An efficient synthesis of quinolines via copper-catalyzed C-N cleavage

Article abstract of DOI:10.1039/c5ob00075k

An efficient method to synthesize substituted quinolines from ketones and 2-amino benzylamines is described. Copper-catalyzed C-N cleavage of amines followed by condensation with ketones deliver quinolines in moderate to high yields. The broad scope of su

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DynamiDcOAI: 1r0t.i1c03lVe9ie/CwL5AiOrntiBck0le0sO0►n7li5nKe
Organic & Biomolecular Chemistry
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Cite this: DOI: 10.1039/c0xx00000x
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ARTICLE TYPE
An Efficient Synthesis of Quinolines Via Copper-catalyzed C-N
Cleavage
Long-Yi Xi, Ruo-Yi Zhang,Lei Zhang, Shan-Yong Chen,* and Xiao-Qi Yu*
Received (in XXX, XXX) XthXXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
An efficient method to synthesize substituted quinolines from ketones and 2-amino benzylamines is
described. Copper-catalyzed C-N cleavage of amines followed by condensation with ketones deliver
quinolines in moderate to high yields. The broad scope of substrates and the use of air as the sole oxidant
make this transformation very attractive.
We initiated our investigation by heating acetophenone, 2-
aminobenzylamine, p-toluenesulfonic and Cu(OTf)2 in ethanol at
35 80 C under air atmosphere for 24 h. As expected, the formation
10 Introduction
o
Quinolines are one of the most ubiquitous moieties found in
natural products1, biologically active molecules2 and
functionalized materials3 (Figure 1), and therefore have caught
much attention from synthetic chemists. As a result, a number of
15 efficient strategies for the preparation of quinolines, such as
Skraup, Combes, Gould−Jacobs, Friedländer, and Doebner−von
Miller reactions, were developed.4 In light of their importance,
the development of new synthetic strategy for the synthesis of
quinolines from readily available materials under mild conditions
20 is still in demand. Transition-metal-catalyzed cleavage of C-N
bonds to generate C-C bonds has attracted considerable
attention,5 because such bonds are common in organic chemistry
and are usually unreactive. We have recently reported a copper-
catalyzed synthesis of pyridines from 1,3-propanediamine and
of 2-phenylquinoline was observed albeit in low yield (Table 1,
entry 1). We observed that the majority of acetophenone
unreacted in the above reaction, therefore we prolonged reaction
time to complete this transformation. To our delight, the yield
40 increased up to 93%, when the mixture was heated for 72 h
(Entries 2 and 3 vs entry 1). It should be noted that using oxygen
as the oxidant was ineffective (Entry 4 vs entry 2), which is
different from our previous result.6 To evaluate reaction
temperature, 1,4-dioxane was used as the solvent. By stirring the
o
45 mixture in 1,4-dioxane at 100 C, this transformation completed
within 36 h, affording the product in 95% yield (Entry 5). After
screening metal catalysts, we found that Cu(OTf)2 was the most
effective catalyst for this reaction (Entry 5 vs entries 6-9). Most
tested solvents were comfortable for this transformation. Among
50 them, toluene gave the best result (Entry 11 vs entries 12-15).
25 acetophenones
via
a
domino
C-N
cleavage/cyclization/aromatization reaction.6 We envisioned that
2-aminobenzylamine would undergo similar reaction to afford
quinolines.7
Table 1.Optimization of reaction conditionsa
Figure 1. Examples of useful quinoline derivatives
Entry
1c
Catalyst
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
CuCl2
CuI
Cu(OAc)2
FeCl3
Zn(OAc)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Solvent
ethanol
ethanol
ethanol
Yield(%)b
23
63
93
45
95
29
50
16
77
23
99
64
93
95
92
2d
3e
4f
5
6
7
8
9
10
11
12
13
14
15g
ethanol
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
toluene
DMSO
CH3CN
DCE
toluene/water
30
Results and discussion
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aReaction conditions: 1a (0.15 mmol), 2a (0.45 mmol), solvent (0.5 mL),
p-toluenesulfonic acid (0.05 mmol), catalyst (0.03 mmol), 36 h, under air
TsOH·H2O (0.05 mmol), Cu(OTf)2 (0.03 mmol), 100 oC, 36 h, under air
atmosphere, isolated yields.
c
o
atmosphere, 100 oC unless otherwise noted. bIsolated yields. 24 h, 80 C;
o
f
o
g
d48 h, 80 C; e72 h, 80 °C ; 48 h, 80 C, O2 balloon. Using toluene/water
unsymmetrical alkyl ketones with 2-amino benzaldehydes often
25 results in mixtures of 2-alkyl versus 2,3-dialkyl quinolines due to
nonregioselective enolate formation.8 Biheteroaryls containing
azines frequently exist in natural products, pharmaceuticals,
bioactive molecules.9 When acetyl pyridines were subjected to
this reaction, excellent yields of pyridyl quinolines were isolated
30 (3w and 3x). 2-Acetyl thiophenes provided the corresponding
products in moderate yields (3y and 3z).While, 2-acetylfuran
afforded low yield of product (3aa), which may be affected by its
instability.
5 (95/5) as the solvent
With optimized conditions in hand, we examined the reaction
of various methyl ketones with 2a (Figure 2). Methyl ketones
bearing an electron-withdrawing or electron-donating substituent
10 provided the corresponding products in good to excellent yields.
This reaction tolerates a range of functionalities, including fluoro,
chloro, bromo, nitro, sulfone, ether, moieties. Notably, free amino
and phenol moieties also survived in this reaction (3s and 3t).
Interestingly, 1-acetylferrocene proceeded well, affording 2-
15 ferrocenylquinoline in 91% yield (3u). Hexan-2-one also
underwent such transformation, providing 2-butyl quinoline (3v)
in 78% yield. Notably, the classic Friedländer annulation of
Figure 3.Scope of disubstituted ketonesa
Figure 2.Scope of ketonesa
35
aReaction conditions: 1 (0.15 mmol), 2a (0.45 mmol), toluene (0.5 mL),
TsOH·H2O (0.05 mmol), Cu(OTf)2 (0.03 mmol), 100 oC, 36 h, under air
atmosphere, isolated yields.
40 Figure 4.Scope of anilinesa
aReaction conditions: 1 (0.15mmol), 2 (0.45mmol), toluene (0.5 mL),
TsOH·H2O (0.05 mmol), Cu(OTf)2 (0.03 mmol), 100 oC, 36 h, under air
45 atmosphere, isolated yields. bPart of ketone remains unchanged.
