Palladium-catalyzed oxidative carbonylation for the synthesis of polycyclic aromatic hydrocarbons (PAHs)

Article abstract of DOI:10.1021/jo502013s

A direct and facile palladium-catalyzed C-H bond oxidative carbonylation reaction and oxidative cyclization for the synthesis of polycyclic aromatic hydrocarbons (PAHs) is reported herein. The intramolecular cyclocarbonylation, through C-H activation and C-C, C-O bond formations under mild conditions, proceeds smoothly with good functional group tolerance in high to excellent yields. The intramolecular palladium-catalyzed direct oxidative C-H bond functionalization for the C-O bond formation is also demonstrated, which provides an efficient approach for the construction of various PAHs.

Full text of DOI:10.1021/jo502013s

Note
pubs.acs.org/joc
Palladium-Catalyzed Oxidative Carbonylation for the Synthesis of
Polycyclic Aromatic Hydrocarbons (PAHs)
Fanghua Ji, Xianwei Li, Wanqing Wu, and Huanfeng Jiang*
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, PR China
S
* Supporting Information
ABSTRACT: A direct and facile palladium-catalyzed C−H bond oxidative carbonylation reaction and oxidative cyclization for
the synthesis of polycyclic aromatic hydrocarbons (PAHs) is reported herein. The intramolecular cyclocarbonylation, through
C−H activation and C−C, C−O bond formations under mild conditions, proceeds smoothly with good functional group
tolerance in high to excellent yields. The intramolecular palladium-catalyzed direct oxidative C−H bond functionalization for the
C−O bond formation is also demonstrated, which provides an efficient approach for the construction of various PAHs.
arbonylation of organic compounds with CO as carbon-
atom source has been continued to be an attractive
C
strategy in organic synthesis.1 Since seminal work by Heck and
co-workers in 1974,2 transition-metal-catalyzed carbonylation
reactions of (pseudo)halides with CO in the presence of
various nucleophiles have been recognized as one of the most
powerful tools to synthesize a variety of carbonyl compounds.3
In recent decades, increased attention has been focused on the
direct C−H activation for C−C and C−heteroatom bond
formation.4 A growing number of palladium- and rhodium-
catalyzed carbonylation reactions of aromatic C−H bonds that
allow for straightforward and atom-economical carbonyl group
formation have been developed by Chatani, Yu, and our group,
etc.5 However, a lack of control over the chemo- and
regioselective activation of a specific C−H bond is still a
challenging task due to the ubiquity and robustness of C−H
bonds. In fact, the problem is a pervasive challenge in the field
of C−H activation. To solve this problem, the application of a
directing group is needed to allow selective C−H bond
activation. A variety of directing groups have evolved to include
nitrogen-containing heterocycles,6 amides,5g,j carboxylic acids,5f
and tertiary amines.7 In some cases, the directed intermolecular
C−H carbonylation reactions require extra synthetic steps to
remove the directing groups, which sacrifices atom economy.
On the other hand, carbonylation with subsequent intra-
molecular cyclization reactions,8 in which the directing groups
act as nucleophiles as well, has been shown to be an efficient
process with high step efficiency and atom economy without
installing and removing any directing groups. In this context,
transition metal-catalyzed C−H bond functionalization reac-
tions have emerged as one of the most powerful trans-
formations in the past decade (Figure 1). The direct
functionalization of C−H and C−X bonds for the construction
of complex molecules holds the synthetic advantages of high
Figure 1. Direct C−H and X−H bond functionalization.
atom-efficiency and chemo- or regioselectivity. Additionally,
this kind of reactions has received substantial attention because
of their ability to synthesize useful motifs in an extremely rapid
manner.
Polycyclic aromatic hydrocarbons (PAHs), which are
characterized by the presence of two or more fused benzene
rings arranged in various configurations,9 have attracted
considerable attention in different research fields such as
pharmaceutical chemistry and materials science (Figure 2).10
Numerous synthetic strategies for the construction of PAHs
have been developed in the past decades due to their
remarkable biological activity, electronic structure and photo-
chemical properties, among which, the palladium-catalyzed
annulation provides a convenient and efficient route for the
synthesis of a wide range of carbocycles.11 The incorporation of
heteroatoms into a PAH system can change its pharmacological
activity and expand the utility in the field of optoelectronic
devices. Nevertheless, traditional methods for the construction
of PAHs usually suffered from tedious synthetic procedures,12
and so simpler and more atom-economical methods to access
structurally diverse PAHs remains highly desirable. Herein, we
report our recent effort on palladium-catalyzed oxidative
functionalization, and more significantly, oxidative C−H bond
carbonylation reactions for the construction of PAHs.
Received: September 1, 2014
© XXXX American Chemical Society
A
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Note
Figure 2. Gilvocarcin ravidomycin family of antibiotics.
a
Table 1. Optimization of the Reaction Conditions
bc
,
entry
Pd cat.
additive
oxidant
solvent
T (°C)
yield (%)
1
Pd(OAc)2
PdCl2
TsOH·H2O
TsOH·H2O
TsOH·H2O
TsOH·H2O
PivOH
BQ
BQ
BQ
BQ
BQ
BQ
BQ
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
CH3CN
DMF
100
100
100
100
100
100
100
100
100
100
100
100
100
80
65
2
n.d.
69
3
Pd2(dba)3
Pd(TFA)2
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
4
trace
23
5
6
LiBr
n.d.
41
7
−
8
TsOH·H2O
TsOH·H2O
TsOH·H2O
TsOH·H2O
TsOH·H2O
TsOH·H2O
TsOH·H2O
TsOH·H2O
TsOH·H2O
TsOH·H2O
MnO2
60
9
Cu(OAc)2·H2O
O2
88
10
11
12
13
14
15
16
17
17
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
30
5
PhMe
n.d.
79
dioxane
dioxane
dioxane
dioxane
110
100
100
50
d
77
e
85
a
Reaction conditions: unless otherwise noted, all reactions were performed with 1a (0.2 mmol), Pd2(dba)3 (15 mol %), additive (1.5 equiv), oxidant
b
c
d
e
(3 equiv), CO (1 balloon), 100 °C, 24 h. Isolated yield. Reactions were carried out in a sealed tube. The catalyst loading was 10 mol %. The
oxidant loading was 1.5 equiv.
Initially, 3-phenylquinolin-4(1H)-one (1a; 0.2 mmol) was
used as the substrate to optimize the reaction conditions.
Fortunately, the desired product 6H-isochromeno[4,3-c]-
quinolin-6-one (2a) was obtained in 65% yield with TsOH·
H2O (1.5 equiv) as additive and BQ (3 equiv) as oxidant,
Pd(OAc)2 (15 mol %) as catalyst in dioxane under CO
atmosphere (Table 1, entry 1). To improve the yield of 2a, we
screened various parameters including catalyst, additive,
oxidant, solvent and reaction temperature. The use of
Pd2(dba)3 as a catalyst gave a further increase in the yield of
product, while PdCl2 and Pd(TFA)2 were ineffective for the
reaction (entries 2−4). Furthermore, different additives were
also investigated, in which LiBr proved to have no effect as an
additive (entry 6), and PivOH gave comparably unfavorable
results (entry 5). Further optimization of oxidants showed that
the use of Cu(OAc)2·H2O as the oxidant resulted in a decent
boost in the yield of 2a, while MnO2 and O2 turned out to be
inferior in the system (entries 8−10). The solvents were vital to
the catalytic system, and the desired product 2a was hardly
obtained with toluene, whereas CH3CN and DMF also gave
disappointing results (entries 11−13). When the reaction
temperature was changed, the yields were decreased to 79 and
50% (entries 14−15). Gratifyingly, when the oxidant and
catalyst loading were reduced to 1.5 equiv and 10 mol %, 2a
could be isolated in 85 and 77% yields, respectively, without
any decrease (entries 16−17).
With the optimized conditions in hand, the scope of the
reaction was investigated (Table 2). The oxidative carbon-
ylation reaction displayed a good functional-group tolerance
and moderate to excellent yields were obtained. In general,
substrates bearing methyl, ethyl, isopropyl, methoxy, ethoxy,
phenoxy, fluoro, and sensitive functional groups such as chloro
and bromo groups, could transfer to the corresponding
products in high to excellent yields, allowing further
functionalization through conventional cross-coupling reactions
(2a−j). Treatment of substrates bearing the strong electron-
withdrawing groups, including CF3 and OCF3, afforded the
desired products in excellent yields. However, when using
polycyclic and heterocyclic compounds 2o and 2p as the
substrates, the desired transformation did not occur and none
of the corresponding products could be detected. No
byproducts were detected in all these reaction systems.
B
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Note
ab
,
Table 2. Synthesis of Carbonylation Products 2
a
The reactions were carried out at 100 °C, using 1 (0.2 mmol), Cu(OAc)2·H2O (0.3 mmol), TsOH·H2O (0.3 mmol), Pd2(dba)3 (10 mol %) in
b
c
dioxane (2 mL) under CO atmosphere for 24 h. Yields refer to the isolated yields. The catalyst was Pd(OAc)2
a b
,
Table 3. Synthesis of Cyclization Products 2
a
The reactions were carried out at 140 °C, using 1 (0.2 mmol), Cu(OAc)2·H2O (0.3 mmol), TsOH·H2O (0.3 mmol), Pd2(dba)3 (10 mol %) in
b
xylene (2 mL) for 12 h. Yields refer to the isolated yields.
