Synthesis of 3-Iodoquinolines by Copper-Catalyzed Tandem Annulation from Diaryliodoniums, Nitriles, and 1-Iodoalkynes

Article abstract of DOI:10.1002/adsc.201600081

A novel method for the synthesis of 3-iodoquinolines was developed by copper-catalyzed tandem annulation from diaryliodoniums, nitriles, and 1-iodoalkynes. It is a method that is characterized by the most convenient operation and wide molecular diversity. (Figure presented.) .

Full text of DOI:10.1002/adsc.201600081

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DOI: 10.1002/adsc.201600081
Synthesis of 3-Iodoquinolines by Copper-Catalyzed Tandem
Annulation from Diaryliodoniums, Nitriles, and 1-Iodoalkynes
Xuesong Wang,a Xingyong Wang,a Dayun Huang,a Chulong Liu,a Xinyan Wang,a,*
and Yuefei Hua,*
a
Department of Chemistry, Tsinghua University, Beijing 100084, Peopleꢀs Republic of China
Fax : (+86)-10-6277-1149; phone: (+86)-10-6279-5380; e-mail: wangxinyan@mail.tsinghua.edu.cn or
yfh@mail.tsinghua.edu.cn
Received: January 19, 2016; Revised: April 29, 2016; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201600081.
Abstract: A novel method for the synthesis of 3-io- ized by the most convenient operation and wide mo-
doquinolines was developed by copper-catalyzed lecular diversity.
tandem annulation from diaryliodoniums, nitriles,
and 1-iodoalkynes. It is a method that is character- Keywords: annulation; copper catalysts; 1-iodoal-
kynes; iodoniums; synthesis of quinolones; tandem
reactions
Introduction
ganic synthesis, such as Buchwald–Hartwig, Heck, So-
nogashira, Suzuki, and Ullmann couplings. Recently,
Quinolines are important heterocycles found in natu- these couplings have been employed to efficiently
ral products and synthetic compounds. Their novel synthesize C-3 subtituted quinolines starting from 3-
structures and properties have made them widely ap- iodoquinolines 1. As shown in Figure 2, compound
plicable in drug discovery[1] and material science.[2] 1 has been recognized as a versatile precursor to suc-
Therefore, the synthesis of quinolines has continuous-
ly been an important research project. In recent years,
numerous novel synthetic methods have been devel-
oped for this purpose[3] even though many well-
known name reactions[4] had been established before,
such as Combes synthesis, Conrad–Limpach–Knorr
synthesis, Friedlꢁnder reaction, and Skraup–Doebner–
Von Miller reaction (Figure 1). Among these meth-
ods, the introduction of a C-3 substituent on the quin-
oline ring usually is much more difficult than that of
C-2 and C-4 substituents, thus significantly limiting
Figure 2. Some metal-catalyzed cross-couplings of 1.
the molecular diversity of quinolines.
In the past decade, metal-catalyzed cross-couplings
of aryl halides have been played a crucial role in or- cessfully achieve the corresponding arylation,[5] alke-
nylation,[6] alkynylation[7] as well as the formations of
[8]
[9]
[10]
À
À
À
C N, C O, and C S
bonds. Since the iodine
atom could not be replaced by other halogen atoms
(such as Br and Cl)[8a,c,10b,c] in these couplings, the im-
portance of the synthesis of 3-iodoquinolines 1 has
been enhanced significantly.[11]
Herein, we would like to report a novel method for
the easy synthesis of 3-iodoquinolines 1 by a copper-
catalyzed tandem annulation from diaryliodoniums 2,
nitriles 3, and 1-iodoalkynes 4 (Scheme 1).
Figure 1. Some synthetic methods for quinolines.
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Table 1. Effects of the solvents and temperature.[a]
Scheme 1. Retrosynthetic analysis of 3-iodoquinolines 1.
Entry Solvent Temp.
[oC]
Reaction under Yield of 1a
N2
[%][b]
Results and Discussion
1
2
3
4
5
6
7
8
9
DCE
DCE
DCE
DCE
toluene 100
dioxane 100
DMSO 100
120
100
90
yes
yes
yes
no
yes
yes
yes
yes
yes
64
76
46
45
61
42
0
Literature reviews have shown that a few methods
have been specifically developed for the synthesis of
3-iodoquinolines 1.[11] Although they have different
advantages, they all went through the linear synthesis
strategy and the iodine atom was introduced into the
target product in the last step. Due to this, a multi-
step synthesis was required for each target product.
Clearly, a multi-component, one-pot synthesis strategy
is one of the best ways to solve this problem.
In 2009, 1-iodoalkyne 4 was first used for the syn-
thesis of 5-iodo-1,2,3-triazoles.[12] In this method, the
cycloaddition of the triple bond was accompanied by
a highly regioselective introduction of an iodine atom
on the 1,2,3-triazole ring.[13] However, 1-iodoalkyne 4
100
DMF
NMP
100
100
0
0
[a]
The mixture of 2a (0.5 mmol), 3a (0.6 mmol), 4a
(0.6 mmol) and Cu(OTf)2 (10 mol%) in solvent (2 mL)
was heated for 12 h.
[b]
Isolated yields.
was rarely applied in the synthesis of the other het- activity than the corresponding terminal alkyne. But
erocycles during the past years.[14,15] This phenomenon the yield of 1a was reduced significantly when the re-
may arise from two reasons: (i) 1-iodoalkyne 4 struc- action was run at 908C (entry 3). It was essential that
turally is an internal alkyne, but its behavior is more the reaction needed to be protected by a nitrogen at-
like that of a terminal alkyne in copper-catalyzed cy- mosphere (entry 4). The results in entries 5–9 indicat-
cloadditions. It can be used as an alternative for a ter- ed that ClCH2CH2Cl was the best solvent for the re-
minal alkyne but not for an internal alkyne; (ii) 1-io- action.