We further explored disubstituted ketones. As shown in figure
3, disubstituted ketones also underwent this transformation
affording 2,3-disubstituted quinolines in moderate to good yields.
20
aReaction conditions: 1 (0.15 mmol), 2a (0.45 mmol), toluene (0.5 mL),
2
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Finally, to widen the scope of substrates, several 2-
aminobenzylamines with a substituent on the aryl ring were
2-phenylquinoline (3a):White solid (30.8 mg, 99%) m.p.84-86
oC 1H NMR (400 MHz, CDCl3) δ 8.26 – 8.15 (m, 4H), 7.87 (d, J
synthesized. These compounds provided quinolines in acceptable 45 = 8.6 Hz, 1H), 7.83 (d, J = 8.2 Hz, 1H), 7.74 (ddd, J = 8.4, 6.9,
yields (Figure 4).
1.4 Hz, 1H), 7.59 – 7.50 (m, 3H), 7.50 – 7.45 (m, 1H) 13C NMR
(100 MHz, CDCl3) δ157.50, 148.40, 139.81, 136.91, 129.86,
129.79, 129.45, 128.98, 127.70, 127.59, 127.30, 126.41, 119.15
HRMS m/z (ESI): calcd. for [C15H11N+H]+: 206.0964, found
50 206.0968
5 Figure 5. Proposed mechanism
2-(p-tolyl)quinoline (3b): White solid (32.5 mg, 99%) m.p. 82-
o
1
83 C H NMR (400 MHz, CDCl3) δ 8.27 (d, J = 8.4 Hz, 1H),
8.12 (dd, J = 16.0, 8.4 Hz, 3H), 7.85 – 7.71 (m, 3H), 7.55 – 7.48
(m, 1H), 7.37 (d, J = 8.0 Hz, 2H), 2.47 (s, 3H) 13C NMR (100
55 MHz, CDCl3) δ 157.11, 148.21, 139.27, 136.74, 136.53, 129.57,
129.50, 129.48, 127.39, 127.37, 127.00, 125.97, 118.68, 21.30
HRMS m/z (ESI): calcd. for [C16H13N+H]+: 220.1121, found
220.1116
2-(4-(tert-butyl)phenyl)quinoline (3c): Yellow oil (38.2 mg,
1
60 97%) H NMR (400 MHz, CDCl3) δ 8.20 (dd, J = 8.5, 4.1 Hz,
On the basis of literature reports,6,7 a plausible mechanistic
proposal is outlined in Figure 5. This transformation begins with
the condensation of acetophenone 1a and 2-aminobenzylamine
10 2a. The resulting imine Ⅰis oxidized to intermediateⅡ, which
undergoes cyclization and elimination to afford quinoline 3a.
2H), 8.17 – 8.08 (m, 2H), 7.87 (d, J = 8.6 Hz, 1H), 7.84 – 7.80 (m,
1H), 7.77 – 7.69 (m, 1H), 7.61 – 7.55 (m, 2H), 7.55 – 7.49 (m,
1H), 1.41 (s, 9H) 13C NMR (100 MHz, CDCl3) δ 157.47, 152.60,
148.41, 137.03, 136.73, 129.79, 129.65, 127.54, 127.38, 127.18,
65 126.17, 125.92, 119.04, 34.85, 31.41 HRMS m/z (ESI): calcd. for
[C19H19N+H]+: 262.1590, found 262.1569
2-([1,1'-biphenyl]-4-yl)quinoline (3d): White solid (33.7 mg,
80%) m.p. 174 – 177 oC 1H NMR (400 MHz, CDCl3) δ 8.27 (d, J
= 8.3 Hz, 2H), 8.22 (t, J = 7.8 Hz, 2H), 7.92 (d, J = 8.6 Hz, 1H),
70 7.84 (d, J = 8.0 Hz, 1H), 7.76 (dd, J = 14.7, 7.8 Hz, 3H), 7.70 (d,
J = 7.3 Hz, 2H), 7.52 (dt, J = 20.8, 7.6 Hz, 3H), 7.40 (t, J = 7.3 Hz,
1H) 13C NMR (100 MHz, CDCl3) δ 156.99, 148.45, 142.16,
140.68, 138.63, 136.91, 129.85, 129.82, 128.98, 128.08, 127.71,
127.67, 127.60, 127.32, 127.26, 126.41, 119.00 HRMS m/z (ESI):
75 calcd. for [C21H15N+H]+: 282.1277, found 282.1274
Conclusions
In conclusion, we have developed an efficient method to
15 synthesize 2- or 2, 3-substituted quinolines via a domino copper-
catalyzed C-N cleavage/cyclization reaction. Various aryl,
heteroaryl and alkyl ketones reacted well with 2-amino
benzylamines, affording quinolines in good to high yields. This
protocol described herein is attractive because of its broad scope
20 of ketones, high efficiency, and the use of air as the oxidant.
2-(naphthalen-2-yl)quinoline (3e): Yellow solid (35.9 mg, 94%)
m.p. 160-162 oC 1H NMR (400 MHz, CDCl3) δ 8.63 (s, 1H), 8.39
(dd, J = 8.6, 1.7 Hz, 1H), 8.24 (d, J = 8.6 Hz, 2H), 8.02 (dd, J =
8.2, 6.3 Hz, 3H), 7.91 (dt, J = 6.8, 3.4 Hz, 1H), 7.84 (d, J = 8.2 Hz,
Experimental section
General Information: Chemicals were purchased and used as
received unless otherwise noted. All reactions were carried out in
a sealed Schlenk tubes and monitored by TCL. H and 13C NMR 80 1H), 7.76 (qd, J = 7.0, 1.9 Hz, 1H), 7.65 – 7.51 (m, 3H) 13C NMR
1
25 spectra were recorded on a BrukerAvance-III 400 instrument
(400 MHz for 1H and 100 MHz for 13C NMR spectroscopy).
(100 MHz, CDCl3) δ 157.25, 148.46, 137.05, 136.92, 133.95,
133.60, 129.84, 128.94, 128.69, 127.83, 127.62, 127.32, 127.25,
126.82, 126.45, 125.17, 119.26 HRMS m/z (ESI): calcd. for
[C19H13N+H]+: 256.1121, found 256.1128
1
CDCl3 was used as the solvent. Chemical shift values for H and
13C NMR were referred to internal Me4Si (0 ppm). Mass spectra
were recorded on a Thermo Scientific LCQ Fleet spectrometer
30 with ESI mode.