Direct oxidative C−H/X−H coupling reactions represent a
great advance as to traditional couplings based on C−X bond.
Since the work of Buchwald on palladium-catalyzed oxidative
C−H/N-H couplings to afford biologically active molecules
carbazoles,12 lots of work on the direct oxidative coupling
between C−H bond and X−H bond have been developed. For
example, Yu’s group developed a palladium-catalyzed C−O
coupling reaction using PdII/PdIV catalytic cycle for the
synthesis of benzofurans using PhI(OAc)2 as the oxidant.13
Recently, Liu et al. realized C−O bond reductive elimination
utilizing Pd0/PdII catalytic cycle with the assistance of NHC
ligand.14,15 Combining this method and the reaction developed
in recent years, we can directly accomplish the synthesis of
C
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Note
purified by column chromatography on silica gel to afford the
corresponding products 2 with petroleum ether/ethyl acetate as the
eluent.
benzofuro[3,2-c]quinolines. As shown in Table 3, various
derivatives could be synthesized in moderate to high yields.
On the basis of above results and previous reports,5f,j,l we
propose a mechanism for this oxidative carbonylation (Scheme
1). Pd(OTs)2 is first formed in situ by the reaction of
Typical Experimental Procedure for Synthesis of 3a−3j. The
mixture of 1 (0.2 mmol), TsOH·H2O (0.3 mmol), Pd2(dba)3 (10 mol
%) and Cu(OAc)2·H2O (0.3 mmol) was stirred in xylene (2.0 mL) at
140 °C, in a 20 mL tube for 12 h. When the reaction was completed
(detected by TLC), the mixture was cooled to room temperature, and
then the solvent was removed under reduced pressure. The residue
was purified by column chromatography on silica gel to afford the
corresponding products 3 with petroleum ether/ethyl acetate as the
eluent
Scheme 1. Proposed Mechanism
3-Phenylquinolin-4(1H)-one (1a). Light yellow solid (1.5 g, 80%):
mp 258−261 °C; IR (KBr) 3733, 2987, 2357, 1743, 1455, 1374, 1243,
1
1048, 931, 848, 611; H NMR (400 MHz, DMSO) δ 12.08 (s, 1H),
8.23 (d, J = 8.0 Hz, 1H), 8.13 (s, 1H), 7.72 (d, J = 7.6 Hz, 2H), 7.66 (t,
J = 7.6 Hz, 1H), 7.60 (d, J = 8.0 Hz, 1H), 7.44−7.32 (m, 3H), 7.28 (t,
J = 7.2 Hz, 1H); 13C NMR (100 MHz, DMSO) δ 174.7, 139.3, 138.1,
136.2, 131.5, 128.4, 127.8, 126.3, 125.9, 125.6, 123.2, 119.7, 118.2.
HRMS (ESI) m/z calcd for C15H12NO [M + H]+, 222.0913, found
222.0917.
6-Methyl-3-phenylquinolin-4(1H)-one (1b). Light yellow solid (1.0
g, 77%): mp >300 °C; IR (KBr) 3741, 2991, 2359, 1763, 1462, 1376,
1
1242, 1055, 928, 850, 629; H NMR (400 MHz, DMSO) δ 8.10 (s,
1H), 8.02 (s, 1H), 7.74 (d, J = 7.6 Hz, 2H), 7.51 (d, J = 8.4 Hz, 1H),
7.45 (dd, J = 8.4, 1.6 Hz, 1H), 7.37 (t, J = 7.6 Hz, 2H), 7.25 (t, J = 7.2
Hz, 1H), 2.43 (s, 3H); 13C NMR (100 MHz, DMSO) δ 174.1, 138.9,
138.4, 136.8, 132.5, 132.1, 128.3, 127.7, 126.0, 126.0, 124.7, 119.1,
119.0, 20.8. HRMS (ESI) m/z calcd for C16H14NO [M + H]+,
236.1070, found 236.1079.
6-Ethyl-3-phenylquinolin-4(1H)-one (1c). White solid (1.7 g,
80%): mp >300 °C; IR (KBr) 3739, 2990, 1763, 1376, 1242, 1055,
927, 848, 624; 1H NMR (400 MHz, DMSO) δ 12.10 (s, 1H), 8.08 (m,
2H), 7.73 (d, J = 6.8 Hz, 2H), 7.54 (s, 2H), 7.39−7.37 (m, 2H), 7.29−
7.27 (m, 1H), 2.75−2.72 (m, 2H), 1.24 (t, J = 6.6 Hz, 3H); 13C NMR
(100 MHz, DMSO) δ 174.6, 138.8, 137.8, 137.6, 136.4, 131.9, 128.4,
127.8, 126.2, 125.8, 123.5, 119.4, 118.3, 27. 9, 15.6. HRMS (ESI) m/z
calcd for C17H15NNaO [M + Na]+, 272.1046, found 272.1053.
6-Isopropyl-3-phenylquinolin-4(1H)-one (1d). Light brown solid
(1.5 g, 75%): mp 237−239 °C; IR (KBr) 3745, 2990, 1763, 1461,
1376, 1242, 1055, 928, 848, 628; 1H NMR (400 MHz, DMSO) δ 8.12
(s, 1H), 8.06 (s, 1H), 7.74 (d, J = 7.6 Hz, 2H), 7.59−7.54 (m, 2H),
7.40 (t, J = 7.6 Hz, 3H), 7.01 (d, J = 7.6, 7.4 Hz, 1H), 3.55−2.58 (m,
1H), 1.37−1.07 (m, 6H); 13C NMR (100 MHz, DMSO) δ 174.6,
143.4, 137.8, 137.7, 136.4, 130.6, 128.4, 127.8, 126.7, 126.2, 125.8,
121.9, 119.4, 118.3, 116.4, 33.1, 23.9. HRMS (ESI) m/z calcd for
C18H18NO [M + H]+, 264.1383, found 264.1387.
Pd2(dba)3 with Cu(OAc)2 and TsOH·H2O. Subsequently, aryl
C−H activation by Pd(OTs)2 affords the arylpalladium species
A, which further reacts with CO to form the intermediate B.
Then, B is transformed into C assisted by leaving p-TsOH.
Finally, reductive elimination of C gives the desired carbon-
ylation product 2 and generates the Pd0 species. Alternatively,
intermediate D is formed in the absence of CO, which
undergoes reductive elimination to give product 3.
In conclusion, we have developed a simple and efficient
strategy for the construction of 6H-isochromeno[4,3-c]-
quinolin-6-ones and benzofuro[3,2-c]quinolines through Pd-
catalyzed oxidative carbonylation or direct annulation process.
The reaction exhibits high atom-efficiency and chemo- or
regioselectivity for the direct functionalization of C−H and C−
X bonds. Notably, this transformation provides a straightfor-
ward and convenient protocol toward the syntheses of PAHs.
6-Methoxy-3-phenylquinolin-4(1H)-one (1e). Light pink solid
(800 mg, 65%): mp >300 °C; IR (KBr) 3741, 2991, 2358, 1763,
1462, 1377, 1242, 1055, 929, 850, 626; 1H NMR (400 MHz, DMSO)
δ 8.09 (s, 1H), 7.77 (d, J = 7.2 Hz, 2H), 7.63 (s, 1H), 7.55 (d, J = 8.8
Hz, 1H), 7.36 (t, J = 7.2 Hz, 2H), 7.24−7.19 (m, 2H), 3.84 (s, 3H);
13C NMR (100 MHz, DMSO) δ 172.9, 155.1, 140.5, 137.7, 128.2,
127.7, 127.5, 125.5, 122.3, 121.0, 117.8, 104.4, 99.5, 55.2. HRMS (ESI)
m/z calcd for C16H14NO2 [M + H]+, 252.1019, found 252.1023.
6-Bromo-3-phenylquinolin-4(1H)-one (1f). Light yellow solid (2g,
81%): mp >300 °C; IR (KBr) 3740, 2990, 2361, 1764, 1464, 1377,
EXPERIMENTAL SECTION
■
General Information. Melting points were measured with a
melting point instrument and were uncorrected. H and 13C NMR
1
spectra were recorded using a 400/600 MHz NMR spectrometer. The
chemical shifts are referenced to signals at 7.24 and 77.0 ppm,
respectively, and chloroform is solvent with TMS as the internal
standard. IR spectra were obtained either as potassium bromide pellets
or as liquid films between two potassium bromide pellets with a
spectrometer. GC−MS was obtained using electron ionization. HRMS
was obtained with a LCMS-IT-TOF mass spectrometer. TLC was
performed by using commercially prepared 100−400 mesh silica gel
plates and visualization was effected at 254 nm.