doalkyne 4 usually goes through a copper-catalyzed
As shown in Table 2, the anions in diphenyliodoni-
and ligand-mediated mechanism.[12,13c,d] No reaction or um and copper salt have significant effects on the re-
inefficient reaction was observed under copper-
free,[15] ligand-free[16] or non-copper catalytic condi-
tions.[17] Therefore, we hypothesized that the terminal
alkyne in copper-catalyzed cycloadditions can be re-
placed by 1-iodoalkyne 4 to directly generate iodo-
substituted cycloadducts. This hypothesis has been
supported by our recent two works.[13a,14a]
Table 2. Effects of the anion part of the salts.[a]
Based on the above analyses, the synthetic methods
for quinolines were investigated. We interestingly
found that many methods have been reported to syn-
thesize 3H-quinolines by using terminal alkynes as
substrates, but only a few were catalyzed by copper
catalysts.[18] Among them, the method reported by
Chen et al. in 2013[18b] attracted our attention for its
readily accessible substrates and three-component,
one-pot procedure. Thus, following Chenꢀs procedure,
the mixture of diphenyliodonium hexafluorophos-
phate (2a), benzonitrile (3a), and 1-iodo-2-phenyle-
thyne (4a) in ClCH2CH2Cl was heated at 1208C for
12 h in the presence of Cu(OTf)2. As shown in
Table 1, the desired product 1a was obtained in 64%
yield (entry 1). However, 1a was obtained in 76%
yield when the same reaction was run at 1008C
(entry 2). These results may stem from the fact that 1-
iodoalkyne has lower thermal stability and higher re-
Entry
Ph2I-X (X=)
[Cu] salt
Yield of 1a [%][b]
1
2
3
4
5
6
7
8
PF6 (2a)
I (2b)
OTf (2c)
Cl (2d)
PF6 (2a)
PF6 (2a)
PF6 (2a)
PF6 (2a)
PF6 (2a)
PF6 (2a)
PF6 (2a)
PF6 (2a)
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
CuBr2
CuCl2
CuI
CuBr
CuCN
76
50
20
5
55
46
34
32
30
28
5
9
10
11
12
CuCl
Cu(acac)2
Cu(OAc)2
0
[a]
The mixture of diphenyliodonium salt 2 (0.5 mmol), 3a
(0.6 mmol), 4a (0.6 mmol) and [Cu] salt (10 mol%) in
DCE (2 mL) was heated for 12 h.
[b]
Isolated yield.
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action and the anions with the weakest nucleophilicity an equivalent of benzenium ion to attack 3a to give
gave the best results. For example, the results in en- N-phenylnitrilium salt 5. Cu(II) may play two catalyt-
tries 1–4 indicated that Ph2I-PF6 (1a) had the highest ic roles as both a Lewis acid and a Lewis base. (i) In
reactivity. Similarly, the results in entries 5–12 showed the first step, Ph2I-PF6 is activated by Lewis acid
that Cu(OTf)2 had the most catalytic activity.
(TfO)2Cu to generate Ph2I+ (2a) by forming Lewis
The ligands were then tested to improve the reac- base (TfO)2CuÀ-PF6. (ii) In the last step, the electro-
tion efficiency, but all attempts failed. For example, philic annulation of the intermediate 7 is catalyzed by
Et3N has been recognized as an excellent ligand for Lewis base (TfO)2CuÀ-PF6 to regenerate Lewis acid
copper-catalyzed cycloadditions of 1-iodoalkyne (TfO)2Cu. Based on the above analyses, we believed
4.[12,13a,d,f] Unfortunately, when Et3N (20 mol%) was that the function of Cu(II) as a Lewis acid may be se-
added into the reaction system (in entry 1, Table 2), riously weakened by addition of a ligand (as a Lewis
1a was obtained in only 46% yield. When DIPEA, base). Since the substrate 3a and the product 1a may
1,10-phenanthroline, pyridine, 2,2’-dipyridine and tri- serve as weak ligands, our method proceeded under
phenylphosphine were used as ligands, complicated ligand-free-like conditions rather than real ligand-free
mixtures were obtained. These results indicated that conditions.
certain roles of the copper ions in the reaction may
be weakened by those ligands.
Finally, the standard conditions for our method
were assigned as shown in Scheme 3 and the scope of
In the literature, the mechanisms for copper-cata- the method was examined. To fixed 1-iodo-2-phenyle-
lyzed reactions of diphenyliodoniums and alkynes thyne (4a), all the tested aryl nitriles gave satisfactory
have been well studied.[18b,19] Although Cu(OTf)2 usu- results (1a–1q). Substrates with aryl rings substituted
ally was used as an initial catalyst, Cu(I) and Cu(III) by EDGs gave higher yields of products (1b–1d) com-
species were hypothesized to be formed in situ by the pared to those substituted by EWGs (1e, 1k, 1m).
disproportionation of Cu(II) during the reaction and But, alkyl nitriles gave the desired products (1p–1q)
played different roles.[20] Thus, a pathway for our in moderate yields, which may be caused by their a-
method was proposed and the functions for three dif- active hydrogens. Thus, PhCH2CN and NCCH2CN
ferent copper ions were assigned. As shown in (with a-active hydrogens) as well as EtO2CCN and
Scheme 2, Cu(I) may be a dual catalyst to convert 2a (OEt)2(O)PCN (with EDGs) were unsuitable sub-
into phenylcopper [PhCu(III)] and to activate 4a by strates for this method. To fixed benzonitrile (3a), all
forming the p-complex 6. PhCu(III) may function as tested 1-iodo-2-arylethynes gave satisfactory results
(1r–1v) and 1s even was obtained in 90% yield. To
our delight, 1w and 1x were obtained in 73% and
70% yields, respectively, from the corresponding 1-
ꢀ
bromo-2-phenylethyne (PhC CBr, 4g) and 1-chloro-
2-phenylethyne (PhC CCl, 4h) under similar condi-
ꢀ
tions. Finally, three substituted diaryliodonium hexa-
fluorophosphates were tested to give the correspond-
ing products 1y, 1z and 1aa in very similar results.
As shown in Figure 3, the structure of product 1u
was confirmed further by a single crystal X-ray dif-
fraction analysis.[21]
Conclusions
In summary, three items have been disclosed in this
article. First, a novel strategy was proposed that the
terminal alkyne in copper-catalyzed cycloadditions
can be replaced by 1-iodoalkyne to directly generate
iodo-substituted cycloadducts. Second, this novel
strategy was proved and the reaction conditions were
optimized by using the synthesis of 3-iodoquinoline as
a model reaction. Finally, a novel method for the syn-
thesis of 3-iodoquinolines was developed by a copper-
catalyzed tandem annulation from diaryliodoniums,
nitriles, and 1-iodoalkynes, by which a series of struc-
turally novel 3-iodoquinolines was synthesized.
Scheme 2. A proposed pathway for the synthesis of 1a.
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Scheme 3. Scope of the method.
