₃-catalyed one-pot three-component domino cyclization/aromatization reaction of ferrocenylacetylene, aldehydes, and amines under an air atmosphere was developed. A series of ferrocene substituted quinolines have been synthesized from simple and readily available starting materials in good yields.

Full text of DOI:10.1016/j.tet.2013.05.026

Accepted Manuscript
Ce(OTf)3-Catalyzed Multicomponent Domino Cyclization–Aromatization of
Ferrocenylacetylene, Aldehydes and Amines: A Straightforward Synthesis of
Ferrocene-Containing Quinolines
Shufeng Chen, Ling Li, Haiying Zhao, Baoguo Li
PII:
S0040-4020(13)00761-8
10.1016/j.tet.2013.05.026
TET 24364
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 28 February 2013
Revised Date: 22 April 2013
Accepted Date: 10 May 2013
Please cite this article as: Chen S, Li L, Zhao H, Li B, Ce(OTf)3-Catalyzed Multicomponent Domino
Cyclization–Aromatization of Ferrocenylacetylene, Aldehydes and Amines: A Straightforward Synthesis
of Ferrocene-Containing Quinolines, Tetrahedron (2013), doi: 10.1016/j.tet.2013.05.026.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Ce(OTf) -Catalyzed Multicomponent Domino
3
Cyclization–Aromatization of Ferrocenylacetylene, Aldehydes
and Amines: A Straightforward Synthesis of
Ferrocene-Containing Quinolines
Shufeng Chen,* Ling Li, Haiying Zhao, Baoguo Li*
College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China
A straightforward and economic method for the synthesis of ferrocene-containing
3
quinolines by the Ce(OTf) -catalyed one-pot three-component domino
cyclization/aromatization reaction of ferrocenylacetylene, aldehydes and amines
under an air atmosphere was developed. A series of ferrocene substituted quinolines
have been synthesized from simple and readily available starting materials in good
yields.
1

ACCEPTED MANUSCRIPT
Ce(OTf) -Catalyzed Multicomponent Domino
3
Cyclization–Aromatization of Ferrocenylacetylene, Aldehydes
and Amines: A Straightforward Synthesis of
Ferrocene-Containing Quinolines
Shufeng Chen,* Ling Li, Haiying Zhao, Baoguo Li*
College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China
E-mail address: shufengchen@imu.edu.cn, baoguol@sohu.com
Abstract: A straightforward and economic method for the synthesis of
3
ferrocene-containing quinolines by the Ce(OTf) -catalyed one-pot three-component
domino cyclization/aromatization reaction of ferrocenylacetylene, aldehydes and
amines under an air atmosphere was developed. A series of ferrocene substituted
quinolines have been synthesized from simple and readily available starting materials
in good yields.
Keywords: aldehyde, amine, cerium triflate, ferrocenylacetylene, multicomponent
reaction, quinoline
1
. Introduction
Transition-metal-catalyzed multicomponent reactions (MCRs) are attractive
methodologies for the synthesis of heterocyclic compounds, and enable the
construction of complex molecules from readily avaliable starting materials in a
2

ACCEPTED MANUSCRIPT
1
one-pot operation with high efficiency. These reactions have some significant
advantages over conventional synthetic methods such as high regioselectivity and
atom economy, low cost, reduction in overall reaction time, and operational simplicity.
Therefore, transition-metal-catalyzed multicomponent processes have become a
2
preferred strategy for chemists to synthesize various polyfunctionalized compounds.
Quinoline is one of the ubiquitous heterocyclic scaffold broadly found in many
natural products and pharmaceutically active substances and frequently used as
3
building block in material science and in organic synthesis. Quinoline-containing
compounds, for example, are associated with a broad range of biological activities,
such as antimicrobial, antimalarial, anti-HIV, antituberculosis, and antitumor
4
activities. Due to their widespread biological activity, the synthesis of quinoline
5
derivatives has been extensively researched over the years. However, the limited
availability of starting materials, harsh reaction conditions as well as tedious workup
procedures are the main drawbacks of many of these methods. To overcome these
difficulties, the development of more convenient and efficient synthetic
methodologies is still desirable. Recently, several transition-metal-catalyzed
three-component reactions of aldehydes, anilines, and alkynes have been developed
6
for the synthesis of substituted quinolines. For example, Kuninobu and coworkers
have reported an efficient synthesis of 2,4-disubstituted quinoline derivatives from
6a
simple starting materials using CuCl and AgOTf as catalysts. This method has been
6b
improved greatly by Wang’s group, although the reaction time is relatively long.
Also, Tu and co-workers have developed an important methodology to construct
3

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3
quinoline scaffold from aldehydes, alkynes and amines in which FeCl was used as a
6c
single catalyst. Similarly, the Cu(OTf)
2
-catalyzed tandem Grignard-type imine
addition/Friedele-Crafts alkenylation of arenes with alkynes for the practical synthesis
6
d
of quinoline-2-carboxylates were described by Liu and coworkers. Moreover, rare
7
earth metals were also found to be the efficient catalysts in this transformation.
However, the harsh reaction conditions (5.5 bar) as well as the preparation of rare
earth catalyst restrict their potential applications in organic synthesis.
On the other hand, ferrocenes are an important group of organometallic compounds
8
which display interesting biological properties and also some specifically designed
9
ferrocenyl conjugates are valuable candidates for antimalarial or anticancer therapies.
Consequently, integration of a ferrocenyl moiety into quinoline derivatives may
10
increase their biological activities or create new medicinal properties. However, as
far as our knowledge is concerned, there are a limited number of previous reports on
11
the synthesis of ferrocene-containing quinolines. In continuation of our efforts to
12
develop novel reaction methodologies for the synthesis of ferrocene derivatives, we
report herein straightforward and practical Ce(OTf) -catalyed one-pot
a
3
three-component domino cyclization/aromatization reaction of ferrocenylacetylene,
aldehydes and amines for the facile synthesis of ferrocene-containing quinolines
(Scheme 1).
4