Typical Experimental Procedure for Synthesis of 4-Halo-2-
aminoquinolines 2a−2u. The mixture of 1 (0.2 mmol), TsOH·H2O
(0.3 mmol), Pd2(dba)3 (10 mol %) and Cu(OAc)2·H2O (0.3 mmol)
was stirred in dioxane (2.0 mL) at 100 °C, in a 20 mL tube with a
balloon CO for 24 h. When the reaction was complete (detected by
TLC), the mixture was cooled to room temperature. The residue was
1
1242, 1055, 928, 849, 631; H NMR (400 MHz, DMSO) δ 8.30 (s,
1H), 8.21 (s, 1H), 7.76−7.69 (m, 3H), 7.57 (d, J = 8.8 Hz, 1H), 7.37
(t, J = 7.6 Hz, 2H), 7.25 (t, J = 7.2 Hz, 1H); 13C NMR (100 MHz,
DMSO) δ 172.6, 141.7, 140.7, 136.8, 133.2, 128.2, 127.9, 127.8, 127.5,
126.0, 123.0, 119.5, 115.2, 112.0. HRMS (ESI) m/z calcd for
C15H10BrNNaO [M + Na]+, 321.9838, found 321.9841.
6-Chloro-3-phenylquinolin-4(1H)-one (1g). White solid (1.2 g,
77%): mp >300 °C; IR (KBr) 3737, 2990, 2356, 1761, 1459, 1376,
1
1242, 1053, 928, 848, 624; H NMR (400 MHz, DMSO) δ 8.21 (s,
1H), 8.15 (s, 1H), 7.73 (d, J = 8.0 Hz, 2H), 7.68 (s, 2H), 7.40 (t, J =
7.4 Hz, 2H), 7.29 (t, J = 7.2 Hz, 1H); 13C NMR (100 MHz, DMSO) δ
173.4, 138.9, 138.2, 135.9, 131.5, 128.3, 127.9, 126.9, 126.5, 124.4,
D
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Note
121.0, 119.9. HRMS (ESI) m/z calcd for C15H10ClNNaO [M + Na]+,
278.0343, found 278.0341.
6-Fluoro-3-phenylquinolin-4(1H)-one (1h). Light brown solid (1.5
2H); 13C NMR (151 MHz, TFA-140311) δ 165.6, 140.6, 135.8, 132.1,
131.0, 130.5, 129.8, 129.5, 129.0, 128.4, 123.1, 121.8, 120.5, 117.3,
115.5, 113.6, 111.7. HRMS (ESI) m/z calcd for C19H14NO [M + H]+,
272.1070, found 272.1069.
g, 67%): mp >300 °C; IR (KBr) 3742, 2990, 2361, 1764, 1464, 1377,
1
1242, 1055, 930, 849, 631; H NMR (400 MHz, DMSO) δ 8.21 (s,
3-Phenyl-1,8-naphthyridin-4(1H)-one (1p). Light yellow solid (1.4
g, 72%): mp >300 °C; IR (KBr) 3739, 2990, 2360, 1764, 1485, 1377,
1242, 1056, 926, 849, 628; 1H NMR (400 MHz, DMSO) δ 9.12 (d, J
= 7.2 Hz, 1H), 8.63 (s, 1H), 7.99 (t, J = 7.8 Hz, 1H), 7.85 (d, J = 7.6
Hz, 2H), 7.76 (d, J = 8.8 Hz, 1H), 7.48−7.42 (m, 3H), 7.36 (t, J = 7.2
Hz, 1H); 13C NMR (100 MHz, DMSO) δ 156.0, 152.7, 150.3, 137.1,
134.4, 128.2, 128.2, 127.4, 127.3, 126.1, 116.8, 115.0. HRMS (ESI) m/
z calcd for C14H11N2O [M + H]+, 223.0866, found 223.0869.
3-(p-Tolyl)quinolin-4(1H)-one (1q). Light brown solid (1.1 g,
90%): mp 287−289 °C; IR (KBr) 3738, 2990, 2360, 1764, 1463, 1377,
1H), 7.87 (d, J = 9.2 Hz, 1H), 7.75−7.73 (m, 3H), 7.58 (t, J = 8.2 Hz,
1H), 7.40 (t, J = 7.2 Hz, 2H), 7.29 (t, J = 7.0 Hz, 1H); 13C NMR (100
MHz, DMSO) δ 173.77, 158.44 (d, J = 240 Hz), 138.50, 136.05 (d, J =
22 Hz), 128.36, 127.83, 126.96 (d, J = 6 Hz), 126.40, 121.15 (d, J = 8
Hz), 120.36 (d, J = 26 Hz), 118.89, 109.41 (d, J = 22 Hz). HRMS
(ESI) m/z calcd for C15H11FNO [M + H]+, 240.0819, found
240.0818.
6-Phenoxy-3-phenylquinolin-4(1H)-one (1i). Light brown solid
(1.1 g, 70%): mp 256−258 °C; IR (KBr) 3738, 2991, 2316, 1764,
1
1
1479, 1376, 1242, 1055, 926, 626; H NMR (400 MHz, DMSO) δ
1242, 1055, 928, 849, 631; H NMR (400 MHz, DMSO) δ 12.16 (s,
12.33 (s, 1H), 8.17 (s, 1H), 7.71 (t, J = 7.4 Hz, 3H), 7.64 (s, 1H),
7.49−7.34 (m, 5H), 7.27 (t, J = 7.0 Hz, 1H), 7.19 (t, J = 7.2 Hz, 1H),
7.09 (d, J = 7.6 Hz, 2H); 13C NMR (100 MHz, DMSO) δ 173.9,
156.6, 153.1, 138.0, 136.1, 135.5, 130.2, 128.4, 127.8, 126.9, 126.3,
124.1, 123.8, 120.7, 118.9, 112.1. HRMS (ESI) m/z calcd for
C21H16NO2 [M + H]+, 314.1176, found 314.1177.
1H), 8.23 (d, J = 8.0 Hz, 1H), 8.11 (s, 1H), 7.67−7.59 (m, 4H), 7.34
(t, J = 7.4 Hz, 1H), 7.20 (d, J = 8.0 Hz, 2H), 2.33 (s, 3H); 13C NMR
(100 MHz, DMSO) δ 174.7, 139.3, 137.7, 135.38, 133.2, 131.4, 128.4,
128.2, 125.8, 125.6, 123.1, 119.7, 118.2, 20.8. HRMS (ESI) m/z calcd
for C16H14NO [M + H]+, 236.1070, found 236.1074.
3-(4-Methoxyphenyl)quinolin-4(1H)-one (1r). Light brown solid
(1.8 g, 88%): mp >300 °C; IR (KBr) 3740, 2990, 2361, 1764, 1463,
1377, 1242, 1055, 928, 849, 631; 1H NMR (400 MHz, DMSO) δ 8.23
(d, J = 7.6 Hz, 1H), 8.09 (s, 1H), 7.83−7.49 (m, 4H), 7.33 (s, 1H),
6.96 (d, J = 8.0 Hz, 2H), 3.80 (s, 3H); 13C NMR (100 MHz, DMSO)
δ 174.5, 157.8, 139.9, 138.2, 131.1, 129.4, 128.7, 125.9, 125.5, 122.9,
119.3, 118.7, 113.3, 55.0. HRMS (ESI) m/z calcd for C16H14NO2 [M
+ H]+, 252.1019, found 252.1025.
3-(Naphthalen-1-yl)quinolin-4(1H)-one (1s). Light yellow solid
(900 mg, 56%): mp 264−266 °C; IR (KBr) 3742, 2990, 2361, 1764,
1463, 1377, 1242, 1055, 928, 849, 631; 1H NMR (400 MHz, DMSO)
δ 12.14 (s, 1H), 8.22 (d, J = 7.2 Hz, 1H), 8.03 (s, 1H), 7.95−7.90(m,
2H), 7.70−7.66 (m, 3H), 7.60−7.15 (m, 5H); 13C NMR (100 MHz,
DMSO) δ 175.2, 139.8, 139.2, 135.0, 133.1, 132.2, 131.6, 127.9, 127.5,
126.5, 125.6, 125.5, 125.4, 123.3, 120.4, 118.4. HRMS (ESI) m/z calcd
for C19H14NO [M + H]+, 272.1070, found 272.1075.
3-Phenyl-6-(trifluoromethoxy)quinolin-4(1H)-one (1j). Light
brown solid (950 mg, 64%): mp >300 °C; IR (KBr) 3743, 2990,
1
2362, 1764, 1463, 1377, 1242, 1055, 927, 849, 631; H NMR (600
MHz, TFA-140311) δ 8.87 (s, 1H), 8.53 (s, 1H), 8.32 (d, J = 9.6 Hz,
1H), 8.08 (dd, J = 9.0, 2.4 Hz, 1H), 7.75−7.74 (m, 2H), 7.66 (d, J =
8.4 Hz, 1H), 7.64−7.60 (m, 2H), 7.50 (d, J = 8.4 Hz, 1H); 13C NMR
(151 MHz, TFA-140311) δ 165.8, 144.1, 136.5, 130.8, 130.2, 129.6,
128.9, 127.9, 124.3, 122.5, 121.8, 121.5, 120.7, 117. 2, 115.3, 113.8,
113.4, 111.5; HRMS (ESI) m/z calcd for C16H11F3NO2 [M + H]+,
306.0736, found 306.0733.