Experimental Section
General
All melting points were determined on a Yanaco melting
point apparatus and are uncorrected. IR spectra were re-
corded as KBr pellets on a Nicolet FT-IR 5DX spectrome-
1
ter. All H NMR (400 MHz) and 13C NMR (100 MHz) spec-
tra were recorded in CDCl3. TMS was used as an internal
reference and J values are given in Hz. HR-MS were ob-
tained on a Bruker micrOTOF-Q II spectrometer. PE is pe-
troleum ether (60–908C).
Typical Procedure for the Synthesis of 2,4-Diphenyl-
3-iodoquinoline (1a)
A suspension of Ph2I-PF6 (2a, 213 mg, 0.5 mmol), PhCN (3a,
ꢀ À
62 mg, 0.6 mmol), PhC C I (4a, 137 mg, 0.6 mmol) and
Cu(OTf)2 (18 mg, 0.05 mmol) in ClCH2CH2Cl (2 mL) in
a Schlenk tube was degassed. After the resultant mixture
was stirred at 1008C for 12 h under N2, it was cooled down
to room temperature and saturated aqueous NaHCO3
(15 mL) was added. The mixture was stirred for 10 min and
Figure 3. The structure of the product 1u.
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then was extracted by CH2Cl2 (3ꢃ15 mL). The combined or-
ganic layers were dried over Na2SO4. Removal of the sol-
vent gave a residue, which was purified by a column chro-
matography (silica gel, PE/EtOAc/Et3N=100/5/1) to afford
1a as white solid; yield: 154.8 mg (76%); mp 118–1208C
(lit.[11b] 118–1228C). 1H NMR (CDCl3, 400 MHz): d=8.16
(d, J=8.3 Hz, 1H), 7.75–7.71 (m, 1H), 7.66–7.63 (m, 2H),
7.56–7.43 (m, 6H), 7.42–7.40 (m, 2H), 7.31–7.29 (m, 2H);
13C NMR (CDCl3, 100 MHz): d=161.8, 154.6, 146.8, 143.6,
142.1, 130.0, 129.3, 129.2 (3C), 129.0, 128.6 (2C), 128.5,
128.4, 127.9 (2C), 127.3, 127.2, 126.8, 98.5.
2-(4-Iodophenyl)-4-phenyl-3-iodoquinoline (1h): White
solid; mp 192–1948C; IR: v=3052, 2929, 1583, 1382 cmÀ1
;
1H NMR (CDCl3, 400 MHz): d=8.14 (d, J=8.2 Hz, 1H),
7.85–7.82 (m, 2H), 7.76–7.71 (m, 1H), 7.59–7.53 (m, 3H),
7.43–7.41 (m, 4H), 7.29–7.27 (m, 2H); 13C NMR (CDCl3,
100 MHz): d=160.7, 154.9, 146.9, 143.0, 141.9, 137.1 (2C),
131.2 (2C), 130.2, 129.3, 129.0 (2C), 128.6 (2C), 128.5, 127.5,
127.4, 126.7, 97.8, 94.8; HR-MS (ESI-TOF): m/z=533.9208,
calcd. for C21H14I2N [M+H]+: 533.9210.
2-(3-Iodophenyl)-4-phenyl-3-iodoquinoline (1i): White
solid; mp 140–1428C; IR: v=3053, 2946, 1557, 1476,
1333 cmÀ1 1H NMR (CDCl3, 400 MHz): d=8.15 (d, J=
;
A similar procedure was used for the preparation of prod-
ucts 1b–1x and 1aa.
8.7 Hz, 1H), 8.00 (t, J=1.4 Hz, 1H), 7.80–7.72 (m, 2H),
7.64–7.52 (m, 4H), 7.43–7.41 (m, 2H), 7.29–7.22 (m, 3H);
13C NMR (CDCl3, 100 MHz): d=160.0, 154.9, 146.7, 145.5,
141.8, 138.0, 137.5, 130.3, 129.5, 129.3, 129.0 (2C), 128.6
(3C), 128.5, 127.5, 127.4, 126.8, 97.8, 93.7; HR-MS (ESI-
TOF): m/z=533.9207, calcd. for C21H14I2N [M+H]+:
533.9210.
2-(4-Methoxyphenyl)-4-phenyl-3-iodoquinoline
(1b):
White solid; mp 192–1948C (lit.[11b] 191–1958C); 1H NMR
(CDCl3, 400 MHz): d=8.15 (d, J=11.4 Hz, 1H), 7.74–7.68
(m, 1H), 7.64 (d, J=11.9 Hz, 2H), 7.56–7.51 (m, 3H), 7.38
(d, J=5.5 Hz, 2H), 7.30–7.27 (m, 2H), 7.03–6.99 (m, 2H),
3.87 (s, 3H); 13C NMR (CDCl3, 100 MHz): d=161.4, 159.8,
154.6, 146.9, 143.2, 136.2, 130.8 (2C), 130.0, 129.3, 129.1
(2C), 128.6 (2C), 128.4, 127.2, 127.0, 126.8, 113.3 (2C), 98.9,
55.3.
2-(2-Iodophenyl)-4-phenyl-3-iodoquinoline (1j): White
solid; mp 142–1448C; IR: v=3058, 2945, 1632, 1560, 1532,
1472, 1336 cmÀ1 1H NMR (CDCl3, 400 MHz): d=8.18 (d,
;
J=8.7 Hz, 1H), 7.95 (d, J=7.4 Hz, 1H), 7.77–7.73 (m, 1H),
7.58–7.41 (m, 7H), 7.36–7.34 (m, 1H), 7.30–7.27 (m, 1H),
7.15–7.11 (m, 1H); 13C NMR (CDCl3, 100 MHz): d=163.3,
154.3, 148.2, 146.7, 141.4, 138.8, 130.1, 129.8, 129.4, 129.3,
129.2, 128.9, 128.7, 128.5 (2C), 128.2, 127.6, 127.5, 126.7,
99.2, 97.8; HR-MS (ESI-TOF): m/z=533.9206, calcd. for
C21H14I2N [M+H]+: 533.9210.
2-(p-Tolyl)-4-phenyl-3-iodoquinoline (1c): White solid;
mp 182–1848C (lit.[11b] 184–1868C); 1H NMR (CDCl3,
400 MHz): d=8.15 (d, J=8.7 Hz, 1H), 7.72–7.68 (m, 1H),
7.56–7.50 (m, 5H), 7.41–7.38 (m, 2H), 7.30–7.27 (m, 4H),
2.43 (s, 3H); 13C NMR (CDCl3, 100 MHz): d=161.8, 154.5,
146.9, 142.1, 140.8, 138.4, 129.9, 129.3, 129.1 (2C), 129.0
(2C), 128.5 (4C), 128.4, 127.2, 127.0, 126.7, 98.7, 21.4.