85 2-(o-tolyl)quinoline (3f): Yellow solid (26.4 mg, 80%) m.p. 73-
o
1
77 C H NMR (400 MHz, CDCl3) δ 8.20 (dd, J = 10.4, 8.7 Hz,
2H), 7.87 (dd, J = 8.1, 1.0 Hz, 1H), 7.75 (ddd, J = 8.4, 6.9, 1.4 Hz,
1H), 7.60 – 7.49 (m, 3H), 7.40 – 7.30 (m, 3H), 2.43 (s, 3H) 13C
NMR (100 MHz, CDCl3) δ 160.38, 147.99, 140.83, 136.19,
90 136.09, 130.99, 129.82, 129.74, 129.71, 128.63, 127.63, 126.82,
126.51, 126.14, 122.49, 20.50 HRMS m/z (ESI): calcd. for
[C16H13N+H]+: 220.1121, found 220.1115
Typical Procedure for the Synthesis of2-phenylquinoline:
A mixture of acetophenone (0.018 mL, 0.15 mmol), Cu(OTf)2
(0.011g, 0.03 mmol), 2-(aminomethyl)aniline (0.054 g, 0.45
mmol), and 4-methylbenzenesulfonic acid (0.001 g, 0.05 mmol)
35 in toluene (0.5 mL) was stirred at 100°C in a sealed 25 mL
Schlenk tube for 36 h. After the reaction was finished, the
reaction mixture was cooled to room temperature. The resulting
mixture was concentrated and taken up by dichloromethane (2 ×
30 mL). The combined organic phases were dried over Na2SO4
40 (anhydrous), concentrated in vacuum, and the resulting residue
was purified by column chromatography on silica gel with
EtOAc/petroleum (1/10) to afford the product.
2-(4-fluorophenyl)quinoline (3g): White solid (30.9 mg, 92%)
m.p. 91-93 oC 1H NMR (400 MHz, CDCl3) δ 8.25 – 8.11 (m, 4H),
95 7.88 – 7.79 (m, 2H), 7.77 – 7.70 (m, 1H), 7.53 (t, J = 7.5 Hz, 1H),
7.25 – 7.15 (m, 2H) 13C NMR (100 MHz, CDCl3) δ 165.12,
162.65, 156.31, 148.30, 137.01, 135.89 (d, J = 3.1 Hz), 129.66
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(dd, J = 31.1, 12.5 Hz), 127.59, 127.16, 126.45, 118.71, 115.98,
115.77 HRMS m/z (ESI): calcd. for [C15H10FN+H]+: 224.0870,
found 224.0856
8.32 (m, 2H), 8.27 (d, J = 8.5 Hz, 1H), 8.18 (d, J = 8.4 Hz, 1H),
8.11 – 8.05 (m, 2H), 7.89 (d, J = 8.6 Hz, 1H), 7.87 – 7.83 (m, 1H),
7.76 (ddd, J = 8.4, 6.9, 1.4 Hz, 1H), 7.58 (ddd, J = 8.1, 6.9, 1.1 Hz,
1H), 3.10 (s, 3H) 13C NMR (100 MHz, CDCl3)δ155.00, 148.25,
60 144.76, 140.74, 137.38, 130.21, 129.89, 128.48, 127.92, 127.64,
127.57, 127.20, 118.86, 44.64 HRMS m/z (ESI): calcd. for
[C16H13NO2S+H]+: 284.0740, found 284.0741
2-(4-chlorophenyl)quinoline (3h): White solid (30.0 mg, 84%)
o
1
5
m.p. 112-114 C H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 8.3
Hz, 1H), 8.12 – 8.05 (m, 3H), 7.78 – 7.68 (m, 3H), 7.52 (dd, J =
6.1, 5.1 Hz, 1H), 7.50 – 7.44(m, 2H) 13C NMR (100 MHz, CDCl3)
δ155.78, 148.15, 137.92, 136.86, 135.47, 129.80, 129.65, 128.95,
128.76, 127.48, 127.15, 126.45, 118.42 HRMS m/z (ESI): calcd.
2-(4-methoxyphenyl)quinoline (3o): Yellow solid (32.3 mg,
92%) m.p. 121-124 oC 1H NMR (400 MHz, CDCl3) δ 8.22 – 8.13
65 (m, 3H), 8.10 (d, J = 8.6 Hz, 1H), 7.77 (dd, J = 8.3, 4.6 Hz, 2H),
7.75 – 7.68 (m, 1H), 7.52 – 7.45 (m, 1H), 7.09 – 7.00 (m, 2H),
3.85(s, 3H) 13C NMR (100 MHz, CDCl3) δ 160.78, 156.81,
148.27, 136.60, 132.17, 129.56, 129.50, 128.87, 127.46, 126.88,
125.89, 118.48, 114.19, 55.34 HRMS m/z (ESI): calcd. for
70 [C16H13NO+H]+: 236.1070, found 236.1067
10 for [C15H10ClN+H]+: 240.0575, found 240.0583
2-(3,4-difluorophenyl)quinoline (3i): Yellow solid (28.9 mg,
o
1
80%) m.p. 68-70 C H NMR (400 MHz, CDCl3) δ 8.21 (d, J =
8.6 Hz, 1H), 8.15 (d, J = 8.5 Hz, 1H), 8.12 – 8.03 (m, 1H), 7.92 –
7.84 (m, 1H), 7.85 – 7.70 (m, 3H), 7.54 (t, J = 7.5 Hz, 1H), 7.34 –
15 7.22 (m, 1H) 13C NMR (100 MHz, CDCl3) δ 154.93, 152.38 (dd,
J = 14, 58 Hz), 149.88 (dd, J = 15, 57Hz), 148.22, 137.21,
136.81(q, J = 4Hz), 130.09, 129.77, 127.61, 127.32, 126.77,
123.58(q, J = 4Hz), 118.35, 117.62(d, J = 17Hz), 116.70(d, J =
18Hz) HRMS m/z (ESI): calcd. for [C15H9F2N+H]+: 242.0776,
20 found 242.0780
2-(3-methoxyphenyl)quinoline (3p): Yellow solid (32.0 mg,
91%) m.p. 106-110 oC 1H NMR (400 MHz, CDCl3) δ 8.20 (d, J =
8.5 Hz, 2H), 7.88 – 7.78 (m, 3H), 7.73 (dd, J = 12.4, 7.8 Hz, 2H),
7.53 (t, J = 7.5 Hz, 1H), 7.45 (t, J = 7.9 Hz, 1H), 7.03 (dd, J = 8.2,
75 2.4 Hz, 1H), 3.93 (s, 3H) 13C NMR (100 MHz, CDCl3) δ 160.19,
157.19, 148.27, 141.22, 136.85, 129.90, 129.81, 129.75, 127.55,
127.33, 126.41, 120.09, 119.19, 115.45, 112.75, 55.49 HRMS
m/z (ESI): calcd. for [C16H13NO+H]+: 236.1070, found 236.1072
2-(3,4-dichlorophenyl)quinoline (3j): Yellow solid (25.8 mg,
63%) m.p. 103-104 oC 1H NMR (400 MHz, CDCl3) δ 8.30 (d, J =
1.9 Hz, 1H), 8.21 (d, J = 8.6 Hz, 1H), 8.15 (d, J = 8.5 Hz, 1H),
7.98 (dd, J = 8.4, 1.8 Hz, 1H), 7.86 – 7.70 (m, 3H), 7.55 (dd, J =
2-(3,4-dimethoxyphenyl)quinoline (3q): Yellow solid (39.8 mg,
25 9.9, 8.4 Hz, 2H) 13C NMR (100 MHz, CDCl3) δ 154.64, 148.23, 80 99%) m.p. 115-118 oC 1H NMR (400 MHz, CDCl3) δ 8.15 (dd, J
139.54, 137.26, 133.62, 133.22, 130.82, 130.14, 129.81, 129.47,
127.62, 127.44, 126.91, 126.63, 118.37 HRMS m/z (ESI): calcd.