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Scheme 1. Synthesis of ferrocene-containing quinolines.
2
. Results and discussion
At the outset of this investigation, we chose ferrocenylacetylene 1, aniline 2a, and
benzaldehyde 3a as the model substrates to optimize the reaction conditions. On
catalysis with La(OTf) at reflux temperature under an air atmosphere, the
corresponding ferrocenesubstituted quinolone 4a was obtained in 64% yield (Table 1,
entry 1). Other rare earth metal salts, such as Y(OTf) , Sc(OTf) , and Yb(OTf)
behaved similarly, giving the desired product in 66, 61, and 55% yield, respectively
entries 2-4). However, the most effective catalyst turned out to be Ce(OTf)
furnishing the product in 75% yield. Other metal triflates and CeCl only gave
2
moderate yields (entries 6, 7 and 8). Only trace of 4a was detected when CeCl •7H O
3
3
3
3
,
(
3
,
3
3
was used as the catalyst under the same reaction conditions (entry 9). These results
indicated that water maybe has important effect on this transformation. Thus, we next
carried out the reaction using 4Å MS as the additive and found that the yield of the
product was not improved obviously (entry 10). Encouraged by these results, we next
carefully examined the effect of the catalyst loading on this three-component reaction
3
(entries 11-13). The results indicated that 10 mol % of Ce(OTf) could give the best
yield of the product under the same conditions. Next, we went on to screen the effect
of solvent on this reaction (entries 11-13). Among the solvents tested, toluene was
5

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found to be the most suitable one. Modest yields of 4a were observed when using
3
other solvents, such as THF, 1,2-dichloroethane and CH CN (entries 14-16). However,
lower yields of 4a were detected when the reaction was performed in dichloromethane
or CH NO (entries 17 and 18).
3
2
a
Table 1. Optimization of reaction conditions.
Time
h)
Yield
(%)
Entry Cat. (mol %)
Solvent
b
(
1
2
3
4
5
6
7
8
La(OTf)
3
(10) toluene
4
3
3
6
4
3
3
7
64
66
61
55
75
58
64
50
Y(OTf) (10) toluene
(10) toluene
3
Sc(OTf)
3
Yb(OTf)
Ce(OTf)
Cu(OTf)
AgOTf (10)
3
(10) toluene
(10) toluene
2
(10) toluene
3
toluene
toluene
CeCl
CeCl
3
(10)
·7H
3
2
O
9
1
toluene
7
trace
(
10)
Ce(OTf)
Ce(OTf) (20) toluene
c
0
3
(10) toluene
4
4
4
9
4
72
74
70
58
68
1
1
3
1
1
1
2
3
4
Ce(OTf)
Ce(OTf)
Ce(OTf)
3
3
3
(5)
(2)
toluene
toluene
(10) THF
(
2 2
CH ) Cl
1
5
Ce(OTf) (10)
6
70
3
2
1
1
1
6
7
8
Ce(OTf)
Ce(OTf)
Ce(OTf)
3
3
3
(10) CH
(10) CH
(10) CH
3
2
3
CN
Cl
NO
4
7
4
59
42
45
2
2
[
a] Ferrocenylacetylene 1 (1.0 equiv.), aniline 2a (1.2 equiv.), and
benzaldehyde 3a (1.2 equiv.) in 2.0 mL of solvent under an air
atmosphere if not otherwise indicated. [b] Yield of isolated product
after chromatography. [c] 4Å MS was added.
6

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To define the generality of the present procedure, we next turn our attentions to this
three-component reaction using ferrocenylacetylene, aniline and a variety of
aldehydes as the substrates and the results are summarized in Table 2. First of all,
different substituents on the phenyl ring of aromatic aldehydes were tested and the
corresponding ferrocene-containing quinoline products 4 were obtained in good yields.
It was found that substrates with a phenyl ring bearing an electron-donating group or
halogen generally gave slightly higher yields (Table 2, 4b-i), while substrates with a
strong electron-withdrawing substituent on the phenyl ring, such as nitro group, gave
slightly lower yields (4l-n). It should be noted that the reaction proceeded readily
when fluoro substituted aromatic aldehydes were used as the substrates (4j and 4k).
The ortho-position effect was obviously observed in the formation of 4i, 4j, and 4l.
Further investigation revealed that this approach was also applicable to the substrates
bearing heteroaromatic ring substituents (4o and 4p). Besides, we were pleasant to
discover that cinnamaldehyde as well as ethyl glyoxalate are also compatible with this
transformation, albeit with slightly low yields (4q and 4r). However, when aliphatic
aldehyde was used instead of aromatic ones, only trace of desired product was
detected.
Table 2. The synthesis of ferrocene-containing quinolines using ferrocenylacetylene,
a
aniline, and various aldehydes
7