2-(o-Tolyl)-4-phenyl-3-iodoquinoline (1d): White solid;
mp 142–1448C (lit.[11b] 140–1468C); 1H NMR (CDCl3,
400 MHz): d=8.17 (d, J=8.7 Hz, 1H) 7.74–7.70 (m, 1H),
7.56–7.50 (m, 3H), 7.44–7.41 (m, 2H), 7.34–7.30 (m, 6H),
2.19 (s, 3H); 13C NMR (CDCl3, 100 MHz): d=162.8, 154.1,
146.9, 143.6, 141.6, 135.3, 130.0, 129.9, 129.3, 129.1, 129.0,
128.5 (3C), 128.4, 128.3, 127.2, 127.1, 126.7, 125.7, 99.9, 19.7.
2-(4-Fluorophenyl)-4-phenyl-3-iodoquinoline (1e): White
2-(4-Nitrophenyl)-4-phenyl-3-iodoquinoline (1k): White
solid; mp 206–2088C; IR: v=3066, 2850, 1600, 1511,
1342 cmÀ1 1H NMR (CDCl3, 400 MHz): d=8.36 (d, J=
;
9.2 Hz, 2H), 8.14 (d, J=8.7 Hz, 1H), 7.85 (d, J=8.7 Hz,
2H), 7.79–7.75 (m, 1H), 7.60–7.55 (m, 3H), 7.49–7.43 (m,
2H), 7.30–7.27 (m, 2H); 13C NMR (CDCl3, 100 MHz): d=
159.4, 155.2, 149.6, 147.8, 146.8, 141.6, 130.6 (2C), 130.5,
129.4, 129.0 (2C), 128.7 (3C), 127.9, 127.6, 126.9, 123.3 (2C),
96.8; HR-MS (ESI-TOF): m/z=453.0092, calcd. for
C21H14IN2O2 [M+H]+: 453.0094.
solid; mp 174–1768C; IR: v=3058, 2929, 1598, 1338 cmÀ1
;
1H NMR (CDCl3, 400 MHz): d=8.14 (d, J=8.7 Hz, 1H),
7.74–7.70 (m, 1H), 7.66–7.63 (m, 2H), 7.58–7.52 (m, 3H),
7.41–7.40 (m, 2H), 7.29–7.27(m, 2H), 7.19–7.15 (m, 2H);
13C NMR (CDCl3, 100 MHz): d=162.8 (d, J=247.3 Hz),
160.7, 154.8, 146.8, 142.0, 139.6, 131.3 (d, J=8.4 Hz, 2C),
130.2, 129.3, 129.0 (2C), 128.6 (2C), 128.5, 127.3 (d, J=
5.4 Hz, 2C), 126.8, 114.9 (d, J=21.4 Hz, 2C), 98.3; HR-MS
(ESI-TOF): m/z=426.0147, calcd. for C21H14FIN [M+H]+:
426.0149.
2-(Naphthalene-1-yl)-4-phenyl-3-iodoquinoline (1l): White
solid; mp 160–1628C; IR: v=3054, 2946, 1640, 1556,
1381 cmÀ1 1H NMR (CDCl3, 400 MHz): d=8.19 (d, J=
;
8.7 Hz, 1H), 7.97–7.92 (m, 2H), 7.79–7.75 (m, 1H), 7.63–
7.47 (m, 9H), 7.44–7.32 (m, 3H); 13C NMR (CDCl3,
100 MHz): d=161.8, 154.3, 147.0, 141.6, 141.5, 133.5, 131.2,
130.1, 129.5, 129.2, 129.0, 128.7, 128.6 (2C), 128.5, 128.3,
127.4, 127.3, 126.8, 126.6, 126.3, 125.9, 125.5, 125.2, 100.4;
HR-MS (ESI-TOF): m/z=458.0401, calcd. for C25H17IN
[M+H]+: 458.0400.
2-(4-Chlorophenyl)-4-phenyl-3-iodoquinoline (1f): White
1
solid; mp 180–1828C (lit.[11b] 180–1868C); H NMR (CDCl3,
2-[4-(Trifluoromethyl)phenyl]-4-phenyl-3-iodoquinoline
(1m): White solid; mp 220–2228C; IR: v=3060, 3029, 2924,
400 MHz): d=8.14 (d, J=8.3 Hz, 1H), 7.76–7.72 (m, 1H),
7.62–7.41 (m, 9H), 7.30–7.27 (m, 2H); 13C NMR (CDCl3,
100 MHz): d=160.6, 154.9, 146.8, 142.0, 141.9, 134.6, 130.8
(2C), 130.2, 129.3, 129.0 (2C), 128.6 (2C), 128.5, 128.2 (2C),
127.4, 127.3, 126.9, 98.0.
1611, 1482 cmÀ1 1H NMR (CDCl3, 400 MHz): d=8.14 (d,
;
J=8.24 Hz, 1H), 7.79–7.72 (m, 5H), 7.59–7.53 (m, 3H), 7.43
(d, J=3.6 Hz, 2H), 7.30–7.28 (m, 2H); 13C NMR (CDCl3,
100 MHz): d=160.4, 155.0, 147.0, 146.9, 141.7, 130.6 (q, J=
32.4 Hz)„ 130.3, 129.8 (2C), 129.4, 129.0 (2C), 128.7 (2C),
128.6, 127.6, 127.5, 126.9, 125.0 (q, J=3.8 Hz, 2C), 124.1 (q,
J=270.8 Hz), 97.4; HR-MS (ESI-TOF): m/z=476.0115,
calcd. for C21H14F3IN [M+H]+: 476.0118.
2-(4-Bromophenyl)-4-phenyl-3-iodoquinoline (1g): White
1
solid; mp 200–2028C (lit.[11b] 201–2048C); H NMR (CDCl3,
400 MHz): d=8.14 (d, J=8.7 Hz, 1H), 7.76–7.72 (m, 1H,),
7.64–7.53 (m, 7H), 7.43–7.41 (m, 2H), 7.29–7.27 (m, 2H);
13C NMR (CDCl3, 100 MHz): d=160.6, 154.9, 146.9, 142.4,
141.9, 131.1 (2C), 131.0 (2C), 130.2, 129.3, 129.0 (2C), 128.6
(2C), 128.5, 127.5, 127.4, 126.7, 122.9, 97.9.