for [C15H9Cl2N+H]+: 274.0185, found 274.0185
= 9.1, 5.9 Hz, 2H), 7.88 (d, J = 2.1 Hz, 1H), 7.86 – 7.75 (m, 2H),
7.74 – 7.67 (m, 1H), 7.65 (dt, J = 8.4, 2.4 Hz, 1H), 7.49 (dd, J =
7.9, 7.0 Hz, 1H), 6.97 (dd, J = 8.4, 3.5 Hz, 1H), 4.04 (s, 3H), 3.94
(d, J = 2.7 Hz, 3H) 13C NMR (100 MHz, CDCl3) δ 156.83,
85 150.34, 149.35, 148.20, 136.68, 132.49, 129.66, 129.48, 127.49,
126.98, 126.03, 120.26, 118.65, 110.97, 110.32, 56.03, 56.00
HRMS m/z (ESI): calcd. for [C17H15NO2+H]+: 266.1176, found
266.1185
2-(4-bromophenyl)quinoline (3k): White solid (34.7 mg, 82%)
30 m.p. 118-119oC 1H NMR (400 MHz, CDCl3) δ 8.18 (dd, J = 15.9,
8.6 Hz, 2H), 8.05 (d, J = 8.5 Hz, 2H), 7.82 (d, J = 8.2 Hz, 2H),
7.77 – 7.70 (m, 1H), 7.67 – 7.62 (m, 2H), 7.54 (dd, J = 11.1, 3.9
Hz, 1H) 13C NMR (100 MHz, CDCl3) δ 156.11, 148.32, 138.57,
137.08, 132.07, 129.96, 129.79, 129.19, 127.60, 127.33, 126.62,
2-(benzo[d][1,3]dioxol-5-yl)quinoline (3r): Gray solid (37.4 mg,
35 124.02, 118.60 HRMS m/z (ESI): calcd. for [C15H10BrN+H]+: 90 99%) m.p. 87-90 C H NMR (400 MHz, CDCl3) δ 8.14 (d, J =
o
1
284.0069, found 284.0047
8.5 Hz, 2H), 7.78 (dt, J = 10.0, 5.1 Hz, 3H), 7.72 (dd, J = 11.6,
4.6 Hz, 1H), 7.65 (dd, J = 8.1, 1.6 Hz, 1H), 7.49 (t, J = 7.5 Hz,
1H), 6.95 (d, J = 8.1 Hz, 1H), 6.03 (s, 2H) 13C NMR (100 MHz,
CDCl3) δ 156.69, 148.88, 148.44, 148.21, 136.75, 134.15, 129.72,
95 129.59, 127.49, 127.04, 126.12, 121.81, 118.66, 108.54, 107.97,
101.45 HRMS m/z (ESI): calcd. for [C16H11NO2+H]+: 250.0863,
found 250.0875
2-(3-bromophenyl)quinoline (3l): Yellow solid (32.5 mg, 76%)
1
m.p. 73-76oC H NMR (400 MHz, CDCl3) δ 8.36 (t, J = 1.8 Hz,
1H), 8.19 (dd, J = 14.0, 8.6 Hz, 2H), 8.07 (dd, J = 7.8, 1.0 Hz,
40 1H), 7.82 (dd, J = 8.3, 4.0 Hz, 2H), 7.78 – 7.71 (m, 1H), 7.61 –
7.51 (m, 2H), 7.38 (t, J = 7.9 Hz, 1H) 13C NMR (100 MHz,
CDCl3) δ 155.68, 148.26, 141.72, 137.13, 132.30, 130.70, 130.42,
130.00, 129.84, 127.59, 127.41, 126.75, 126.14, 123.25, 118.77
HRMS m/z (ESI): calcd. for [C15H10BrN+H]+: 284.0069, found
45 284.0077
3-(quinolin-2-yl)aniline (3s): Brown solid (24.1 mg, 73%) m.p.