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8

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[
a] All the reactions were carried out in the scale of 1.0 mmol of ferrocenylacetylene 1, 1.2 mmol of aniline 2a and
1
3
.2 mmol of aldehyde in the presence of 10.0 mol% of Ce(OTf) in 2 mL of toluene and isolated yields were
reported.
Subsequently, we examined the scope of amines, as shown in Table 3. Various
substitutions on the phenyl ring of anilines could be tolerated, and the reaction gave
moderate yields of the products 4u-y. It is noteworthy that many useful substituents,
such as halogen atoms and a hydroxyl group, were successfully introduced into the
ferrocene-containing quinoline product. Furthermore, the reaction of 4-nitroaniline
also proceeded smoothly to afford product 4z in moderate yield.
Table 3. The synthesis of ferrocene-containing quinolines using ferrocenylacetylene,
a
benzaldehyde and substituted anilines
9

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[
a] All the reactions were carried out in the scale of 1.0 mmol of ferrocenylacetylene 1, 1.2 mmol of amine
3
and 1.2 mmol of benzaldehyde 3a in the presence of 10.0 mol% of Ce(OTf) in 2 mL of toluene and isolated
yields were reported.
However, it has been noted that this method is not applicable to the general alkynes
aryl- or alkyl-substituted alkyne). The results showed that phenylacetylene,
(
4
-chloro-1-ethynylbenzene and 1-hexyne were all not suitable for this transformation
under the same reaction conditions and only trace of the corresponding quinoline was
detected by GC-MS.
Based on the experimental results above and the previous understanding of this type
of reactions, we proposed the following possible mechanism for this
Ce(OTf)
3
-catalyed three-component reaction, as shown in Scheme 2. In the presence
, ferrocenylacetylene reacted with the imine intermediate, which is
of Ce(OTf)
3
1
0

ACCEPTED MANUSCRIPT
generated in situ from benzaldehyde and aniline, leads to the formation of the
intermediate A. Lose of a protone from intermediate A generates intermediate B,
which undergoes electrocyclization to form the cyclized intermediate C. Protonation
of intermediate C to give dihydroquinoline intermediate D, which is oxidized by O in
2
air affords the final ferrocene-containing quinoline product 4a. Therefore, we believe
that this one-pot reaction undergoes domino imine formation, cyclization and
oxidation.
3
Scheme 2. Possible mechanism for Ce(OTf) -catalyed domino cyclization/aromatization reaction
of ferrocenylacetylene, aldehyde and amine.
3
. Conclusion
In conclusion, we have developed a straightforward and economic method for the
synthesis of ferrocene-containing quinolines by the Ce(OTf) -catalyed one-pot
3
three-component domino cyclization/aromatization reaction of ferrocenylacetylene,
aldehydes and amines for the first time. A series of ferrocene substituted quinolines
11

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have been synthesized from simple and readily available starting materials in good
yields. Due to the increasing importance of quinolines and ferrocenes in bioorganic
chemistry, this method will be a valuable choice for organic synthesis and it may open
up new possibility to incorporate quinolines with ferrocenes chemistry. Further
studies on the applications of these novel ferrocene-containing quinolines are being
actively pursued in our laboratory.
4
. Experimental section
4
.1 General Information
All reagents were used as received from commercial sources, unless specified
otherwise, or prepared as described in the literature. All solvents were distilled under
a nitrogen atmosphere prior to use. Toluene was dried over Na with benzophenone as
indicator. For chromatography, 200-300 mesh silica gel (Qingdao, China) was
1
13
employed. H and C NMR spectra were recorded at 500 MHz and 125 MHz
FT-NMR spectrometer. Chemical shifts are reported in ppm using tetramethylsilane
3
as internal standard when CDCl was used as solvent. IR spectra were recorded on a
FT-IR instrument. The HRMS analysis was obtained on a GCTOF mass spectrometer.
Melting points were determined with melting points apparatus and are uncorrected.
4
3
.2 General Procedure for the Ce(OTf) -Catalyzed Three-Component Domino
Cyclization/Aromatization Reaction of Ferrocenylacetylene, Aldehydes and
Amines
3
Ce(OTf) (0.1 mmol), ferrocenylacetylene (1.0 mmol), aldehyde (1.2 mmol), amine
1
2

ACCEPTED MANUSCRIPT
(1.2 mmol), and toluene (2.0 mL) were added sequentially into a dried reaction tube
equipped with a reflux condenser under an air atmosphere. The resulting mixture was
stirred for 5 min at room temperature and then heated at 110 °C for the indicated time.
The mixture was cooled to room temperature. The solvent was removed in a vacuum,
and the resulting residue was purified on a silica gel column (EtOAc/Petroleum ether)
to provide the desired ferrocene-containing quinoline product 4.
4
.3. Data for new compounds
-Ferrocenyl-2-phenylquinoline (4a): Red solid; Mp: 149-152 C; H NMR (500
MHz, CDCl ) δ 4.18 (s, 5H), 4.47 (t, J = 1.5 Hz, 2H), 4.78 (t, J =1.5 Hz, 2H),
o
1
4
3
7
.47~7.56 (m, 4H), 7.67~7.71 (m, 1H), 8.12 (s, 1H), 8.19 (t, J = 8.0 Hz, 3H), 8.56 (d,
13
J = 8.0 Hz, 1H); C NMR (125 MHz, CDCl
3
) δ 69.5, 70.1, 70.6, 83.8, 119.8, 125.7,
1
25.8, 126.1, 127.6, 129.0, 129.3, 130.4, 140.0, 146.9, 149.0, 156.6; HRMS calcd for
+
C
25
H
20FeN [M+H] : 390.0950, found: 390.0937.
-Ferrocenyl-2-p-tolylquinoline (4b): Red solid; Mp: 132-135 C; H NMR (500
MHz, CDCl ) δ 2.44 (s, 3H), 4.20 (s, 5H), 4.49 (s, 2H), 4.79 (s, 2H), 7.35 (d, J = 8.0
Hz, 2H), 7.50 (t, J = 8.0 Hz, 1H), 7.69 (t, J = 7.5 Hz, 1H), 8.09~8.19 (m, 4H), 8.55 (d,
o
1
4
3
1
3
J = 8.5 Hz, 1H); C NMR (125 MHz, CDCl
25.6, 125.8, 126.0, 127.5, 129.3, 129.7, 130.4, 137.2, 139.4, 146.7, 149.1, 156.6;
ESI-MS (m/z,): 404 (100); Anal. calcd for C H FeN: C, 77.43; H, 5.25; N, 3.47;
3
) δ 21.5, 69.4, 70.1, 70.6, 84.0, 119.7,
1
26
21
Found: C, 77.76; H, 4.93; N, 3.40.
-Ferrocenyl-2-(4-methoxyphenyl)quinoline (4c): Red solid; Mp: 163-165 C; H
NMR (500 MHz, CDCl ) δ 3.90 (s, 3H), 4.21 (s, 5H), 4.51 (s, 2H), 4.80 (s, 2H), 7.07
o
1
4
3
1
3