2-(Thiophen-2-yl)-4-phenyl-3-iodoquinoline (1n): White
solid; mp 92–948C; IR: v=3064, 2960, 1637, 1559,
1432 cmÀ1
;
1H NMR (CDCl3, 400 MHz): d=8.13 (d, J=
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8.7 Hz, 1H), 7.89–7.88 (m, 1H), 7.73–7.69 (m, 1H), 7.59–
7.50 (m, 4H), 7.40–7.33 (m, 2H), 7.28–7.25 (m, 2H), 7.16–
7.13 (m, 1H); 13C NMR (CDCl3, 100 MHz): d=155.3, 154.4,
146.7, 145.2, 142.4, 130.2, 129.9, 129.2, 129.0 (2C), 128.6
(2C), 128.4, 128.0, 127.3, 127.2, 126.8, 126.7, 97.2; HR-MS
(ESI-TOF): m/z=413.9810, calcd. for C19H13INS, [M+H]+:
413.9808.
2-Phenyl-4-(4-bromophenyl)-3-iodoquinoline (1u): White
1
solid; mp 212–2148C (lit.[11b] 212–2148C); H NMR (CDCl3,
400 MHz): d=8.16 (d, J=8.3 Hz, 1H), 7.76–7.69 (m, 3H),
7.64–7.61 (m, 2H), 7.51–7.37 (m, 5H), 7.20–7.17 (m, 2H);
13C NMR (CDCl3, 100 MHz): d=161.8, 153.4, 146.8, 143.5,
140.8, 131.9 (2C), 130.8 (2C), 130.2, 129.5, 129.2 (2C), 128.6,
128.0 (2C), 127.5, 127.0, 126.4, 122.8, 98.3.
2-Phenyl-4-(2-fluorophenyl)-3-iodoquinoline (1v): White
solid; mp 106–1088C; IR: v=3060, 2929, 1617, 1567,
2-(Thiophen-3-yl)-4-phenyl-3-iodoquinoline (1o): White
solid; mp 116–1188C; IR: v=3103, 3054, 2950, 1641, 1561,
1378 cmÀ1 1H NMR (CDCl3, 400 MHz): d=8.19 (d, J=
;
1439 cmÀ1 1H NMR (CDCl3, 400 MHz): d=8.14 (d, J=
;
8.3 Hz, 1H), 7.75 (t, J=8.2 Hz, 1H), 7.68–7.66 (m, 2H),
7.56–7.34 (m, 7H), 7.30–7.26 (m, 2H); 13C NMR (CDCl3,
100 MHz): d=161.8, 159.0 (d, J=246.0 Hz), 149.4, 146.8,
143.4, 131.1 (d, J=2.9 Hz), 130.9 (d, J=7.6 Hz), 130.2, 129.6,
129.4, 129.2 (2C), 128.6, 128.0 (2C), 127.6, 127.2, 126.1,
124.5 (d, J=2.9 Hz), 116.2 (d, J=21.0 Hz), 99.0; HR-MS
(ESI-TOF): m/z=426.0146, calcd. for C21H14FIN [M+H]+:
426.0149.
8.3 Hz, 1H), 7.76–7.69 (m, 2H), 7.58–7.50 (m, 4H), 7.41–
7.37 (m, 3H), 7.28–7.26 (m, 2H); 13C NMR (CDCl3,
100 MHz): d=157.3, 154.7, 146.8, 144.0, 142.2, 130.0, 129.3,
129.2, 129.0 (2C), 128.6 (2C), 128.4, 127.3, 127.2, 126.8,
126.4, 124.8, 98.4; HR-MS (ESI-TOF): m/z=413.9811,
calcd. for C19H13INS [M+H]+: 413.9808.
2-Methyl-4-phenyl-3-iodoquinoline (1p): White solid; mp
126–1288C; IR: v=3055, 2999, 2923, 1636, 1558, 1368 cmÀ1
;
2,4-Diphenyl-3-bromoquinoline (1w):[11j] White solid; mp
92–948C; 1H NMR (CDCl3, 400 MHz): d=8.18 (d, J=
8.7 Hz, 1H), 7.75–7.71 (m, 3H), 7.59–7.46 (m, 6H), 7.44 (m,
2H), 7.37–7.35 (m, 2H); 13C NMR (CDCl3, 100 MHz): d=
158.9, 149.6, 146.4, 140.9, 138.0, 129.8, 129.6, 129.4 (2C),
129.2 (2C), 128.7, 128.5 (2C), 128.4, 128.0 (2C), 127.9, 127.3,
126.4, 118.5.
1H NMR (CDCl3, 400 MHz): d=8.04 (d, J=8.2 Hz, 1H),
7.71–7.67 (m, 1H), 7.57–7.51 (m, 3H), 7.34–7.32 (m, 2H),
7.22–7.19 (m, 2H), 3.05 (s, 3H); 13C NMR (CDCl3,
100 MHz): d=159.8, 153.7, 146.8, 141.9, 129.8, 129.0 (2C),
128.6 (2C), 128.5, 128.4, 126.8, 126.7, 126.4, 100.4, 31.6; HR-
MS (ESI-TOF): m/z=346.0085, calcd. for C16H13IN [M+
H]+: 346.0087.
2,4-Diphenyl-3-chloroquinoline (1x):[11j] White solid; mp
106–1088C; 1H NMR (CDCl3, 400 MHz): d=8.18 (d, J=
8.2 Hz, 1H), 7.82–7.79 (m, 2H), 7.72–7.68 (m, 1H), 7.58–
7.43 (m, 8H), 7.40–7.38 (m, 2H); 13C NMR (CDCl3,
100 MHz): d=157.5, 146.9, 146.1, 139.4, 135.8, 129.7, 129.6,
129.5 (2C), 129.4 (2C), 128.8, 128.5 (2C), 128.4, 128.1 (2C),
127.7, 127.2, 126.4, 126.1.
2-Butyl-4-phenyl-3-iodoquinoline (1q): White solid; mp
60–628C; IR: v=3058, 2959, 1637, 1553, 1378 cmÀ1
;
1H NMR (CDCl3, 400 MHz): d=8.06 (d, J=8.7 Hz, 1H),
7.70–7.65 (m, 1H), 7.57–7.51 (m, 3H), 7.32–7.31 (m, 2H),
7.22–7.19 (m, 2H), 3.30–3.22 (m, 2H), 1.89–1.82 (m, 2H),
1.59–1.49 (m, 2H), 1.01 (t, J=7.3, 3H); 13C NMR (CDCl3,
100 MHz): d=162.8, 153.9, 146.9, 142.2, 129.7, 129.0 (2C),
128.6, 128.5 (2C), 128.3, 126.9, 126.8, 126.4, 100.2, 43.0, 31.3,
22.8, 14.0; HR-MS (ESI-TOF): m/z=388.0554, calcd. for
C19H19IN [M+H]+: 388.0557.