3-Phenyl-6-(trifluoromethyl)quinolin-4(1H)-one (1k). Light yellow
solid (1.3 g, 73%): mp >300 °C; IR (KBr) 3738, 2990, 2360, 1763,
1462, 1376, 1242, 1055, 932, 848, 632; 1H NMR (600 MHz,
TFA-140311) δ 9.24 (s, 1H), 9.14 (s, 1H), 8.59 (dd, J = 21.0, 9.0 Hz,
2H), 7.95−7.94(m, 4H), 7.83−7.81 (m, 2H); 13C NMR (151 MHz,
TFA-140311) δ 167.1, 145.7, 139.8, 131.7, 131.1, 130.4, 129.1, 127.9,
122.3, 120.9, 119.5, 117.3, 115.5, 113.6, 111.7. HRMS (ESI) m/z calcd
for C16H10F3NNaO [M + Na]+, 312.0607, found 312.0602.
3-(4-Fluorophenyl)quinolin-4(1H)-one (1t). Light brown solid (1.3
g, 65%): mp 244−246 °C; IR (KBr) 3741, 2990, 2362, 1764, 1464,
1
1376, 1242, 1055, 928, 849, 631; H NMR (400 MHz, DMSO) δ
8-Methyl-3-phenylquinolin-4(1H)-one (1l). Light brown solid (1.7
12.22 (s, 1H), 8.23 (d, J = 8.0 Hz, 1H), 8.17 (s, 1H), 7.80−7.77 (m,
2H), 7.69−7.61 (m, 2H), 7.36 (t, J = 7.4 Hz, 1H), 7.22 (t, J = 9.0 Hz,
2H); 13C NMR (100 MHz, DMSO) δ 174.6, 160.9 (d, J = 240 Hz),
139.3, 138.1, 132.4 (d, J = 3 Hz), 131.6, 130.2 (d, J = 7.8 Hz), 128.8,
125.8, 125.5, 123.3, 118.7, 118.2, 114.5 (d, J = 20.9 Hz), 114.0. HRMS
(ESI) m/z calcd for C15H11FNO [M + H]+, 240.0819, found
240.0823.
g, 86%): mp >300 °C; IR (KBr) 3738, 2990, 2360, 1763, 1462, 1376,
1
1242, 1054, 930, 848, 631; H NMR (400 MHz, DMSO) δ 8.11 (d, J
= 8.0 Hz, 1H), 8.00 (s, 1H), 7.72 (d, J = d, J = 5.9 Hz 7.6 Hz, 2H),
7.51 (d, J = 6.8 Hz, 1H), 7.40 (t, J = 7.6 Hz, 2H), 7.32−7.23 (m, 2H),
2.52 (s, 3H); 13C NMR (100 MHz, DMSO) δ 175.0, 138.0, 137.9,
136.1, 132.2, 128.4, 127.9, 126.4, 126.3, 126.0, 123.5, 122.9, 119.8,
17.1. HRMS (ESI) m/z calcd for C16H13NNaO [M + Na]+, 258.0889,
found 258.0886.
6H-Isochromeno[4,3-c]quinolin-6-one (2a). Light pink solid(42
mg, 85%): mp 246−248 °C; IR (KBr) 3427, 2987, 1763, 1453, 1376,
1
3-Phenyl-7-(trifluoromethyl)quinolin-4(1H)-one (1m). White solid
1242, 1056, 954, 850, 794, 629; H NMR (400 MHz, CDCl3) δ 9.54
(500 mg, 55%): mp >300 °C; IR (KBr) 3740, 2990, 2361, 1763, 1462,
(s, 1H), 8.49−8.44 (m, 2H), 8.30 (d, J = 8.2 Hz, 1H), 8.13 (d, J = 8.2
Hz, 1H), 7.92 (t, J = 7.2 Hz, 1H), 7.81 (t, J = 7.2 Hz, 1H), 7.67 (dd, J
= 15.6, 7.6 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ 159.5, 152.9,
148.2, 144.9, 135.2, 133.0, 130.8, 130.7, 129.2, 128.8, 127.4, 121.6,
121.1, 120.7, 118.2, 108.8. HRMS (ESI) m/z calcd for C16H10NO2 [M
+ H]+, 248.0706, found 248.0709.
3-Methyl-6H-isochromeno[4,3-c]quinolin-6-one (2b). White solid
(43 mg, 83%): mp 239−241 °C; IR (KBr) 3447, 2990, 1764, 1458,
1377, 1242, 1056, 927, 851, 794, 630; 1H NMR (400 MHz, CDCl3) δ
9.48 (s, 1H), 8.46 (d, J = 7.6 Hz, 1H), 8.31 (d, J = 7.6 Hz, 1H), 8.26
(s, 1H), 8.02 (d, J = 8.0 Hz, 1H), 7.91 (t, J = 7.4 Hz, 1H), 7.67−7.61
(m, 2H), 2.60 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 159.8, 152.3,
147.1, 144.0, 137.7, 135.2, 133.3, 132.9, 130.6, 129.0, 128.7, 121.1,
120.7, 120.5, 108.8, 99.6, 21.5. HRMS (ESI) m/z calcd for C17H12NO2
[M + H]+, 262.0863, found 262.0862.
3-Ethyl-6H-isochromeno[4,3-c]quinolin-6-one (2c). White solid
(44 mg, 80%): mp 201−203 °C; IR (KBr) 3504, 2990, 1763, 1459,
1377, 1242, 1056, 927, 847, 791, 631; 1H NMR (400 MHz, CDCl3) δ
9.46 (s, 1H), 8.41 (d, J = 8.0 Hz, 1H), 8.28−8.19 (m, 2H), 7.99 (d, J =
7.2 Hz, 1H), 7.87 (t, J = 7.6 Hz, 1H), 7.63−7.59 (m, 2H), 2.87 (q, J =
7.6 Hz, 2H), 1.36 (t, J = 7.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ
1
1376, 1242, 1054, 928, 849, 631; H NMR (600 MHz, TFA-140311) δ
9.00 (s, 1H), 8.92 (d, J = 9.0 Hz, 1H), 8.59 (s, 1H), 8.26 (d, J = 8.4
Hz, 1H), 7.78 (s, 3H), 7.70−7.63 (m, 2H); 13C NMR (151 MHz,
TFA-140311) δ 166.3, 145.5, 137.9, 131.0, 130.3, 128.9, 127.8, 125.7,
125.3, 122.4, 121.4, 117.1, 115.3, 113.4, 111.5. HRMS (ESI) m/z calcd
for C16H11F3NO [M + H]+, 290.0787, found 290.0787.
5,7-Dimethyl-3-phenylquinolin-4(1H)-one (1n). Light brown solid
(1.6 g, 87%): mp 211−214 °C; IR (KBr) 3739, 2990, 2359, 1764,
1462, 1377, 1242, 1055, 928, 850, 631; 1H NMR (400 MHz, DMSO)
δ 7.92 (s, 1H), 7.65 (d, J = 7.6 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.25
(t, J = 7.2 Hz, 1H), 7.17 (s, 1H), 6.84 (s, 1H), 6.45 (d, J = 7.6 Hz,
1H), 2.81 (s, 3H), 2.35 (s, 3H); 13C NMR (100 MHz, DMSO) δ
177.1, 141.2, 140.5, 139.6, 138.0, 136.5, 128.6, 127.6, 127.4, 126.1,
122.3, 121.1, 115.6, 23.5, 20.9. HRMS (ESI) m/z calcd for C17H16NO
[M + H]+, 250.1226, found 250.1226.
3-Phenylbenzo[h]quinolin-4(1H)-one (1o). Light pink solid (1.0 g,
70%): mp >300 °C; IR (KBr) 3738, 2990, 2361, 1763, 1463, 1376,
1242, 1054, 930, 849, 632; 1H NMR (600 MHz, TFA-140311) δ 9.02 (s,
1H), 8.99 (d, J = 7.8 Hz, 1H), 8.68 (d, J = 9.0 Hz, 1H), 8.55−8.39 (m,
2H), 8.34−8.18 (m, 2H), 7.97 (d, J = 6.6 Hz, 3H), 7.86 (d, J = 6.6 Hz,
E
dx.doi.org/10.1021/jo502013s | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
160.0, 152.6, 144.1, 135.4, 133.5, 132.1, 130.8, 129.2, 121.3, 120.9,
119.5, 29.1, 15.4. HRMS (ESI) m/z calcd for C18H14NO2 [M + H]+,
276.1019, found 276.1020.
3-(Trifluoromethyl)-6H-isochromeno[4,3-c]quinolin-6-one (2k).
White solid (58 mg, 92%): mp 217−219 °C; IR (KBr) 3744, 2990,
1
1763, 1462, 1376, 1242, 1056, 927, 839, 794, 630; H NMR (400
3-Isopropyl-6H-isochromeno[4,3-c]quinolin-6-one (2d). White
MHz, CDCl3) δ 9.61 (s, 1H), 8.75 (s, 1H), 8.44 (d, J = 8.0 Hz, 1H),
8.30 (d, J = 8.0 Hz, 1H), 8.21 (d, J = 8.4 Hz, 1H), 7.95−7.94 (m, 2H),
7.69 (t, J = 7.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 159.3, 153.3,
149.5, 147.6, 135.8, 132.7, 131.2, 130.6, 130.1, 129.8, 129.4, 126.7 (d, J
= 3 Hz), 123.72 (d, J = 271 Hz), 121.6, 121.1, 120.3−120.2 (q, J = 4.6,
J = 9.1 Hz), 117.8, 110.0. HRMS (ESI) m/z calcd for C17H8F3NO2 [M
+ H]+, 316.0585 found, 316.0587.