ACCEPTED MANUSCRIPT
(d, J = 9.0 Hz, 2H), 7.50 (t, J = 7.5 Hz, 1H), 7.69 (t, J = 7.5 Hz, 1H), 8.09~8.17 (m,
1
3
4
8
1
7
3
H), 8.56 (d, J = 8.5 Hz, 1H); C NMR (125 MHz, CDCl ) δ 55.5, 69.4, 70.0, 70.6,
3.9, 114.4, 119.3, 125.4, 125.7, 125.8, 128.9, 129.2, 130.2, 132.5, 146.6, 149.0,
+
56.1, 160.8; EI-MS (m/z,): 420 [(M+H) , 100]; Anal. calcd for C H FeNO: C,
26
21
4.48; H, 5.05; N, 3.34; Found: C, 74.47; H, 5.07; N, 3.22.
-(4-Ferrocenylquinolin-2-yl)-2-methoxyphenol (4d): Red solid; Mp: 95-98 C; H
NMR (500 MHz, CDCl ) δ 4.01 (s, 3H), 4.20 (s, 5H), 4.49 (s, 2H), 4.79 (s, 2H), 6.36
s, 1H), 7.05 (d, J = 8.0 Hz, 1H), 7.49 (t, J = 7.5 Hz, 1H), 7.61 (d, J = 7.0 Hz, 1H),
o
1
4
3
(
7
=
.68 (t, J = 7.5 Hz, 1H), 7.89 (s, 1H), 8.09 (s, 1H), 8.18 (d, J = 8.0 Hz, 1H), 8.55 (d, J
13
3
8.5 Hz, 1H); C NMR (125 MHz, CDCl ) δ 56.0, 69.3, 69.9, 70.5, 83.8, 110.0,
114.6, 119.4, 120.7, 125.3, 125.7, 125.8, 129.2, 129.9, 132.2, 146.7, 147.2, 147.2,
+
1
48.8, 156.2; HRMS calcd for C26
H22FeNO
2
[M+H] : 436.1005, found: 436.0989.
1
N,N-Dimethyl-4-(4-ferrocenylquinolin-2-yl)benzenamine (4e): Red oil; H NMR
(
500 MHz, CDCl ) δ 3.05 (s, 6H), 4.19 (s, 5H), 4.46 (s, 2H), 4.75 (s, 2H), 6.85 (d, J =
3
8
.5 Hz, 2H), 7.44 (t, J = 7.5 Hz, 1H), 7.65 (t, J = 7.5 Hz, 1H), 8.10~8.15 (m, 4H), 8.49
1
3
(
d, J = 8.0 Hz, 1H); C NMR (125 MHz, CDCl
3
) δ 40.5, 69.3, 70.0, 70.6, 84.3, 112.4,
119.1, 124.9, 125.7, 125.7, 127.6, 128.5, 129.1, 130.0, 146.1, 149.1, 151.4, 156.6;
+
HRMS calcd for C27
H
25FeN
2
[M+H] : 433.1362, found: 433.1360.
1
2
-(4-Chlorophenyl)-4-ferrocenylquinoline (4f): Red oil; H NMR (500 MHz,
3
CDCl ) δ 4.16 (s, 5H), 4.47 (s, 2H), 4.76 (s, 2H), 7.23 (m, 3H), 7.68 (t, J = 7.5 Hz,
13
1
H), 8.04 (s, 1H), 8.11~8.17 (m, 3H), 8.57 (d, J = 8.5 Hz, 1H); C NMR (125 MHz,
3
CDCl ) δ 69.6, 70.1, 70.6, 83.6, 119.2, 125.8, 125.9, 126.1, 128.8, 129.1, 129.5, 130.4,
1
4