1
118-122oC H NMR (400 MHz, CDCl3) δ 8.18 (dd, J = 8.2, 5.6
100 Hz, 2H), 7.82 (dd, J = 10.8, 4.8 Hz, 2H), 7.72 (ddd, J = 8.4, 6.9,
1.4 Hz, 1H), 7.59 – 7.55 (m, 1H), 7.55 – 7.45 (m, 2H), 7.31 (t, J =
7.8 Hz, 1H), 6.79 (ddd, J = 7.9, 2.4, 0.9 Hz, 1H), 3.83 (s, 2H) 13C
NMR (100 MHz, CDCl3) δ 157.59, 148.22, 147.06, 140.80,
136.74, 129.80, 129.69, 127.54, 127.29, 126.27, 119.28, 117.99,
105 116.26, 114.18 HRMS m/z (ESI): calcd. for [C15H12N2+H]+:
221.1073, found 211.1091
2-(4-nitrophenyl)quinoline (3m): Yellow solid (22.9 mg, 61%)
o
1
m.p. 124-126 C H NMR (400 MHz, CDCl3) δ 8.39 – 8.32 (m,
4H), 8.28 (d, J = 8.6 Hz, 1H), 8.18 (d, J = 8.5 Hz, 1H), 7.88 (dd, J
= 15.5, 8.4 Hz, 2H), 7.82 – 7.74 (m, 1H), 7.59 (t, J = 7.5 Hz, 1H)
50 13C NMR (100 MHz, CDCl3) δ 154.58, 148.36, 148.33, 145.51,
137.43, 130.33, 130.02, 128.38, 127.67, 127.65, 127.38, 124.11,
118.83 HRMS m/z (ESI): calcd. for [C15H10N2O2+H]+: 251.0815,
found 251.0825
2-(quinolin-2-yl)phenol (3t): Yellow solid (20.2 mg, 61%) m.p.
110-111 oC 1H NMR (400 MHz, CDCl3) δ 15.31 (s, 1H), 8.26 (d,
J = 8.9 Hz, 1H), 8.04 (dd, J = 8.6, 2.5 Hz, 2H), 7.96 (dd, J = 8.0,
110 1.5 Hz, 1H), 7.82 (d, J = 8.1 Hz, 1H), 7.75 (ddd, J = 8.4, 7.0, 1.4
2-(4-(methylsulfonyl)phenyl)quinoline (3n): Yellow solid (38.6
55 mg, 91%) m.p. 157-158 oC 1H NMR (400 MHz, CDCl3) δ 8.39 –
4
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Organic & Biomolecular Chemistry
Hz, 1H), 7.61 – 7.52 (m, 1H), 7.44 – 7.35 (m, 1H), 7.13 (dd, J = 55 127.35, 126.40, 124.89, 116.69 HRMS m/z (ESI): calcd. for
8.2, 1.1 Hz, 1H), 7.06 – 6.94 (m, 1H) 13C NMR (100 MHz,
CDCl3) δ 161.10, 158.01, 144.74, 137.71, 132.14, 130.57, 127.63,
127.03, 126.77, 126.59, 119.02, 118.83, 118.72, 117.28 HRMS
m/z (ESI): calcd. for [C15H11NO+H]+: 222.0913, found 222.0916
[C13H8ClNS+H]+: 246.0139, found 246.0135
2-(furan-2-yl)quinoline (3aa): Black solid (7.0 mg, 24%) m.p.
72-73 oC 1H NMR (400 MHz, CDCl3) δ 8.14 (dd, J = 8.2, 6.5 Hz,
2H), 7.81 (d, J = 8.7 Hz, 1H), 7.77 (d, J = 8.1 Hz, 1H), 7.73 –
5
2-ferrocenylquinoline (3u): Red solid (42.9 mg, 91%) m.p. 140- 60 7.67 (m, 1H), 7.66 – 7.61 (m, 1H), 7.52 – 7.45 (m, 1H), 7.22 (d, J
o
1
142 C H NMR (400 MHz, CDCl3) δ 8.05 (t, J = 9.1 Hz, 2H),
7.76 (dd, J = 8.1, 1.1 Hz, 1H), 7.68 (ddd, J = 8.3, 6.9, 1.5 Hz, 1H),
7.58 (d, J = 8.6 Hz, 1H), 7.48 (ddd, J = 8.0, 6.9, 1.1 Hz, 1H), 5.12
= 3.4 Hz, 1H), 6.59 (dd, J = 3.4, 1.7 Hz, 1H) 13C NMR (100 MHz,
CDCl3) δ 153.75, 149.10, 148.17, 144.24, 136.78, 128.98, 129.44,
127.67, 127.24, 126.31, 117.57, 112.33, 110.25 HRMS m/z (ESI):
calcd. for [C13H9NO+H]+: 196.0757, found 196.0764
10 – 5.06 (m, 2H), 4.50 – 4.46 (m, 2H), 4.10 – 4.03 (m, 5H) 13C
NMR (100 MHz, CDCl3) δ 159.58, 148.32, 135.54, 129.48,
129.04, 127.59, 126.76, 125.47, 119.62, 83.99, 70.53, 69.74,
68.05 HRMS m/z (ESI): calcd. for [C19H15FeN+H]+:314.0627,
found 314.0635
65 3-methyl-2-phenylquinoline (4a): Yellow oil ( 22.7 mg, 69%)
1H NMR (400 MHz, CDCl3) δ 8.14 (d, J = 8.4 Hz, 1H), 8.02 (s,
1H), 7.78 (d, J = 8.1 Hz, 1H), 7.67 (t, J = 7.6 Hz, 1H), 7.60 (d, J =
7.0 Hz, 2H), 7.55 – 7.41 (m, 4H), 2.47 (s, 3H) 13C NMR (100
MHz, CDCl3) δ 160.64, 146.71, 140.95, 136.85, 129.39, 129.33,
15 2-pentylquinoline (3v): Yellow oil (23.4 mg, 78%) 1H NMR
(400 MHz, CDCl3) δ 8.05 (dd, J = 8.4, 3.6 Hz, 2H), 7.76 (d, J = 70 128.96, 128.87, 128.43, 128.30, 127.69, 126.83, 126.52, 20.78
8.1 Hz, 1H), 7.67 (ddd, J = 8.4, 7.0, 1.4 Hz, 1H), 7.51 – 7.44 (m,
1H), 7.29 (d, J = 8.4 Hz, 1H), 3.01 – 2.92 (m, 2H), 1.86 – 1.76 (m,
2H), 1.45 – 1.31 (m, 4H), 0.90 (t, J = 7.1 Hz, 3H) 13C NMR (100
20 MHz, CDCl3) δ 163.26, 148.00, 136.29, 129.43, 128.92, 127.59,
126.81, 125.74, 121.49, 39.50, 31.89, 29.94, 22.71, 14.17 HRMS