1-Methyl-6H-isochromeno[4,3-c]quinolin-6-one (2l). White solid
(35 mg, 68%): mp 279−281 °C; IR (KBr) 3858, 2988, 1763, 1453,
1376, 1242, 1056, 929, 848, 787, 631; 1H NMR (400 MHz, CDCl3) δ
9.58 (s, 1H), 8.47 (d, J = 7.6 Hz, 1H), 8.37 (d, J = 8.0 Hz, 1H), 8.32
(d, J = 7.6 Hz, 1H), 7.93 (t, J = 7.6 Hz, 1H), 7.68−7.65 (m, 2H), 7.57
(t, J = 7.4 Hz, 1H), 2.84 (s, 3H); 13C NMR (101 MHz, CDCl3) δ
160.2, 153.3, 147.9, 144.1, 137.3, 135.6, 133.6, 131.4, 1301.0, 129.4,
127.4, 121.4, 121.1, 119.9, 118.4, 108.8, 18.2. HRMS (ESI) m/z calcd
for C17H12NO2 [M + H]+, 262.0863, found 262.0863.
solid (52 mg, 90%): mp 183−185 °C; IR (KBr) 3507, 2989, 1763,
1
1459, 1376, 1242, 1056, 927, 837, 760, 630; H NMR (400 MHz,
CDCl3) δ 9.43 (s, 1H), 8.40 (d, J = 8.0 Hz, 1H), 8.25−8.23 (m, 2H),
8.01 (d, J = 8.6 Hz, 1H), 7.87 (t, J = 7.6 Hz, 1H), 7.68 (d, J = 8.6 Hz,
1H), 7.60 (t, J = 7.6 Hz, 1H), 3.15 (dt, J = 13.6, 7.0 Hz, 1H), 1.38 (d, J
= 6.8 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 160.1, 152.9, 151.2,
148.8, 147.6, 144.4, 135.5, 133.6, 130.9, 130.9, 129.3, 129.1, 121.4,
121.0, 118.1, 109.0, 34.5, 23.9. HRMS (ESI) m/z calcd for C19H16NO2
[M + H]+, 290.1176, found 290.1178.
3-Methoxy-6H-isochromeno[4,3-c]quinolin-6-one (2e). White
solid (48 mg, 87%): mp 260−262 °C; IR (KBr) 3446, 2988, 1763,
1
1456, 1376, 1242, 1057, 930, 848, 790, 631; H NMR (400 MHz,
CDCl3) δ 9.40 (s, 1H), 8.47 (d, J = 8.0 Hz, 1H), 8.31 (d, J = 8.0 Hz,
1H), 8.01 (d, J = 8.8 Hz, 1H), 7.92 (t, J = 7.6 Hz, 1H), 7.80−7.58 (m,
2H), 7.42 (dd, J = 9.2, 2.4 Hz, 1H), 4.02 (s, 3H); 13C NMR (101
MHz, CDCl3) δ 159.9, 158.5, 151.8, 144.6, 142.3, 135.2, 133.3, 130.6,
130.5, 129.1, 123.5, 121.2, 120.8, 119.1, 109.0, 99.0, 55.7. HRMS (ESI)
m/z calcd for C17H12NO3 [M + H]+, 278.0812, found 278.0811.
3-Bromo-6H-isochromeno[4,3-c]quinolin-6-one (2f). White solid
(52 mg, 81%): mp 263−265 °C; IR (KBr) 3506, 2990, 1764, 1459,
1376, 1242, 1056, 927, 850, 789, 631; 1H NMR (400 MHz, CDCl3) δ
9.58 (s, 1H), 8.67 (s, 1H), 8.49 (d, J = 7.8 Hz, 1H), 8.33 (d, J = 7.8
Hz, 1H), 8.02 (d, J = 8.6 Hz, 1H), 7.96 (t, J = 7.6 Hz, 1H), 7.88 (d, J =
8.6 Hz, 1H), 7.71 (t, J = 7.6 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ
171.1, 159.6, 152.0, 147.4, 145.7, 135.7, 134.5, 133.1, 131.2, 131.1,
129.9, 124.4, 122.0, 121.6, 121.2, 109.8. HRMS (ESI) m/z calcd for
C16H9BrNO2 [M + H]+, 325.9811, found 325.9814.
3-Chloro-6H-isochromeno[4,3-c]quinolin-6-one (2g). White solid
(50 mg, 90%): mp 2379−281 °C; IR (KBr) 3397, 2988, 1762, 1455,
1375, 1242, 1056, 954, 851, 754, 683; 1H NMR (400 MHz, CDCl3) δ
9.54 (s, 1H), 8.48−8.46 (m, 2H), 8.32 (d, J = 8.4 Hz, 1H), 8.07 (d, J =
8.4 Hz, 1H), 7.95 (t, J = 7.4 Hz, 1H), 7.74−7.68 (m, 2H); 13C NMR
(101 MHz, CDCl3) δ 159.6, 152.1, 147.1, 145.6, 135.7, 133.9, 133.1,
131.9, 131.1, 131.0, 129.9, 121.6, 121.2, 121.1. HRMS (ESI) m/z calcd
for C16H9ClNO2 [M + H]+, 282.0316, found 282.0312.
3-Fluoro-6H-isochromeno[4,3-c]quinolin-6-one (2h). White solid
(43 mg, 82%): mp 255−257 °C; IR (KBr) 3442, 2987, 1763, 1453,
1375, 1242, 1055, 929, 849, 795, 631; 1H NMR (400 MHz, CDCl3) δ
9.49 (s, 1H), 8.45 (d, J = 8.0 Hz, 1H), 8.31 (d, J = 8.0 Hz, 1H), 8.16−
8.09 (m, 1H), 8.05 (d, J = 8.8 Hz, 1H), 7.93 (t, J = 7.6 Hz, 1H), 7.68
(t, J = 7.6 Hz, 1H), 7.54 (t, J = 8.6 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 161.2 (d, J = 248 Hz), 159.7, 152.6, 145.9, 144.7, 135.7,
133.1, 132.0 (d, J = 9.2 Hz), 131.1, 129.8, 121.6, 121.2 (d, J = 2 Hz),
121.0, 109.6, 106.0 (d, J = 24 Hz). HRMS (ESI) m/z calcd for
C16H9FNO2 [M + H]+, 266.0612, found 266.0608.
2-(Trifluoromethyl)-6H-isochromeno[4,3-c]quinolin-6-one (2m).
White solid (57 mg, 91%): mp >300 °C; IR (KBr) 3743, 2988,
1
1763, 1458, 1376, 1242, 1056, 930, 848, 793, 631; H NMR (400
MHz, CDCl3) δ 9.65 (s, 1H), 8.61 (d, J = 8.8 Hz, 1H), 8.49 (d, J = 8.0
Hz, 1H), 8.43 (s, 1H), 8.35 (d, J = 8.0 Hz, 1H), 7.97 (t, J = 7.9 Hz,
1H), 7.86 (d, J = 8.4 Hz, 1H), 7.72 (t, J = 7.6 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 158.4, 151.7, 146.8, 145.9, 134.8, 131.8, 131. 5, 130.2,
129.1, 126.2−126.0 (q, J = 4.3 Hz, J = 8.6 Hz), 124.0, 122.6 (d, J = 271
Hz), 122.4, 120.7, 120.3, 119.3, 109.5. HRMS (ESI) m/z calcd for
C17H9F3NO2 [M + H]+, 316.0580, found 316.0577.
2,4-Dimethyl-6H-isochromeno[4,3-c]quinolin-6-one (2n). White
solid (47 mg, 85%): mp 270−272 °C; IR (KBr) 3743, 2989, 1764,
1
1457, 1376, 1242, 1056, 931, 850, 794, 631; H NMR (400 MHz,
CDCl3) δ 9.48 (s, 1H), 8.43 (d, J = 8.0 Hz, 1H), 8.30 (d, J = 8.0 Hz,
1H), 7.91 (t, J = 7.4 Hz, 1H), 7.74 (s, 1H), 7.64 (t, J = 7.6 Hz, 1H),
3.08 (s, 3H), 2.52 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 160.0,
155.0, 145.1, 141.0, 135.4, 135.3, 133.9, 132.6, 130.6, 129.9, 129.1,
127.0, 121.3, 120.3, 115.9, 108.8, 24.5, 21.6. HRMS (ESI) m/z calcd
for C18H14NO2 [M + H]+, 276.1019, found 276.1016.
8-Methyl-6H-isochromeno[4,3-c]quinolin-6-one (2q). White solid
(45 mg, 87%): mp 223−225 °C; IR (KBr) 3745, 2990, 1763, 1458,
1376, 1242, 1055, 929, 849, 787, 630; 1H NMR (400 MHz, CDCl3) δ
9.43 (s, 1H), 8.41−8.39 (m, 1H), 8.17 (s, 1H), 8.12−8.05 (m, 2H),
7.74 (t, J = 6.8 Hz, 1H), 7.66−7.61 (m, 2H), 2.48 (s, 3H); 13C NMR
(101 MHz, CDCl3) δ 160.1, 152.5, 148.5, 145.3, 140.0, 136.7, 130.7,
129.2, 127.6, 121.8, 121.3, 120.8, 118.5, 109.2, 21.4. HRMS (ESI) m/z
calcd for C17H12NO2 [M + H]+, 262.0863, found 262.0867.