ACCEPTED MANUSCRIPT
+
1
35.5, 138.3, 147.2, 149.0, 155.2; HRMS calcd for C25
H
19FeNCl [M+H] : 424.0551,
found: 424.0554.
1
2
-(4-Bromophenyl)-4-ferrocenylquinoline (4g): Red oil; H NMR (500 MHz,
CDCl ) δ 4.16 (s, 5H), 4.47 (t, J = 1.5 Hz, 2H), 4.76 (t, J = 1.5 Hz, 2H), 7.49~7.52 (m,
3
1
1
1
H), 7.64~7.70 (m, 3H), 8.05 (m, 3H), 8.17 (d, J = 8.0 Hz, 1H), 8.57 (d, J = 8.0 Hz,
1
3
3
H); C NMR (125 MHz, CDCl ) δ 69.6, 70.1, 70.5, 83.6, 119.1, 123.9, 125.8, 125.9,
26.1, 129.1, 129.5, 130.4, 132.1, 138.7, 147.3, 148.9, 155.2; HRMS calcd for
+
C
25
H
19FeNBr [M+H] : 468.0047, found: 468.0038.
o
2
-(3,4-Dichlorophenyl)-4-ferrocenylquinoline (4h): Yellow solid; Mp: 184-189 C;
1
H NMR (500 MHz, CDCl ) δ 4.20 (s, 5H), 4.53 (t, J = 2.0 Hz, 2H), 4.81 (t, J = 2.0
3
Hz, 2H), 7.55~7.61 (m, 2H), 7.71~7.74 (m, 1H), 8.00~8.02 (m, 2H), 8.17 (d, J = 8.5
13
Hz, 1H), 8.33 (s, 1H), 8.64 (d, J = 8.0 Hz, 1H); C NMR (125 MHz, CDCl
3
) δ 69.6,
7
1
0.0, 70.5, 83.3, 112.4, 118.9, 125.8, 126.1, 126.5, 129.4, 129.6, 130.4, 130.8, 133.2,
+
33.5, 139.8, 147.6, 148.9, 153.8; EI-MS (m/z,): 458 [(M+H) , 100]; Anal. calcd for
: C, 65.54; H, 3.74; N, 3.06; Found: C, 65.88; H, 3.86; N, 2.94.
-(2-Chlorophenyl)-4-ferrocenylquinoline (4i): Yellow solid; Mp: 174-176 C; H
NMR (500 MHz, CDCl ) δ 4.21 (s, 5H), 4.48 (s, 2H), 4.78 (s, 2H), 7.38~7.45 (m, 2H),
.53~7.57 (m, 2H), 7.70~7.74 (m, 2H), 8.04 (s, 1H), 8.19 (d, J = 8.5 Hz, 1H), 8.55 (d,
25 2
C H17FeNCl
o
1
2
3
7
13
J = 8.0 Hz, 1H); C NMR (125 MHz, CDCl ) δ 69.4, 70.0, 70.7, 83.3, 123.3, 125.7,
3
1
1
26.1, 126.2, 127.3, 129.3, 129.9, 130.2, 130.3, 131.9, 132.4, 139.9, 146.1, 148.7,
+
56.5; HRMS calcd for C25
H
19FeNCl [M+H] : 424.0558, found: 424.0551.
1
4
-Ferrocenyl-2-(2-fluorophenyl)quinoline (4j): Red oil; H NMR (500 MHz, CDCl
3
)
1
5

ACCEPTED MANUSCRIPT
δ 4.20 (s, 5H), 4.46 (t, J = 1.5 Hz, 2H), 4.76 (t, J = 1.5 Hz, 2H), 7.21~7.24 (m, 1H),
7
8
.33 (t, J = 7.5 Hz, 1H), 7.41~7.45 (m, 1H), 7.50~7.53 (m, 1H), 7.67~7.70 (m, 1H),
.13~8.16 (m, 1H), 8.19 (d, J = 8.5 Hz, 1H), 8.23 (d, J = 2.5 Hz, 1H), 8.46 (d, J = 8.0
13
Hz, 1H); C NMR (125 MHz, CDCl ) δ 69.3, 70.1, 70.8, 83.6, 116.2, 116.4, 123.4,
3
1
1
23.5, 124.8, 125.7, 126.1, 126.2, 128.1, 128.2, 129.3, 130.3, 130.7, 130.8, 131.6,
+
46.6, 148.9, 153.1, 159.9, 161.9; HRMS calcd for C25
H
19FeNF [M+H] : 408.0846,
found: 408.0855.
1
4
-Ferrocenyl-2-(4-fluorophenyl)quinoline (4k): Red oil; H NMR (500 MHz,
CDCl ) δ 4.16 (s, 5H), 4.46 (s, 2H), 4.76 (s, 2H), 7.21 (t, J = 8.5 Hz, 2H), 7.50 (t, J =
3
7
.5 Hz, 1H), 7.68 (t, J = 7.5 Hz, 1H), 8.04 (s, 1H), 8.15~8.18 (m, 3H), 8.57 (d, J = 8.5
1
3
Hz, 1H); C NMR (125 MHz, CDCl
3
) δ 69.5, 70.0, 70.5, 83.6, 115.8, 116.0, 125.7,
1
25.8, 125.9, 129.3, 129.4, 130.3, 136.1, 147.1, 149.0, 155.4, 162.8, 164.8; HRMS
+
calcd for C25H19FeNF [M+H] : 408.0846, found: 408.0850.
o
1
4
-Ferrocenyl-2-(2-nitrophenyl)quinoline (4l): Red solid; Mp: 59-61 C; H NMR
500 MHz, CDCl ) δ 4.20 (s, 5H), 4.50 (s, 2H), 4.77 (s, 2H), 7.56~7.63 (m, 2H),
.70~7.81 (m, 4H), 8.00 (d, J = 8.5 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 8.56 (d, J = 8.5
(
3
7
13
Hz, 1H); C NMR (125 MHz, CDCl
3
) δ 69.6, 70.1, 70.7, 83.0, 121.0, 124.5, 125.8,
1
26.1, 126.4, 129.4, 129.6, 130.3, 131.7, 132.8, 136.0, 147.5, 148.6, 149.3, 154.8;
+
HRMS calcd for C H FeN O [M+H] : 435.0791, found: 435.0793.
25
19
2
2
o
1
4
-Ferrocenyl-2-(3-nitrophenyl)quinoline (4m): Red solid; Mp: 158-160 C; H
NMR (500 MHz, CDCl ) δ 4.19 (s, 5H), 4.52 (s, 2H), 4.81 (s, 2H), 7.56 (t, J = 7.5 Hz,
H), 7.66~7.74 (m, 2H), 8.09 (s, 1H), 8.18 (d, J = 8.5 Hz, 1H), 8.28 (d, J = 8.0 Hz,
3
1
1
6