m/z (ESI): calcd. for [C14H17N+H]+: 200.1434, found 200.1432
HRMS m/z (ESI): calcd. for [C16H13N+H]+: 220.1121, found
220.1121
1
3-ethyl-2-phenylquinoline (4b): Yellow oil (16.1 mg, 46%) H
NMR (400 MHz, CDCl3) δ 8.14 (d, J = 8.4 Hz, 1H), 8.06 (s, 1H),
75 7.82 (dd, J = 8.1, 1.0 Hz, 1H), 7.67 (ddd, J = 8.4, 6.9, 1.4 Hz, 1H),
7.58 – 7.52 (m, 3H), 7.52 – 7.44 (m, 3H), 2.80 (dd, J = 11.0, 4.0
Hz, 2H), 1.20 (t, J = 7.5 Hz, 3H) 13C NMR (100 MHz,
CDCl3)δ160.75, 146.42, 140.99, 135.40, 135.03, 129.36, 128.91,
128.82, 128.41, 128.19, 127.83, 127.04, 126.48, 26.13, 14.85
2-(pyridin-3-yl)quinoline (3w): Brown solid (28.9 mg, 93%)
m.p. 65-67 oC 1H NMR (400 MHz, CDCl3) δ 9.35 (d, J = 1.8 Hz,
25 1H), 8.69 (dd, J = 4.8, 1.6 Hz, 1H), 8.54 – 8.46 (m, 1H), 8.24 (d, J
= 8.6 Hz, 1H), 8.17 (d, J = 8.7 Hz, 1H), 7.84 (dd, J = 10.8, 8.4 Hz, 80 HRMS m/z (ESI): calcd. for [C17H15N+H]+: 234.1277, found
2H), 7.74 (ddd, J = 8.4, 6.9, 1.4 Hz, 1H), 7.54 (ddd, J = 8.1, 6.9,
1.1 Hz, 1H), 7.44 (ddd, J = 8.0, 4.8, 0.7 Hz, 1H) 13C NMR (100
MHz, CDCl3) δ 154.63, 150.25, 148.84, 148.36, 137.26, 135.15,
30 135.03, 130.08, 129.76, 127.63, 126.86, 123.77, 118.58 HRMS
m/z (ESI): calcd. for [C14H10N2+H]+: 207.0917, found 207.0914
234.1284
1
2-phenyl-3-propylquinoline(4c): Yellow oil (18.0mg, 48%) H
NMR (400 MHz, CDCl3)δ 8.14 (d, J = 8.5 Hz, 1H), 8.04 (s, 1H),
7.83 – 7.78 (m, 1H), 7.67 (ddd, J = 8.4, 6.9, 1.4 Hz, 1H), 7.58 –
85 7.51 (m, 3H), 7.51 – 7.42 (m, 3H), 2.79 – 2.72 (m, 2H), 1.57 (dt,
J = 14.9, 7.5 Hz, 2H), 0.87 (t, J = 7.3 Hz, 3H) 13C NMR (100
MHz, CDCl3) δ 160.87, 146.45, 141.05, 135.86, 133.93, 129.36,
128.92, 128.85, 128.39, 128.15, 127.71, 127.03, 126.48, 35.01,
23.80, 14.03 HRMS m/z (ESI): calcd. for [C18H17N+H]+:
2-(pyridin-4-yl)quinoline (3x): Brown solid (27.4 mg, 89%) m.p.
95-98 oC 1H NMR (400 MHz, CDCl3) δ 8.77 (d, J = 5.9 Hz, 2H),
8.26 (d, J = 8.5 Hz, 1H), 8.18 (d, J = 8.5 Hz, 1H), 8.05 (dd, J =
35 4.5, 1.6 Hz, 2H), 7.88 (d, J = 8.6 Hz, 1H), 7.84 (d, J = 8.1 Hz,
1H), 7.76 (ddd, J = 8.4, 6.9, 1.4 Hz, 1H), 7.57 (ddd, J = 8.0, 6.9, 90 248.1434, found 248.1431
1.1 Hz, 1H) 13C NMR (100 MHz, CDCl3) δ 154.41, 150.55,
148.29, 146.65, 137.37, 130.20, 130.01, 127.63, 127.29, 121.69,
118.47 HRMS m/z (ESI): calcd. for [C14H10N2+H]+: 207.0917,
40 found 207.0920
11H-indeno[1,2-b]quinoline (4d): Yellow solid (24.7 mg, 76%)
m.p. 169-170 oC 1H NMR (400 MHz, CDCl3) δ 8.31 (dd, J = 6.4,
2.0 Hz, 1H), 8.21 (d, J = 8.5 Hz, 1H), 8.15 (s, 1H), 7.80 (dd, J =
8.1, 1.2 Hz, 1H), 7.70 (ddd, J = 8.4, 6.9, 1.5 Hz, 1H), 7.61 – 7.57
2-(thiophen-2-yl)quinoline (3y): White solid (20.0 mg, 63%) 95 (m, 1H), 7.54 – 7.47 (m, 3H), 4.00 (s, 2H) 13C NMR (100 MHz,
o
1
m.p. 127-128 C H NMR (400 MHz, CDCl3) δ 8.17 – 8.07 (m,
2H), 7.77 (dd, J = 13.3, 4.6 Hz, 2H), 7.74 – 7.67 (m, 2H), 7.48
(dd, J = 8.0, 6.7 Hz, 2H), 7.16 (dd, J = 4.9, 3.8 Hz, 1H) 13C NMR
45 (100 MHz, CDCl3) δ 152.42, 148.19, 145.48, 136.72, 129.92,
129.35, 128.70, 129.19, 127.59, 127.28, 126.20, 125.95, 117.74
HRMS m/z (ESI): calcd. for [C13H9NS+H]+: 212.0528, found
212.0528
CDCl3) δ 161.76, 148.11, 145.19, 140.42, 134.68, 131.23, 130.05,
129.17, 128.90, 127.88, 127.59, 127.45, 125.74, 125.56, 122.11,
34.08 HRMS m/z (ESI): calcd. for [C16H11N+H]+: 218.0964,
found 218.0956
100 1,2,3,4-tetrahydroacridine (4e): Yellow solid (22.4 mg, 82%)
m.p. 50-53 oC 1H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 8.5 Hz,
1H), 7.78 (s, 1H), 7.68 (d, J = 8.0 Hz, 1H), 7.58 (dd, J = 13.9, 6.7
Hz, 1H), 7.42(t, J = 7.4 Hz, 1H), 3.12 (t, J = 6.5 Hz, 2H), 3.01 –
2.90 (t, J = 6.5 Hz, 2H), 2.04 – 1.93 (m, 2H), 1.93 – 1.83 (m, 2H)
2-(5-chlorothiophen-2-yl)quinoline (3z): White solid (20.2 mg,