2,4-Diphenyl-6-methyl-3-iodoquinoline (1y):[11j] White
1
solid; mp 152–1568C; H NMR (CDCl3, 400 MHz): d=8.05
(d, J=8.72 Hz, 1H), 7.64–7.61 (m, 2H), 7.58–7.51 (m, 4H),
7.50–7.41 (m, 3H), 7.29–7.26 (m, 2H), 7.14 (s, 1H), 2.40 (s,
3H); 13C NMR (CDCl3, 100 MHz): d=160.8, 153.8, 145.4,
143.7, 142.3, 137.3, 132.3, 129.2 (3C), 129.1 (2C), 128.6 (2C),
128.4, 128.3, 127.9 (2C), 127.3, 125.5, 98.6, 21.7.
2,4-Diphenyl-6-chloro-3-iodoquinoline (1z): White solid;
mp 172–1748C (lit.[11b] 169–1748C); 1H NMR (CDCl3,
400 MHz): d=8.09 (d, J=8.72 Hz, 1H), 7.67–7.62 (m, 3H),
7.59–7.54 (m, 3H), 7.52–7.46 (m, 3H), 7.37 (d, J=2.28 Hz,
1H), 7.29–7.26 (m, 2H); 13C NMR (CDCl3, 100 MHz): d=
162.1, 153.9, 145.3, 143.3, 141.4, 133.1, 131.0 (2C), 129.1
(2C), 128.9 (2C), 128.8 (2C), 128.7, 128.7, 128.0 (2C), 127.8,
125.5, 99.8.
2,4-Diphenyl-6-bromo-3-iodoquinoline (1aa): White solid;
mp 184–1868C (lit.[11b] 146–1528C); 1H NMR (CDCl3,
400 MHz): d=8.02 (d, J=8.72 Hz, 1H), 7.77 (m, 1H), 7.65–
7.62 (m, 2H), 7.60–7.54 (m, 4H), 7.51–7.45 (m, 3H), 7.27
(m, 2H); 13C NMR (CDCl3, 100 MHz): d=162.3, 153.8,
145.4, 143.3, 141.3, 133.6, 131.1, 129.1 (2C), 128.9 (2C),
128.8 (2C), 128.8 (2C), 128.7, 128.2, 128.0 (2C), 121.4, 99.8.
2-Phenyl-4-(p-tolyl)-3-iodoquinoline (1r): White solid; mp
150–1528C
(lit.[11b]
150–1538C);
1H NMR
(CDCl3,
400 MHz): d=8.16 (d, J=8.2 Hz, 1H), 7.73–7.69 (m, 1H),
7.65–7.63 (m, 2H), 7.51–7.36 (m, 7H), 7.18 (d, J=7.8 Hz,
2H), 2.48 (s, 3H); 13C NMR (CDCl3, 100 MHz): d=161.8,
154.8, 146.8, 143.7, 139.1, 138.3, 130.0, 129.3, 129.3 (2C),
129.2 (2C), 128.9 (2C), 128.5, 127.9 (2C), 127.4, 127.1, 126.9,
98.8, 21.5.
2-Phenyl-4-(4-fluorophenyl)-3-iodoquinoline (1s): White
solid; mp 178–1808C; IR: v=3056, 2929, 1649, 1598,
1378 cmÀ1 1H NMR (CDCl3, 400 MHz): d=8.16 (d, J=
;
8.3 Hz, 1H), 7.75–7.71 (m, 1H), 7.65–7.62 (m, 2H), 7.52–
7.39 (m, 5H), 7.28–7.24 (m, 4H); 13C NMR (CDCl3,
100 MHz): d=162.7 (d, J=247.0 Hz), 161.9, 153.6, 146.7,
143.6, 137.9, 131.0 (d, J=7.6 Hz, 2C), 130.1, 129.5, 129.2
(2C), 128.6, 127.9 (2C), 127.4 (2C), 126.5, 115.8 (d, J=
21.9 Hz, 2C), 98.8. HR-MS (ESI-TOF): m/z=426.0145,
calcd. for C21H14FIN [M+H]+: 426.0149.
2-Phenyl-4-(4-chlorophenyl)-3-iodoquinoline (1t): White
solid; mp 192–1948C; IR: v=3072, 2952, 1558, 1381 cmÀ1
;
1H NMR (CDCl3, 400 MHz): d=8.16 (d, J=8.3 Hz, 1H),
7.75–7.71 (m, 1H), 7.65–7.63 (m, 2H), 7.56–7.37 (m, 7H),
7.24 (d, J=8.3 Hz, 2H); 13C NMR (CDCl3, 100 MHz): d=
161.8, 153.4, 146.8, 143.5, 140.3, 134.6, 130.6 (2C), 130.2,
129.5, 129.2 (2C), 129.0 (2C), 128.6, 128.0 (2C), 127.4, 127.1,
126.4, 98.4; HR-MS (ESI-TOF): m/z=441.9861, calcd for
C21H14ClIN [M+H]+: 441.9854.
Supporting Information
1
Copies of the H NMR and 13C NMR spectra for all com-
pounds and 1a–1z and 1aa and the CIF file for the single
crystal X-ray diffraction analysis of 1u are available in the
Supporting Information.
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FULL PAPERS
asc.wiley-vch.de
2013, 54, 1471–1474; d) R. M. Cross, N. K. Namelikon-
da, T. S. Mutka, L. Luong, D. E. Kyle, R. Manetsch, J.
Med. Chem. 2011, 54, 8321–8327; e) M. J. Mphahlele,
M. M. Mphahlele, Tetrahedron 2011, 67, 4689–4695.
[8] a) B. Boganyi, J. Kaman, Tetrahedron 2013, 69, 9512–
9519; b) B. P. Fors, N. R. Davis, S. L. Buchwald, J. Am.
Chem. Soc. 2009, 131, 5766–5768; c) K. T. J. Loones,
B. U. W. Maes, R. A. Dommisse, Tetrahedron 2007, 63,
8954–8961.
[9] D. Maiti, Chem. Commun. 2011, 47, 8340–8342.