ACCEPTED MANUSCRIPT
13
1
H), 8.52 (d, J = 7.5 Hz, 1H), 8.65 (d, J = 8.5 Hz, 1H), 9.04 (s, 1H); C NMR (125
MHz, CDCl
3
) δ 69.8, 70.1, 70.5, 83.2, 118.8, 122.4, 123.8, 125.9, 126.3, 126.4, 129.8,
+
1
1
4
29.8, 130.5, 133.3, 141.5, 147.9, 148.8, 148.9, 153.5; EI-MS (m/z,): 435 [(M+H) ,
00]; Anal. calcd for C H FeN O : C, 69.14; H, 4.18; N, 6.45; Found: C, 69.43; H,
25
18
2
2
.27; N, 6.42.
-Ferrocenyl-2-(4-nitrophenyl)quinoline (4n): Red solid; Mp: 176-178 C; H
NMR (500 MHz, CDCl ) δ 4.22 (s, 5H), 4.56 (s, 2H), 4.83 (s, 2H), 7.61 (t, J = 7.5 Hz,
H), 7.62 (t, J = 7.5 Hz, 1H), 8.14 (s, 1H), 8.21 (d, J = 8.0 Hz, 1H), 8.37~8.42 (m,
o
1
4
3
1
4
13
H), 8.67 (t, J = 8.5 Hz, 1H); C NMR (125 MHz, CDCl ) δ 69.8, 70.1, 70.5, 83.2,
3
119.3, 124.1, 125.9, 126.4, 126.6, 128.2, 129.8, 130.6, 145.8, 147.9, 148.3, 149.0,
+
1
53.7; HRMS calcd for C25
H
19FeN
2
O
2
[M+H] : 435.0801, found: 435.0796.
o
1
2
-(Furan-2-yl)-4-ferrocenylquinoline (4o): Red solid; Mp: 192-194 C; H NMR
3
(500 MHz, CDCl ) δ 4.21 (s, 5H), 4.51 (s, 2H), 4.80 (s, 2H), 6.61 (d, J = 1.5 Hz, 1H),
7
.25 (s, 1H), 7.50 (t, J = 7.5 Hz, 1H), 7.66~7.68 (m, 2H), 8.11~8.15 (m, 2H), 8.52 (d,
13
J = 8.5 Hz, 1H); C NMR (125 MHz, CDCl
3
) δ 69.5, 70.1, 70.6, 83.5, 109.9, 112.3,
118.0, 125.6, 125.8, 126.2, 129.5, 130.1, 144.1, 147.0, 148.3, 148.9, 154.0; EI-MS
+
(
m/z,): 380 [(M+H) , 100]; Anal. calcd for C23
Found: C, 72.95; H, 4.54;N, 3.63.
-Ferrocenyl-2-(thiophen-2-yl)quinoline (4p): Red solid; Mp: 155-157 C; H
NMR (500 MHz, CDCl ) δ 4.17 (s, 5H), 4.46 (t, J = 1.5 Hz, 2H), 4.75 (t, J = 1.5 Hz,
H), 7.15~7.17 (m, 1H), 7.44~7.47 (m, 2H), 7.63~7.66 (m, 1H), 7.76 (t, J = 1.5 Hz,
H17FeNO: C, 72.84; H, 4.52; N, 3.69;
o
1
4
3
2
1
13
H), 8.05 (s, 1H), 8.10 (d, J = 8.5 Hz, 1H), 8.49 (d, J = 8.5 Hz, 1H); C NMR (125
1
7