8-Methoxy-6H-isochromeno[4,3-c]quinolin-6-one (2r). White
solid (44 mg, 80%): mp 260−262 °C; IR (KBr) 3746, 2988, 1764,
1
1457, 1376, 1242, 1056, 931, 850, 787, 630; H NMR (400 MHz,
3-Phenoxy-6H-isochromeno[4,3-c]quinolin-6-one (2i). White
CDCl3) δ 9.50 (s, 1H), 8.48 (d, J = 8.0 Hz, 1H), 8.23 (d, J = 8.8 Hz,
1H), 8.13 (d, J = 8.4 Hz, 1H), 7.84 (s, 1H), 7.78 (t, J = 7.2 Hz, 1H),
7.67 (t, J = 7.4 Hz, 1H), 7.48 (d, J = 8.4 Hz, 1H), 3.97 (s, 3H); 13C
NMR (101 MHz, CDCl3) δ 160.5, 160.2, 151.8, 145.2, 138.2, 130.5,
129.3, 127.6, 126.7, 124.9, 123.1, 122.5, 121.7, 111.8, 109.4, 100.0,
55.9. HRMS (ESI) m/z calcd for C17H12NO3 [M + H]+, 278.0812,
found 278.0809.
solid (57 mg, 85%): mp 235−237 °C; IR (KBr) 3447, 2990, 1763,
1
1461, 1376, 1242, 1056, 928, 850, 795, 630; H NMR (400 MHz,
CDCl3) δ 9.44 (s, 1H), 8.43 (d, J = 8.2 Hz, 1H), 8.30 (d, J = 8.2 Hz,
1H), 8.10 (d, J = 9.2 Hz, 1H), 7.91 (t, J = 8.0 Hz, 1H), 7.86 (d, J = 2.4
Hz, 1H), 7.65 (t, J = 7.6 Hz, 1H), 7.55 (dd, J = 9.0, 2.6 Hz, 1H), 7.42
(t, J = 7.8 Hz, 2H), 7.21 (t, J = 7.4 Hz, 1H), 7.13 (d, J = 8.0 Hz, 2H);
13C NMR (101 MHz, CDCl3) δ 159.9, 156.9, 156.2, 152.3, 145.6,
143.8, 135.5, 133.4, 131.4, 131.0, 130.2, 129.5, 124.5, 124.5, 121.5,
121.2, 119.6, 119.5, 109.4, 107.4. HRMS (ESI) m/z calcd for
C22H14NO3 [M + H]+, 340.0968, found 340.0974.
6H-Benzo[5,6]isochromeno[4,3-c]quinolin-6-one (2s). Light yel-
low solid (56 mg, 95%): mp 205−207 °C; IR (KBr) 3747, 2955, 1763,
1
1453, 1375, 1242, 1057, 958, 851, 767, 628; H NMR (400 MHz,
CDCl3) δ 9.95 (s, 1H), 8.8−8.84 (m, 1H), 8.53 (d, J = 8.4 Hz, 1H),
8.32 (d, J = 8.4 Hz, 1H), 8.13 (d, J = 8.4 Hz, 1H), 8.01−7.98 (m, 2H),
7.83 (t, J = 7.6 Hz, 1H), 7.76−7.73 (m, 2H), 7.69 (t, J = 7.6 Hz, 1H);
13C NMR (101 MHz, CDCl3) δ 160.4, 153.8, 148.5, 147.7, 137.2,
133.1, 131.4, 130.3, 129.6, 129.4, 128.8, 128.1, 127.7, 127.6, 127.2,
124.4, 122.2, 119.8, 118.5, 110.4. HRMS (ESI) m/z calcd for
C20H12NO2 [M + H]+, 298.0863, found 298.0859.
8-Fluoro-6H-isochromeno[4,3-c]quinolin-6-one (2t). White solid
(47 mg, 89%): mp 265−267 °C; IR (KBr) 3736, 2990, 1763, 1458,
1376, 1242, 1056, 931, 849, 790, 630; 1H NMR (400 MHz, CDCl3) δ
9.53 (s, 1H), 8.49 (d, J = 8.0 Hz, 1H), 8.36−8.32 (m, 1H), 8.17 (d, J =
3-(Trifluoromethoxy)-6H-isochromeno[4,3-c]quinolin-6-one (2j).
White solid (59 mg, 90%): mp >300 °C; IR (KBr) 3504, 2989,
1
1761, 1461, 1375, 1242, 1055, 931, 843, 786, 632; H NMR (400
MHz, CDCl3) δ 9.52 (s, 1H), 8.43 (d, J = 7.6 Hz, 1H), 8.28 (d, J = 8.0
Hz, 1H), 8.24 (s, 1H), 8.14 (d, J = 9.2 Hz, 1H), 7.92 (t, J = 7.6 Hz,
1H), 7.67 (t, J = 7.6 Hz, 1H), 7.62 (d, J = 8.8 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 159.4, 152.7, 147.9, 146.9, 145.8, 135.7, 132.9, 131.7,
131.1, 129.9, 124.9, 121.8, 121.6, 121.2, 119.2, 119.0, 112.6, 109.7.
HRMS (ESI) m/z calcd for C17H9F3NO3 [M + H]+, 332.0529, found
332.0531.
F
dx.doi.org/10.1021/jo502013s | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
8.4 Hz, 1H), 8.12 (dd, J = 8.4, 2.4 Hz, 1H), 7.83 (t, J = 7.4 Hz, 1H),
7.72−7.63 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 162.8 (d, J = 233
Hz), 161.5, 159.0, 152.8, 148.4, 144.9, 131.3, 129.9 (d, J = 3 Hz),
129.1, 128.0, 124.1 (d, J = 7 Hz), 123.8, 123.1, 123.0, 121.9, 116.8 (d, J
= 23 Hz), 108.6. HRMS (ESI) m/z calcd for C16H9FNO2 [M + H]+,
266.0612, found 266.0609.
Benzofuro[3,2-c]quinoline (3a). Light yellow solid (37 mg, 85%):
mp 124−126 °C; IR (KBr) 3424, 2989, 2362, 1455, 1376, 1242, 1056,
931, 851, 759, 630; 1H NMR (400 MHz, CDCl3) δ 9.48 (s, 1H), 8.41
(d, J = 8.0 Hz, 1H), 8.27 (d, J = 8.4z, 1H), 8.09 (d, J = 7.6 Hz, 1H),
7.80−7.74 (m, 2H), 7.69 (t, J = 7.6 Hz, 1H), 7.54 (t, J = 7.6 Hz, 1H),
7.47 (t, J = 7.6 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 157.5, 156.0,
147.4, 144.4, 129.8, 129.3, 127.2, 127.0, 124.1, 122.7, 120.8, 120.6,
117.2, 116.3, 112.1. HRMS (ESI) m/z calcd for C15H10NO [M + H]+,
220.0757, found 220.0758.
9-Methoxybenzofuro[3,2-c]quinoline (3h). Light yellow solid (38
mg, 77%): mp 139−141 °C; IR (KBr) 3747, 2987, 2361, 1457, 1374,
1
1242, 1056, 947, 847, 765, 633; H NMR (400 MHz, CDCl3) δ 9.39
(s, 1H), 8.33 (d, J = 8.0 Hz, 1H), 8.24 (d, J = 8.4 Hz, 1H), 7.90 (d, J =
8.8 Hz, 1H), 7.73 (t, J = 7.4 Hz, 1H), 7.65 (t, J = 7.4 Hz, 1H), 7.23 (s,
1H), 7.04 (d, J = 8.4 Hz, 1H), 3.92 (s, 3H); 13C NMR (101 MHz,
CDCl3) δ 160.3, 157.6, 157.6, 146.9, 144.0, 130.0, 129.1, 127.2,
121.11, 120.8, 117.4, 116.8, 115.9, 112.8, 97.2, 56.1. HRMS (ESI) m/z
calcd for C16H12NO2 [M + H]+, 250.0863, found 250.0867.
9-Fluorobenzofuro[3,2-c]quinoline (3i). Light yellow solid (39 mg,
83%): mp 148−150 °C; IR (KBr) 3742, 2988, 2360, 1457, 1375, 1242,
1056, 955, 845, 765, 629; 1H NMR (400 MHz, CDCl3) δ 9.45 (s, 1H),
8.36 (d, J = 8.0 Hz, 1H), 8.29 (d, J = 8.4 Hz, 1H), 8.03−7.99 (m, 1H),
7.80 (t, J = 7.4 Hz, 1H), 7.71 (t, J = 7.4 Hz, 1H), 7.47 (d, J = 8.8 Hz,
1H), 7.23 (t, J = 8.8 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 162.3
(d, J = 245 Hz), 158.14 (d, J = 2.4 Hz), 156.18 (d, J = 14 Hz), 146.93,
143.79, 129.69, 129.43, 127.26, 121.15 (d, J = 10 Hz), 120.61, 118.98,
118.96, 116.97, 115.83, 112.32 (d, J = 24 Hz), 100.28 (d, J = 27 Hz).
HRMS (ESI) m/z calcd for C15H9FNO [M + H]+, 238.0663, found
238.0661.