50 55%) m.p. 100-104 oC 1H NMR (400 MHz, CDCl3) δ 8.11 (d, J =
8.6 Hz, 1H), 8.04 (d, J = 8.5 Hz, 1H), 7.76 (t, J = 6.5 Hz, 1H), 105 13C NMR (100 MHz, CDCl3) δ 159.39, 146.67, 135.08, 131.05,
7.73 – 7.65 (m, 2H), 7.53 – 7.46 (m, 1H), 7.45 (d, J = 4.0 Hz,
1H), 6.95 (d, J = 4.0 Hz, 1H) 13C NMR (100MHz, CDCl3) δ
151.54, 148.07, 144.21, 136.81, 133.60, 130.10, 129.25, 127.63,
128.57, 128.34, 127.28, 126.98, 125.61, 33.67, 29.35, 23.33,
23.00 HRMS m/z (ESI): calcd. for [C13H13N+H]+: 184.1121
found 184.1121
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7,8,9,10-tetrahydro-6H-cyclohepta[b]quinoline (4f): White
solid (20.0 mg, 68%) m.p. 91-94 oC 1H NMR (400 MHz, CDCl3)
δ 7.99 (d, J = 8.4 Hz, 1H), 7.79 (s, 1H), 7.70 (d, J = 8.0 Hz, 1H),
7.61 (dd, J = 11.2, 4.0 Hz, 1H), 7.44 (t, J = 7.4 Hz, 1H), 3.28 –
2H), 7.17 (dd, J = 9.0, 8.4 Hz, 1H), 2.45 (s, 3H) 13C NMR (100
MHz, CDCl3) δ 158.23, 158.04(d, J = 253), 149.23(d, J = 3Hz),
139.96, 136.50, 130.03 (d, J=3Hz), 129.76, 129.16 (d, J = 9Hz),
127.61, 125.59 (d, J = 4Hz), 119.04 (d, J = 2Hz), 117.80 (d, J =
5
3.15 (m, 2H), 3.01 – 2.88 (m, 2H), 1.95 – 1.67 (m, 6H) 13C NMR 60 16Hz), 109.76 (d, J = 21Hz), 21.51 HRMS m/z (ESI): calcd. for
(100 MHz, CDCl3) δ 164.79, 146.31, 136.61, 134.68, 128.56,
128.52, 127.43, 126.90, 125.83, 40.16, 35.55, 32.34, 28.95, 27.11
HRMS m/z (ESI): calcd. for [C14H15N+H]+: 198.1277, found
198.1275
[C16H12N+H]+: 238.1027, found 238.1024
5-fluoro-2-(4-methoxyphenyl)quinoline(4m):White solid (16.3
mg, 43%) m.p. 93-94 oC 1H NMR (400 MHz, CDCl3) δ 8.43 (d, J
= 8.8 Hz, 1H), 8.17 – 8.12 (m, 2H), 7.93 (d, J = 8.6 Hz, 1H), 7.88
1
10 2,3-diphenylquinoline (4g): Colorless oil ( 18.9 mg, 45%) H 65 (d, J = 8.8 Hz, 1H), 7.62 (td, J = 8.1, 6.2 Hz, 1H), 7.19 – 7.11 (m,
NMR (400 MHz, CDCl3) δ 8.22 (d, J = 8.5 Hz, 1H), 8.19 (s, 1H),
7.88 (d, J = 8.1 Hz, 1H), 7.75 (ddd, J = 8.4, 6.9, 1.4 Hz, 1H), 7.60
– 7.54 (m, 1H), 7.49 – 7.43 (m, 2H), 7.35 – 7.24 (m, 8H) 13C
NMR (100 MHz, CDCl3) δ 158.54, 147.42, 140.55, 140.11,
1H), 7.08 – 7.01 (m, 2H), 3.89 (s, 3H) 13C NMR (100 MHz,
CDCl3) δ 161.18, 157.81 (d, J = 153), 157.79, 149.25 (d, J = 2Hz),
131.84, 129.98 (d, J = 4Hz), 129.20, 129.10, 125.45 (d, J = 4Hz),
118.72 (d, J = 2Hz), 117.58 (d, J = 16Hz), 114.36 (d, J = 7Hz),
15 137.71, 134.66, 130.14, 129.89, 129.75, 129.56, 128.36, 128.14, 70 109.60 (d, J = 19Hz), 55.53 HRMS m/z (ESI): calcd. for
128.07, 127.61, 127.35, 127.31, 126.88 HRMS m/z (ESI): calcd.
for [C21H15N+H]+: 282.1277, found 282.1281
[C16H12FNO+H]+: 254.0976, found 254.0977
Acknowledgement
ethyl 2-phenylquinoline-3-carboxylate (4h): Yellow oil (17.4
mg, 42%) 1H NMR (400 MHz, CDCl3) δ 8.65 (s, 1H), 8.19 (d, J =
20 8.5 Hz, 1H), 7.95 – 7.89 (m, 1H), 7.81 (ddd, J = 8.4, 6.9, 1.4 Hz,
1H), 7.67 – 7.56 (m, 3H), 7.50 – 7.43 (m, 3H), 4.24 – 4.14 (q, J =
2Hz, 2H), 1.08 (t, J = 7.1 Hz, 3H) 13C NMR (100 MHz, CDCl3) δ
168.10, 158.24, 148.45, 140.86, 139.18, 131.65, 129.63, 128.66,
128.32, 128.29, 127.33, 125.93, 125.60, 61.65, 13.80 HRMS m/z
25 (ESI): calcd. for [C18H15NO2+H]+: 278.1176, found 278.1180
This work was supported financially by the National Program on
Key Basic Research Project of China (973 Program,
75 2013CB328900) and the National Science Foundation of China
(grant nos. 21202107 and 21321061).
Notes andreferences
Key Laboratory of Green Chemistry & Technology, Ministry of Education,
College of Chemistry, Sichuan University, Chengdu 610064, PR China.
80 Tel.: (86)-28-85415886; fax: (86)-28-85415886
7-methyl-2-phenylquinoline (4i): White solid (27.6 mg, 84%)
E-mail: chensy@scu.edu.cn; xqyu@scu.edu.cn
1
m.p. 98-101 oC H NMR (400 MHz, CDCl3) δ 8.21 – 8.12 (m,
1.