ACCEPTED MANUSCRIPT
MHz, CDCl
3
) δ 69.5, 70.1, 70.6, 83.6, 118.4, 125.6, 125.6, 125.8, 126.2, 128.2, 128.4,
+
1
29.5, 130.0, 145.6, 146.8, 148.8, 151.5; EI-MS (m/z,): 396 [(M+H) , 100]; Anal.
calcd for C23
-Ferrocenyl-2-styrylquinoline (4q): Red solid; Mp: 113-115 C; H NMR (500
MHz, CDCl ) δ 4.20 (s, 5H), 4.50 (t, J = 1.5 Hz, 2H), 4.79 (t, J = 1.5 Hz, 2H),
.32~7.34 (m, 1H), 7.40~7.43 (m, 3H), 7.49~7.52 (m, 1H), 7.67~7.71 (m, 3H), 7.75 (s,
H17FeNS: C, 69.88; H, 4.33; N, 3.54; Found: C, 70.22; H, 4.33; N, 3.52.
o
1
4
3
7
1
1
3
H), 7.88 (s, 1H), 8.10 (d, J = 8.5 Hz, 1H), 8.57 (d, J = 8.5 Hz, 1H); C NMR (125
) δ 69.4, 70.0, 70.5, 83.6, 120.0, 125.5, 125.8, 126.2, 127.3, 128.6, 128.8,
29.1, 129.4, 129.9, 134.1, 136.6, 146.4, 148.9, 155.0; HRMS calcd for C H FeN
MHz, CDCl
3
1
27
22
+
[
M+H] : 416.1096, found: 416.1088.
o
Ethyl 4-ferrocenylquinoline-2-carboxylate (4r): Red solid; Mp: 166-168 C; IR
-
1 1
(
KBr): 3078, 1717, 1581, 1138, 846 cm ; H NMR (500 MHz, CDCl
.5 Hz, 3H), 4.19 (s, 5H), 4.53 (t, J = 2.0 Hz, 2H), 4.57~4.61 (m, 2H), 4.82 (t, J = 2.0
Hz, 2H), 7.62~7.65 (m, 1H), 7.74~7.77 (m, 1H), 8.32 (d, J = 8.5 Hz, 1H), 8.45 (s, 1H),
3
) δ 1.52 (t, J =
7
1
3
8
8
3
.59 (d, J = 8.5 Hz, 1H); C NMR (125 MHz, CDCl ) δ 14.4, 62.2, 69.7, 70.1, 70.7,
2.7, 121.7, 125.7, 127.8, 128.0, 129.7, 131.4, 147.3, 148.2, 148.3, 165.8; HRMS
+
calcd for C22
H
20FeNO
2
[M+H] : 386.0843, found: 386.0854.
o
1
4
-Ferrocenyl-6-methyl-2-phenylquinoline (4s): Red solid; Mp: 174-176 C; H
NMR (500 MHz, CDCl ) δ 2.55 (s, 3H), 4.19 (s, 5H), 4.48 (s, 2H), 4.77 (s, 2H), 7.45
3
(t, J = 7.5 Hz, 1H), 7.52~7.55 (m, 3H), 8.08~8.10 (m, 2H), 8.17 (d, J = 7.5 Hz, 2H),
1
3
8
1
.36 (s, 1H); C NMR (125 MHz, CDCl
3
) δ 22.2, 69.3, 70.0, 70.6, 84.1, 119.8, 124.7,
26.0, 127.5, 128.9, 129.1, 130.1, 131.5, 135.4, 140.1, 145.9, 147.5, 155.7; EI-MS
1
8

ACCEPTED MANUSCRIPT
+
(
m/z,): 404 [(M+H) , 100]; Anal. calcd for C26
Found: C, 77.76; H, 5.21; N, 3.47.
-Ferrocenyl-2-phenylquinolin-6-ol (4t): Red solid; Mp: 191-193 C; H NMR
H21FeN: C, 77.43; H, 5.52; N, 3.47;
o
1
4
(
500 MHz, DMSO) δ 4.25 (s, 5H), 4.57 (s, 2H), 4.94 (s, 2H), 7.32~7.34 (m, 1H), 7.47
t, J = 7.0 Hz, 1H), 7.56 (t, J = 7.5 Hz, 2H), 7.94~7.98 (m, 2H), 8.14 (s, 1H), 8.26 (d,
(
13
J = 7.0 Hz, 2H); 10.11 (s, 1H); C NMR (125 MHz, CDCl
3
) δ 69.8, 70.2, 70.3, 83.7,
1
1
4
07.3, 119.1, 122.3, 127.1, 127.3, 129.2, 129.4, 131.9, 139.5, 144.0, 144.6, 152.6,
+
55.8; EI-MS (m/z,): 406 [(M+H) , 100]; Anal. Calcd for C25
H19FeNO: C, 74.09; H,
.73; N, 3.46; Found: C, 74.12; H, 4.74; N, 3.42.
o
1
6
-Chloro-4-ferrocenyl-2-phenylquinoline (4u): Red solid; Mp: 188-190 C; H
NMR (500 MHz, CDCl ) δ 4.21 (s, 5 H), 4.51 (s, 2H), 4.76 (s, 2H), 7.47~7.54 (m,
3
13
3
H), 7.63 (d, J = 8.0 Hz, 1H), 8.06~8.16 (m, 4H), 8.73 (s, 1H); C NMR (125 MHz,
CDCl
3
) δ 69.8, 70.1, 70.3, 83.1, 120.2, 125.0, 126.6, 127.5, 129.0, 129.5, 130.1, 131.3,
+
1
31.9, 139.5, 146.2, 147.4, 156.8; EI-MS (m/z,): 424 [(M+H) , 100]; Anal. Calcd for
C
25
H
18FeNCl: C, 70.87; H, 4.28; N, 3.31; Found: C, 71.20; H, 4.29;N, 3.25.
-Bromo-4-ferrocenyl-2-phenylquinoline (4v): Red solid; Mp: 222-224 C; H
NMR (500 MHz, CDCl ) δ 4.22 (s, 5H), 4.53 (s, 2H), 4.77 (s, 2H), 7.48~7.54 (m, 3H),
.76 (d, J = 8.5 Hz, 1H), 8.05 (d, J = 8.0 Hz, 2H), 8.15 (d, J = 7.0 Hz, 2H), 8.95 (s,
o
1
6
3
7
1
1
1
3
H); C NMR (125 MHz, CDCl ) δ 69.8, 70.1, 70.3, 83.1, 119.6, 120.1, 127.0, 127.5,
3
28.4, 129.0, 129.5, 132.1, 132.6, 139.5, 146.1, 147.6, 156.9; EI-MS (m/z,): 468
+
[
(M+H) , 100]; Anal. Calcd for C25
H
18FeNBr: C, 64.14; H, 3.88; N, 2.99; Found: C,
6
4.31; H, 3.91; N, 2.97.
1
9