1,3-Dimethylbenzofuro[3,2-c]quinoline (3j). Light brown solid (40
mg, 81%): mp 158−161 °C; IR (KBr) 3504, 2989, 2361, 1457, 1376,
1242, 1055, 930, 8503, 752, 631; 1H NMR (400 MHz, CDCl3) δ 9.42
(s, 1H), 8.07 (d, J = 7.6 Hz, 1H), 7.91 (s, 1H), 7.73 (d, J = 8.0 Hz,
1H), 7.52 (t, J = 7.6 Hz, 1H), 7.46 (t, J = 7.4 Hz, 1H), 7.29 (s, 1H),
3.08 (s, 3H), 2.56 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 158.7,
155.7, 148.4, 143.7, 139.4, 133.2, 130.6, 126.9, 126.4, 124.0, 122.2,
120.3, 116.1, 115.1, 112.0, 22.2, 21.7. HRMS (ESI) m/z calcd for
C17H14NO [M + H]+, 248.1070, found 248.1070.
2-Methoxybenzofuro[3,2-c]quinoline (3b). Light yellow solid (43
mg, 87%): mp 135−137 °C; IR (KBr) 3722, 2989, 2362, 1464, 1376,
1
1242, 1056, 930, 843, 751, 630; H NMR (400 MHz, CDCl3) δ 9.33
(s, 1H), 8.15 (d, J = 8.6 Hz, 1H), 8.07 (d, J = 7.6 Hz, 1H), 7.73 (d, J =
8.6 Hz, 1H), 7.62−7.61 (m, 1H), 7.53 (t, J = 7.8 Hz, 1H), 7.47 (d, J =
7.6 Hz, 1H), 7.40 (dd, J = 9.2, 2.8 Hz, 1H), 4.03 (s, 3H); 13C NMR
(101 MHz, CDCl3) δ 158.0, 156.6, 155.6, 143.0, 141.3, 131.0, 126.9,
123.7, 122.5, 121.5, 120.4, 117.6, 116.2, 111.7, 98.3, 55.4. HRMS (ESI)
m/z calcd for C16H12NO2 [M + H]+, 250.0863, found 250.0867.
2-(Trifluoromethoxy)benzofuro[3,2-c]quinoline (3c). Light brown
solid (48 mg, 89%): mp 142−144 °C; IR (KBr) 3747, 2988, 2361,
1
1459, 1374, 1244, 1057, 930, 842, 752, 631; H NMR (400 MHz,
CDCl3) δ 9.46 (s, 1H), 8.28 (d, J = 8.8 Hz, 1H), 8.18 (s, 1H), 8.07 (t,
J = 6.8 Hz, 1H), 7.74 (d, J = 8.0 Hz, 1H), 7.60−7.54 (m, 2H), 7.50 (t,
J = 7.4 Hz); 13C NMR (100 MHz, CDCl3) δ 157.0, 156.1, 147.4,
145.4, 144.7, 132.2, 127.8, 124.3, 123.1, 122.3, 121.9, 120.8, 117.0,
112.2, 111.2. HRMS (ESI) m/z calcd for C16H9F3NO2 [M + H]+,
304.0580, found 304.0582.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H and 13C NMR spectra of all synthesized compounds. This
material is available free of charge via the Internet at http://
pubs.acs.org.
2-Phenoxybenzofuro[3,2-c]quinoline (3d). Light brown solid (49
mg, 79%): mp 159−161 °C; IR (KBr) 3743, 2989, 2361, 1459, 1376,
1
1242, 1056, 926, 849, 752, 630; H NMR (400 MHz, CDCl3) δ 9.37
(s, 1H), 8.24 (d, J = 9.2 Hz, 1H), 8.05 (d, J = 7.6 Hz, 1H), 7.74 (s,
1H), 7.67 (d, J = 8.0 Hz, 1H), 7.52 (m, 2H), 7.44 (t, J = 7.6 Hz, 3H),
7.22 (t, J = 7.4 Hz, 1H), 7.17 (d, J = 8.0 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ 156.8, 156.3, 156.2, 155.8, 143.9, 142.6, 131.7, 130.0,
127.2, 124.1, 123.9, 122.5, 122.5, 120.6, 119.7, 117.8, 116.5, 112.0,
106.1. HRMS (ESI) m/z calcd for C21H14NO2 [M + H]+, 312.1019,
found 312.1026.
AUTHOR INFORMATION
Corresponding Author
*Fax: (+86) 20-8711-2906. E-mail: jianghf@scut.edu.cn.
Notes
■
The authors declare no competing financial interest.
2-Fluorobenzofuro[3,2-c]quinoline (3e). Light brown solid (38
ACKNOWLEDGMENTS
mg, 80%): mp 148−149 °C; IR (KBr) 3745, 2988, 2361, 1461, 1374,
■
1
1242, 1056, 955, 844, 750, 631; H NMR (400 MHz, CDCl3) δ 9.45
We are grateful to the National Basic Research Program of
China (973 Program) (2011CB808600), the National Natural
Science Foundation of China (21172076 and 21202046), the
G u a n g d o n g N a t u r a l S c i e n c e F o u n d a t i o n
(10351064101000000), and the Fundamental Research Funds
for the Central Universities (2014ZP0004 and 2014ZZ0046).
(s, 1H), 8.30−8.26 (m, 1H), 8.09 (d, J = 7.6 Hz, 1H), 7.99 (d, J = 8.4
Hz, 1H), 7.76 (d, J = 8.4 Hz, 1H), 7.60−7.47 (m, 3H); 13C NMR (100
MHz, CDCl3) δ 162.8 (d, J = 240 Hz), 157.1 (d, J = 10 Hz), 156.0,
143.5, 132.5 (d, J = 9.4 Hz), 127.7, 124.2, 122.4, 120.8, 119.3 (d, J = 20
Hz), 112.2, 104.7 (d, J = 20 Hz). HRMS (ESI) m/z calcd for
C15H9FNO [M + H]+, 238.0663, found 238.0662.
2-Chlorobenzofuro[3,2-c]quinoline (3f). Light brown solid (30 mg,
60%): mp 139−141 °C; IR (KBr) 3419, 2988, 2361, 1457, 1375, 1242,
1056, 954, 848, 754, 632; 1H NMR (400 MHz, CDCl3) δ 9.45 (s, 1H),
8.36 (s, 1H), 8.18 (d, J = 8.8 Hz, 1H), 8.08 (d, J = 7.6 Hz, 1H), 7.74
(d, J = 8.0 Hz, 1H), 7.69 (d, J = 8.8 Hz, 1H), 7.56 (t, J = 7.6 Hz, 1H),
7.48 (t, J = 7.4 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 156.1, 155.7,
145.3, 144.2, 132.7, 131.2, 129.8, 127.4, 124.0, 122.1, 120.5, 119.6,
117.5, 116.6, 111.9. HRMS (ESI) m/z calcd for C15H9ClNO [M +
H]+, 254.0367, found 254.0364.
REFERENCES
■
(1) (a) Liu, G.-S.; Jia, L. J. Am. Chem. Soc. 2004, 126, 14716.
(b) Barnard, C. F. J. Organometallics. 2008, 27, 5402. (c) Liu, Q.;
Zhang, H.; Lei, A. Angew. Chem., Int. Ed. 2011, 50, 10788. (d) Guan,
Z.-H.; Chen, M.; Ren, Z.-H. J. Am. Chem. Soc. 2012, 134, 17490.
(e) Wu, X.-F.; Neumann, H.; Beller, M. Chem. Rev. 2013, 113, 1.
(2) (a) Schoenberg, A.; Bartoletti, I.; Heck, R. F. J. Org. Chem. 1974,
39, 3318. (b) Schoenberg, A.; Heck, R. F. J. Am. Chem. Soc. 1974, 96,
7761. (c) Schoenberg, A.; Heck, R. F. J. Org. Chem. 1974, 39, 3327.
9-Methylbenzofuro[3,2-c]quinoline (3g). Light yellow solid (38
(3) (a) Brennfuhrer, A.; Neumann, H.; Beller, M. Angew. Chem., Int.
mg, 81%): mp 148−150 °C; IR (KBr) 3746, 2953, 2361, 1457, 1375,
̈
1
Ed. 2009, 48, 4114. (b) Grigg, R.; Mutton, S. P. Tetrahedron 2010, 66,
5515. (c) Wu, X.-F.; Neumann, H.; Beller, M. Chem. Soc. Rev. 2011,
40, 4986.
1242, 1057, 944, 857, 761, 631; H NMR (400 MHz, CDCl3) δ 9.42
(s, 1H), 8.36 (d, J = 8.4 Hz, 1H), 8.24 (d, J = 8.8 Hz, 1H), 7.91 (d, J =
8.0 Hz, 1H), 7.74 (t, J = 7.8 Hz, 1H), 7.65 (t, J = 7.4 Hz, 1H), 7.51 (s,
1H), 7.25 (s, 1H), 2.55 (s, 3H); 13C NMR (101 MHz, CDCl3) δ
157.3, 156.4, 147.0, 144.1, 137.9, 129.7, 129.0, 126.9, 125.3, 120.7,
120.0, 120.0, 117.2, 116.4, 112.3, 22.0. HRMS (ESI) m/z calcd for
C16H12NO [M + H]+, 234.0913, found 234.0917.
(4) (a) Shilov, A. E.; Shul’pin, G. B. Chem. Rev. 1997, 97, 2879.
(b) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147.