2.
(a) J. P. Michael, Nat. Prod. Rep. 2008, 25, 166; (b) M.
Groisy-Delcey, A. Groisy, D. Carrez, C. Huel, A. Chaironi,
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(a) J. E. Charris, J. N. Dominguez, N. Gamboa, J. R.
Rodrigues and J. E. Angel, Eur. J. Med. Chem. 2005, 40,
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M. Jain, R. P. Reddy and R. Jain, Eur. J. Med. Chem. 2010,
45, 3245; (d) A. T. Vu, S. T. Cohn, E. S. Manas, H. A.
Harris and R. E. Mewshaw, Bioorg. Med. Chem. Lett. 2005,
15, 4520.
(a) C.-H. Cheng, R.-M .Chen, C.-W. Huang and C.-C. Yang,
U.S. Patent 20050025995A1, 2005; (b) Y. Tokoro, A.
Nagai, K. Kokadoand Y. Chujo, Macromolecules 2009, 42,
2988; (c) H. Tong, L. Wang, X. Jing and F. Wang,
Macromolecules 2003, 36, 2584.
(a) Z. H. Skraup, Ber. Dtsch. Chem. Ges. 1880, 13, 2086; (b)
A. Combes, Bull. Soc. Chim. Fr. 1883, 49, 89; (c) Gould, R.
G. and W. A. Jacobs, J. Am. Chem. Soc. 1939, 61, 2890; (d)
F. Friedländer, Ber. Dtsch. Chem. Ges. 1882, 15, 2572; (e)
O. Doebnerand W. von Miller, Ber. Dtsch. Chem. Ges.
1881,14,2812.
3H), 7.99 (s, 1H), 7.80 (d, J = 8.5 Hz, 1H), 7.71 (d, J = 8.3 Hz,
30 1H), 7.58 – 7.51 (m, 2H), 7.47 (ddd, J = 7.3, 3.7, 1.2 Hz, 1H),
7.36 (dd, J = 8.3, 1.5 Hz, 1H), 2.59 (s, 3H) 13C NMR (100 MHz,
CDCl3) δ 157.36, 148.57, 139.99, 139.91, 136.52, 129.29, 128.89,
128.83, 128.62, 127.61, 127.18, 125.30, 118.28, 22.02 HRMS
m/z (ESI): calcd. for [C16H13N+H]+: 220.1121, found 220.1123
85
35 7-methoxy-2-phenylquinoline (4j): Yellow oil (13.0 mg, 37%)
1H NMR (400 MHz, CDCl3) δ 8.19 – 8.09 (m, 3H), 7.71 (dd, J =
11.5, 8.7 Hz, 2H), 7.53 (dt, J = 9.4, 1.5 Hz, 3H), 7.49 – 7.43 (m,
1H), 7.19 (dd, J = 8.9, 2.5 Hz, 1H), 3.98 (s, 3H) 13C NMR (100
MHz, CDCl3) δ 161.00, 157.79, 150.08, 139.98, 136.52, 129.30,
40 128.92, 128.57, 127.63, 122.51, 119.63, 117.04, 107.70, 55.67
HRMS m/z (ESI): calcd. for [C16H13NO+H]+: 236.1070, found
236.1058
90
95
3.
4.
5-fluoro-2-phenylquinoline (4k): Yellow solid ( 15.4 mg, 46%)
m.p. 62-64 oC 1H NMR (400 MHz, CDCl3) δ 8.49 (d, J = 8.8 Hz,
45 1H), 8.23 – 8.14 (m, 2H), 7.96 (dd, J = 16.7, 8.7 Hz, 2H), 7.65 (td,
100
105
110
J = 8.1, 6.2 Hz, 1H), 7.60 – 7.44 (m, 3H), 7.24 – 7.14 (m, 1H) 13
C
NMR (100 MHz, CDCl3) δ 158.32, 158.04 (d, J = 253),149.22 (d,
J = 3Hz), 139.35, 130.20 (d, J = 4Hz), 129.81, 129.28 (d, J =
8Hz), 129.05, 127.76, 125.70 (d, J = 4Hz), 119.24 (d, J = 2Hz),
50 117.94 (d, J = 16Hz), 109.98 (d, J = 19Hz) HRMS m/z (ESI):
calcd. for [C15H10FN+H]+: 224.0870, found 224.0867
5.
For selected examples, see: (a) A. Roglans, A. Pla-Quintana
and M. Moreno-Mañas, Chem. Rev. 2006, 106, 4622; (b) S.
Guo, B. Qian, Y. Xie, C. Xia and H. Huang, Org. Lett. 2011,
13, 522; (c) R. D. Patil and S. Adimurthy, Adv. Synth. Catal.
2011, 353, 1695; (d) R.-Y. Tang, X.-K. Guo, J.-N. Xiang
5-fluoro-2-(p-tolyl)quinoline (4l): White solid (17.4mg, 49%)
m.p. 67-70 oC 1H NMR (400 MHz, CDCl3) δ 8.46 (d, J = 8.8 Hz,
1H), 8.08 (d, J = 8.2 Hz, 2H), 7.96 (d, J = 8.6 Hz, 1H), 7.91 (d, J
55 = 8.8 Hz, 1H), 7.63 (td, J = 8.1, 6.2 Hz, 1H), 7.34 (d, J = 8.1 Hz,
6
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Organic & Biomolecular Chemistry
and J.-H. Li, J. Org. Chem. 2013, 78, 11163; (e) Z. Ling, L.
Yun, L. Liu, B. Wu and X. Fu, Chem. Commun. 2013, 49,
4214; (f) X. Chen, T. Chen, Y. Zhou, D. Han, L.-B. Han
and S.-F. Yin, Org. Bio. Chem. 2014, 12, 3802; (g) W. Hao,
W. Geng, W.-X. Zhang and Z. Xi, Chem. Eur. J. 2014, 20,
2605; (h) L. Gao, H. Tang and Z. Wang, Chem. Commun.
2014, 50, 4085.
5
6.
L.-Y. Xi, R.-Y. Zhang, S. Liang, S.-Y. Chen and X.-Q. Yu,
Org. Lett. 2014, 16, 5269.
10 7.
During the preparation of this manuscript, transition metal-
free synthesis of 2-aryl quinolines from 2-
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