[10] a) J. Colomb, G. Becker, S. Fieux, L. Zimmer, T. Bill-
ard, J. Med. Chem. 2014, 57, 3884–3890; b) S. Bol-
den Jr, X. Y. Zhu, J. R. Etukala, C. Boateng, T. Mazu,
H. Flores-Rozas, M. R. Jacob, S. I. Khan, L. A. Walker,
S. Y. Ablordeppey, Eur. J. Med. Chem. 2013, 70, 130–
142; c) C. A. Boateng, X. Y. Zhu, M. R. Jacob, S. I.
Khan, L. A. Walker, S. Y. Ablordeppey, Eur. J. Med.
Chem. 2011, 46, 1789–1797.
[11] a) M. S. Reddy, N. Thirupathi, Y. K. Kumar, RSC Adv.
2012, 2, 3986–3992; b) S. Ali, H.-T. Zhu, X.-F. Xia, K.-
G. Ji, Y.-F. Yang, X.-R. Song, Y.-M. Liang, Org. Lett.
2011, 13, 2598–2601; c) S. V. Ryabukhin, V. S. Naum-
chik, A. S. Plaskon, O. O. Grygorenko, A. A. Tolma-
chev, J. Org. Chem. 2011, 76, 5774–5781; d) X. Zhang,
T. Yao, M. A. Campo, R. C. Larock, Tetrahedron 2010,
66, 1177–1187; e) Z. Huo, I. D. Gridnev, Y. Yamamoto,
J. Org. Chem. 2010, 75, 1266–1270; f) P. R. Likhar,
M. S. Subhas, S. Roy, M. L. Kantam, B. Sridhar, R. K.
Seth, S. Biswas, Org. Biomol. Chem. 2009, 7, 85–93;
g) K. O. Hessian, B. L. Flynn, Org. Lett. 2006, 8, 243–
246; h) X. Zhang, M. A. Campo, T. Yao, R. C. Larock,
Org. Lett. 2005, 7, 763–766; i) P. J. Campos, E. Anon,
M. C. Malo, C.-Q. Tan, M. A. Rodriguez, Tetrahedron
1998, 54, 6929–6938; j) P. J. Campos, C.-Q. Tan, M. A.
Rodriguez, E. Anon, J. Org. Chem. 1996, 61, 7195–
7197.
Acknowledgements
This work was supported by the National Natural Scientific
Foundation of China (Nos. 21372142 and 21472107).
References
[1] For selected reviews, see: a) O. Afzal, S. Kumar, M. R.
Haider, M. R. Ali, R. Kumar, M. Jaggi, S. Bawa, Eur. J.
Med. Chem. 2015, 97, 871–910; b) R. A. Jones, S. S.
Panda, C. D. Hall, Eur. J. Med. Chem. 2015, 97, 335–
355; c) R. S. Keri, S. A. Patil, Biomed. Pharmacother.
2014, 68, 1161–1175; d) A. P. Gorka, A. de Dios, P. D.
Roepe, J. Med. Chem. 2013, 56, 5231–5246; e) S. Mu-
kherjee, M. Pal, Drug Discovery Today 2013, 18, 389–
398.
[2] For selected reviews, see: a) G. N. Lipunova, E. V.
Nosova, V. N. Charushin, O. N. Chupakhin, Comment
Inorg. Chem. 2014, 34, 142–177; b) F. Artizzu, M. L.
Mercuri, A. Serpe, P. Deplano, Coord. Chem. Rev.
2011, 255, 2514–2529; c) M. Albrecht, M. Fiege, O.
Osetska, Coord. Chem. Rev. 2008, 252, 812–824.
[3] For selected reviews, see: a) J. B. Bharate, R. A. Vish-
wakarma, S. B. Bharate, RSC Adv. 2015, 5, 42020–
42053; b) S. M. Prajapati, K. D. Patel, R. H. Vekariya,
S. N. Panchal, H. D. Patel, RSC Adv. 2014, 4, 24463–
24476; c) R. I. Khusnutdinov, A. R. Bayguzina, U. M.
Dzhemilev, J. Organomet. Chem. 2014, 768, 75–114;
d) J. Barluenga, F. Rodriguez, F. J. Fananas, Chem.
Asian J. 2009, 4, 1036–1048; e) S. Madapa, Z. Tusi, S.
Batra, Curr. Org. Chem. 2008, 12, 1116–1183.
[4] For selected reviews, see: a) J. Marco-Contelles, E.
Perez-Mayoral, A. Samadi, M. C. Carreiras, E. Soriano,
Chem. Rev. 2009, 109, 2652–2671; b) C.-C. Cheng, S.-J.
Yan, Org. React. 1982, 28, 37–201; c) R. H. F. Manske,
M. Kukla, Org. React. 1953, 7, 59–72; d) R. H. Reitse-
ma, Chem. Rev. 1948, 43, 47–68; e) F. W. Bergstrom,
Chem. Rev. 1944, 35, 77–277.
[12] J. E. Hein, J. C. Tripp, L. B. Krasnova, K. B. Sharpless,
V. V. Fokin, Angew. Chem. 2009, 121, 8162–8165;
Angew. Chem. Int. Ed. 2009, 48, 8018–8021.
[13] a) J. Zhang, W. Chen, B. Wang, Z. Zhao, X. Wang, Y.
Hu, RSC Adv. 2015, 5, 14561–14566; b) C. Vidal, J.
Darcꢄa-ꢅlvarez, Green Chem. 2014, 16, 3515–3521; c) S.
Lal, H. S. Rzepa, S. Dꢄez-Gonzꢆlez, ACS Catal. 2014, 4,
2274–2287; d) B. T. Worrell, J. A. Malik, V. V. Fokin,
Science 2013, 340, 457–460; e) D. Fu, J. Zhang, S. Cao,
J. Fluorine Chem. 2013, 156, 170–176; f) W. S. Brother-
ton, R. J. Clark, L. Zhu, J. Org. Chem. 2012, 77, 6443–
6455; g) J. Garcꢄa-ꢅlverez, J. Dꢄez, J. Gimeno, F. J.
Suꢆrez, C. Vincent, Eur. J. Inorg. Chem. 2012, 5854–
[5] a) A.-M. Lord, M. F. Mahon, M. D. Lloyd, M. D.
Threadgill, J. Med. Chem. 2009, 52, 868–877; b) E. K.
Yum, O.-K. Yang, S. K. Kang, H. G. Cheon, S. S. Kim,
J.-K. Choi, Bull. Korean Chem. Soc. 2004, 25, 1091–
1094; c) H. Nakamura, T. Kamakura, S. Onagi, Org.
Lett. 2006, 8, 2095–2098.