ACCEPTED MANUSCRIPT
o
1
7
-Chloro-4-ferrocenyl-2-phenylquinoline (4w): Yellow solid; Mp: 200-202 C; H
NMR (500 MHz, CDCl ) δ 4.21 (s, 5H), 4.39 (s, 2H), 4.60 (s, 2H), 7.43 (d, J = 7.0 Hz,
H), 7.48~7.52 (m, 2H), 7.57 (t, J = 7.8 Hz, 2H), 8.11 (d, J = 8.5 Hz, 1H), 8.24 (d, J =
3
1
7
1
13
.0 Hz, 2H), 8.70 (s, 1H); C NMR (125 MHz, CDCl ) δ 67.6, 69.6, 72.8, 90.2, 125.4,
3
25.4, 127.3, 128.6, 129.0, 129.0, 129.7, 129.7, 130.7, 138.9, 145.9, 150.1, 155.9;
+
EI-MS (m/z,): 424 [(M+H) , 100]; Anal. calcd for C25
H18FeNCl: C, 70.87; H, 4.28; N,
3
.31; Found: C, 71.12; H, 4.29; N, 3.23.
-Chloro-4-ferrocenyl-2-phenylquinoline (4x): Red solid; Mp: 171-173 C; H
NMR (500 MHz, CDCl ) δ 4.20 (s, 5H), 4.51 (t, J = 2.0 Hz, 2H), 4.78 (t, J = 2.0 Hz,
o
1
8
3
2
H), 7.39~7.43 (m, 1H), 7.49 (t, J = 7.5 Hz, 1H), 7.56 (t, J = 7.5 Hz, 2H), 7.82~7.83
13
(
m, 1H), 8.23 (s, 1H), 8.30~8.32 (m, 2H), 8.48~8.50 (m, 1H); C NMR (125 MHz,
CDCl
3
) δ 69.5, 70.0, 70.6, 83.5, 120.0, 124.8, 125.1, 127.3, 127.5, 128.9, 129.4, 129.6,
+
1
34.4, 139.3, 145.0, 147.6, 156.3; EI-MS (m/z,): 424 [(M+H) , 100]; Anal. calcd for
C H FeNCl: C, 70.87; H, 4.28; N, 3.31; Found: C, 71.15; H, 4.30; N, 3.26.
25
18
o
1
4
-Ferrocenyl-8-fluoro-2-phenylquinoline (4y): Red solid; Mp: 157-159 C; H
NMR (500 MHz, CDCl
.53~7.56 (m, 2H), 8.12 (s, 1H), 8.22~8.24 (m, 2H), 8.33 (d, J = 8.0 Hz, 1H); C
NMR (125 MHz, CDCl ) δ 69.6, 70.1, 70.6, 83.5, 113.2, 113.4, 120.4, 121.5, 125.0,
21.1, 127.6, 127.7, 129.0, 129.6, 139.4, 139.5, 147.1, 156.5, 157.6, 159.7; EI-MS
3
) δ 4.19 (s, 5H), 4.49 (s, 2H), 4.77 (s, 2H), 7.36~7.49 (m, 3H),
13
7
3
1
+
(
m/z,): 408 [(M+H) , 100]; Anal. calcd for C25
Found: C, 73.90; H, 4.41; N, 3.42.
-Ferrocenyl-7-nitro-2-phenylquinoline (4z): Red solid; Mp: 188-190 C; H NMR
H18FeNF: C, 73.73; H, 4.45; N, 3.44;
o
1
4
2
0

ACCEPTED MANUSCRIPT
(
500 MHz, CDCl
3
) δ 4.10 (s, 5H), 4.43 (s, 2H), 4.65 (s, 2H), 7.55~7.69 (m, 4H), 7.85
13
(
s, 1H), 8.24~8.25 (m, 2H), 8.37 (d, J = 7.0 Hz, 1H), 8.59 (s, 1H); C NMR (125
MHz, CDCl
3
) δ 69.0, 69.7, 70.2, 87.4, 119.5, 123.7, 124.4, 127.5, 127.5, 129.2, 130.2,
+
1
35.2, 138.6, 146.1, 148.7, 149.4, 157.3; EI-MS (m/z,): 435 [(M+H) , 100]; Anal.
calcd for C25
.44.
2 2
H18FeN O : C, 69.14; H, 4.18; N, 6.45; Found: C, 69.44; H, 4.17; N,
6
Acknowledgements
This project is generously supported by National Natural Science Foundation of
China (Nos. 21262023 and 20902044) and the Program for Young Talents of Science
and Technology in Universities of Inner Mongolia Autonomous Region
(NJYT-12-B03)
Supplementary data
1
13
Copies of the H NMR and C NMR spectra for all new compounds in this article
could be found in the support information.
References and notes
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Supporting Information
Ce(OTf) -Catalyzed Multicomponent Domino
3
Cyclization–Aromatization of Ferrocenylacetylene, Aldehydes
and Amines: A Straightforward Synthesis of
Ferrocene-Containing Quinolines
Shufeng Chen,* Ling Li, Haiying Zhao, Baoguo Li*
College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China
E-mail address: shufengchen@imu.edu.cn, baoguol@sohu.com
CONTENTS
1
1
2
.
.
H NMR spectra…………………………………………………………………………...….S2
1
3
C NMR spectra…………………………………………………………………….……....S15
S1

ACCEPTED MANUSCRIPT
1
1
. H NMR spectra
CH3
N
Fe
4b
S2

ACCEPTED MANUSCRIPT
OCH3
N
Fe
4c
H3CO
OH
N
Fe
4
d
S3

ACCEPTED MANUSCRIPT
N(CH3)2
N
Fe
4e
Cl
N
Fe
4f
S4

ACCEPTED MANUSCRIPT
Br
N
Fe
4g
Cl
Cl
N
Fe
4h
S5