(c) Colby, D. A.; Bergman, R. G.; Ellman, J. A. Chem. Rev. 2010, 110,
624. (d) Sun, C.-L.; Li, B.-J.; Shi, Z.-J. Chem. Rev. 2011, 111, 1293.
G
dx.doi.org/10.1021/jo502013s | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
(e) Cho, S. H.; Kim, J. Y.; Kwak, J.; Chang, S. Chem. Soc. Rev. 2011,
40, 5068. (f) Engle, K. M.; Mei, T.-S.; Wasa, M.; Yu, J.-Q. Acc. Chem.
Res. 2012, 45, 788.
(5) For selected examples on transition-metal-catalyzed C−H bond
carbonylation, see: (a) Asaumi, T.; Matsuo, T.; Fukuyama, T.; Ie, Y.;
Kakiuchi, F.; Chatani, N. J. Org. Chem. 2004, 69, 4433. (b) Orito, K.;
Horibata, A.; Nakamura, T.; Ushito, H.; Nagasaki, H.; Yuguchi, M.;
Yamashita, S.; Tokuda, M. J. Am. Chem. Soc. 2004, 126, 14342.
(c) Giri, R.; Yu, J.-Q. J. Am. Chem. Soc. 2008, 130, 14082. (d) Houlden,
(13) (a) Cheung, C. W.; Buchwald, S. L. J. Org. Chem. 2012, 77,
7526. (b) Tsang, W. C. P.; Munday, R. H.; Brasche, G.; Zheng, N.;
Buchwald, S. L. J. Org. Chem. 2008, 73, 7603.
(14) (a) Cheng, X.-F.; Li, Y.; Su, Y.-M.; Yin, F.; Wang, J.-Y.; Sheng, J.;
Vora, H. U.; Wang, X.-S.; Yu, J.-Q. J. Am. Chem. Soc. 2013, 135, 1236.
(b) Mei, T.-S.; Leow, D.; Xiao, H.; Laforteza, B. N.; Yu, J.-Q. Org. Lett.
2013, 15, 3058.
(15) Xiao, B.; Gong, T.-J.; Liu, Z.-J.; Liu, J.-H.; Luo, D.-F.; Xu, J.; Liu,
L. J. Am. Chem. Soc. 2011, 133, 9250.
C. E.; Hutchby, M.; Bailey, C. D.; Ford, J. G.; Tyler, S. N. G.; Gagne,
́
M. R.; Lloyd-Jones, G. C.; BookerMilburn, K. I. Angew. Chem., Int. Ed.
2009, 48, 1830. (e) Inoue, S.; Shiota, H.; Fukumoto, Y.; Chatani, N. J.
Am. Chem. Soc. 2009, 131, 6898. (f) Guan, Z.-H.; Ren, Z.-H.; Spinella,
S. M.; Yu, S.; Liang, Y.-M.; Zhang, X. J. Am. Chem. Soc. 2009, 131, 729.
(g) Giri, R.; Lam, J. K.; Yu, J.-Q. J. Am. Chem. Soc. 2010, 132, 686.
(h) Haffemayer, B.; Gulias, M.; Gaunt, M. J. Chem. Sci. 2011, 2, 312.
(i) Lu, Y.; Leow, D.; Wang, X.; Engle, K. M.; Yu, J.-Q. Chem. Sci. 2011,
2, 967. (j) Ma, B.; Wang, Y.; Peng, J.; Zhu, Q. J. Org. Chem. 2011, 76,
6362. (k) Chen, H.; Cai, C.; Liu, X.; Li, X.; Jiang, H. Chem. Commun.
2011, 47, 12224. (l) Xing, Q.; Shi, L.; Lang, R.; Xia, C.; Li, F. Chem.
Commun. 2012, 48, 11023. (m) Zhang, H.; Shi, R.; Gan, P.; Liu, C.;
Ding, A.; Wang, Q.; Lei, A. Angew. Chem., Int. Ed. 2012, 51, 5204.
(n) Xie, P.; Xie, Y.; Qian, B.; Zhou, H.; Xia, C.; Huang, H. J. Am.
Chem. Soc. 2012, 134, 9902. (o) Luo, S.; Luo, F.-X.; Zhang, X.-S.; Shi,
Z.-J. Angew. Chem., Int. Ed. 2013, 52, 10598. (p) Liang, D.; Hu, Z.;
Peng, J.; Huang, J.; Zhu, Q. Chem. Commun. 2013, 49, 173. (q) Li, J.;
Yang, S.; Wu, W.; Jiang, H. Chem. Commun. 2014, 50, 1381. (r) Xu, Y.;
Zhao, J.; Chen, H.; Wu, W.; Jiang, H. Chem. Commun. 2014, 50, 2488.
(6) (a) Chatani, N.; Ie, Y.; Kakiuchi, F.; Murai, S. J. Org. Chem. 1997,
62, 2604. (b) Liu, B.; Jian, H.-Z.; Shi, B.-F. Org. Biomol. Chem. 2014,
12, 2538.
(7) Li, H.; Cai, G.-X.; Shi, Z.-J. Dalton Trans. 2010, 39, 10442.
(8) (a) Ferguson, J.; Zeng, F.; Alwis, N.; Alper, H. Org. Lett. 2012, 14,
5602. (b) Inamoto, K.; Kadokawa, J.; Kondo, Y. Org. Lett. 2013, 15,
3962. (c) Lee, T.-H.; Jayakumar, J.; Cheng, C.-H.; Chuang, S.-H.
Chem. Commun. 2013, 49, 11797. (d) Chen, M.; Ren, Z.-H.; Wang, Y.-
Y.; Guan, Z.-H. Angew. Chem., Int. Ed. 2013, 52, 14196. (e) Yoo, E. J.;
́
Wasa, M.; Yu, J.-Q. J. Am. Chem. Soc. 2010, 132, 17378. (f) Lo pez, B.;
Rodriguez, A.; Santos, D.; Albert, J.; Ariza, X.; Garcia, J.; Granell, J.
Chem. Commun. 2011, 47, 1054. (g) Hasegawa, N.; Charra, V.; Inoue,
S.; Fukumoto, Y.; Chatani, N. J. Am. Chem. Soc. 2011, 133, 8070.
(h) Wrigglesworth, J. W.; Cox, B.; Lloyd-Jones, G. C.; Booker-
Milburn, K. I. Org. Lett. 2011, 13, 5326. (i) Ferguson, J.; Zeng, F.;
Alwis, N.; Alper, H. Org. Lett. 2013, 15, 1998. (j) Rajeshkumar, V.;
Lee, T.-H.; Chuang, S.-C. Org. Lett. 2013, 15, 1468. (k) Liang, Z.;
Zhang, J.; Liu, Z.; Wang, K.; Zhang, Y. Tetrahedron. 2013, 69, 6519.
(l) Li, W.; Liu, C.; Zhang, H.; Ye, K.; Zhang, G.; Zhang, W.; Duan, Z.;
You, S.; Lei, A. Angew. Chem., Int. Ed. 2014, 53, 2443.
(9) Fetzer, J. C. Polycyclic Aromat. Compd. 2007, 27, 143−162.
(10) (a) Samorí, P.; Fechtenkotter, A.; Jackel, F.; Bohme, T.; Mullen,
̈
̈
̈
̈
K.; Rabe, J. P. J. Am. Chem. Soc. 2001, 123, 11462−11467. (b) Samorí,
P.; Severin, N.; Simpson, C. D.; Mullen, K.; Rabe, J. P. J. Am. Chem.
̈
Soc. 2002, 124, 9454−9457. (c) Berresheim, A. J.; Mullen, K. Chem.
̈
Rev. 1999, 99, 1747−1786. (d) Watson, M. D.; Fechtenkotter, A.;
Mullen, K. Chem. Rev. 2001, 101, 1267−1300. (e) Bendikov, M.;
Wudl, F.; Perepichka, D. F. Chem. Rev. 2004, 104, 4891−4945.
(f) Anthony, J. E. Chem. Rev. 2006, 106, 5028−5048. (g) Sergeyev, S.;
Pisula, W.; Geerts, Y. H. Chem. Soc. Rev. 2007, 36, 1902−1929.
het, J. M. J. Chem. Rev. 2007, 107, 1066−1096.
(i) Weil, T.; Vosch, T.; Hofkens, J.; Peneva, K.; Mullen, K. Angew.
Chem., Int. Ed. 2010, 49, 9068−9093.
̈
̈
(h) Murphy, A. R.; Frec
́
̈
(11) (a) Larock, R. C. Top. Organomet. Chem. 2005, 14, 147.
(b) Zeni, G.; Larock, R. C. Chem. Rev. 2006, 106, 4644.
(12) (a) Mallory, F. B.; Wood, C. S.; Gordon, J. T. J. Am. Chem. Soc.
1964, 86, 3094. (b) Iuliano, A.; Piccioli, P.; Fabbri, D. Org. Lett. 2004,
6, 3711. (c) Bonifacio, M. C.; Robertson, C. R.; Jung, J.-Y.; King, B. T.
J. Org. Chem. 2005, 70, 8522. (d) Zhang, Z.; Sangaiah, R.; Gold, A.;
Ball, L. M. Org. Biomol. Chem. 2011, 9, 5431.
H
dx.doi.org/10.1021/jo502013s | J. Org. Chem. XXXX, XXX, XXX−XXX