[6] a) H. P. Kokatla, D. Sil, S. S. Malladi, R. Balakrishna,
A. R. Hermanson, L. M. Fox, X. Wang, A. Dixit, S. A.
David, J. Med. Chem. 2013, 56, 6871–6885; b) M. J.
Mphahlele, L. G. Lesenyeho, H. R. Makelane, Tetrahe-
dron 2010, 66, 6040–6046; c) M. J. Mphahlele, Tetrahe-
dron 2010, 66, 8261–8266.
[7] a) A. Nilsen, G. P. Miley, I. P. Forquer, M. W. Mather,
K. Katneni, Y. Li, S. Pou, A. M. Pershing, A. M. Stick-
les, E. Ryan, J. X. Kelly, J. S. Doggett, K. L. White, D. J.
Hinrichs, R. W. Winter, S. A. Charman, L. N. Zakharov,
I. Bathurst, J. N. Burrows, A. B. Vaidya, M. K. Riscoe,
J. Med. Chem. 2014, 57, 3818–3834; b) L. N. Tumey,
D. H. Boschelli, N. Bhagirath, J. Shim, E. A. Murphy,
D. Goodwin, E. M. Bennett, M. Wang, L.-L. Lin, B.
Press, M. Shen, R. K. Frisbie, P. Morgan, S. Mohan, J.
Shin, V. R. Rao, Bioorg. Med. Chem. Lett. 2014, 24,
2066–2072; c) J. Colomb, T. Billard, Tetrahedron Lett.
ˇ
5863; h) M. Jurꢄcek, K. Stout, P. H. Kouwer, A. E.
Rowan, Org. Lett. 2011, 13, 3494–3497; i) J. Garcꢄa-ꢅl-
verez, J. Dꢄez, J. Gimeno, Green Chem. 2010, 12, 2127–
2130.
[14] a) W. Chen, J. Zhang, B. Wang, Z. Zhao, X. Wang, Y.
Hu, J. Org. Chem. 2015, 80, 2413–2417; b) J. A. Cross-
ley, D. L. Browne, J. Org. Chem. 2010, 75, 5414–5416.
[15] J. Tummatorn, P. Poonsilp, P. Nimnual, J. Janprasit, C.
Thongsornkleeb, S. Ruchirawat, J. Org. Chem. 2015, 80,
4516–4525.
[16] B. H. M. Kuijpers, G. C. T. Dijkmans, S. Groothuys,
P. J. L. M. Quaedflieg, R. H. Blaauw, F. L. van Delft,
F. P. J. T. Rutjes, Synlett 2005, 3059–3062.
Adv. Synth. Catal. 0000, 000, 0 – 0
7
ꢂ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

FULL PAPERS
asc.wiley-vch.de
[17] J. S. Oakdale, R. K. Sit, V. V. Fokin, Chem. Eur. J. 2014,
20, 11101–11110.
16, 5600–5603; d) A. J. Walkinshaw, W. Xu, M. G.
Suero, M. J. Gaunt, J. Am. Chem. Soc. 2013, 135,
12532–12535; e) E. Cahard, N. Bremeyer, M. J. Gaunt,
Angew. Chem. 2013, 125, 9454–9458; Angew. Chem.
Int. Ed. 2013, 52, 9284–9288; f) R. J. Phipps, L. McMur-
ray, S. Ritter, H. A. Duong, M. J. Gaunt, J. Am. Chem.
Soc. 2012, 134, 1073–10776.
[18] a) U. Balijapalli, S. K. Iyer, Eur. J. Org. Chem. 2015,
5089–5098; b) Y. Wang, C. Chen, J. Peng, M. Li,
Angew. Chem. 2013, 125, 5431–5435; Angew. Chem.
Int. Ed. 2013, 52, 5323–5327; c) X.-L. Chen, J.-M.
Zhang, W.-L. Shang, B.-Q. Lu, J.-A. Jin, J. Fluorine
Chem. 2012, 133, 139–145; d) K. C. Majumdar, R. K.
Nandi, S. Ganai, A, Taher, Synlett 2011, 116–120;
e) H. Huang, H. Jiang, K. Chen, H. Liu, J. Org. Chem.
2009, 74, 5476–5480; f) Y. Kuninobu, Y. Inoue, K.
Takai, Chem. Lett. 2007, 36, 1422–1423; g) J. S. Yadav,
B. V. S. Reddy, R. S. Rao, V. Naveenkumar, K, Na-
gaiah, Synthesis 2003, 1610–1614; h) H. Z. S. Huma, R.
Halder, S. S. Kalra, J. Das, J. Iqbala, Tetrahedron Lett.
2002, 43, 6485–6488.
[19] For selected recent references, and references cited
therein: a) ꢅ. Sinai, D. Vangel, T. Gꢆti, P. Bombicz, Z.
Novꢆk, Org. Lett. 2015, 17, 4136–4139; b) J. Chen, C.
Chen, J. Chen, G. Wang, H. Qu, Chem. Commun. 2015,
51, 1356–1359; c) Z. Liu, D. Zhu, B. Luo, N. Zhang, Q.
Liu, Y. Hu, R. Pi, P. Huang, S. Wen, Org. Lett. 2014,
[20] a) A. J. Hickman, M. S. Sanford, Nature 2012, 484, 177–
185; b) B. Chen, X.-L. Hou, Y.-X. Li, Y.-D. Wu, J. Am.
Chem. Soc. 2011, 133, 7668–7671; c) A. E. King, L. M.
Huffman, A. Casitas, M. Costas, X. Ribas, S. S. Stahl, J.
Am. Chem. Soc. 2010, 132, 12068–12073; d) R. J.
Phipps, M. J. Gaunt, Science 2009, 323, 1593–1597;
e) X. Ribas, D. A. Jackson, B. Donnadieu, J. Mahꢇa, T.
Parella, R. Xifra, B. Hedman, K. O. Hodgson, A.
Llobet, T. D. P. Stack, Angew. Chem. 2002, 114, 3117–
3120; Angew. Chem. Int. Ed. 2002, 41, 2991–2994.
[21] CCDC 1447247 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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FULL PAPERS
Synthesis of 3-Iodoquinolines by Copper-Catalyzed Tandem
Annulation from Diaryliodoniums, Nitriles, and 1-
Iodoalkynes
9
Adv. Synth. Catal. 2016, 358, 1 – 9
Xuesong Wang, Xingyong Wang, Dayun Huang,
Chulong Liu, Xinyan Wang,* Yuefei Hu*
Adv. Synth. Catal. 0000, 000, 0 – 0
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ꢂ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!