Efficient Approach to Construct Unsymmetrical Biaryls through Oxidative Coupling Reactions of Aromatic Primary Alcohols and Arylboronic Acids with a Rhodium Catalyst

Article abstract of DOI:10.1021/acs.organomet.6b00238

Unsymmetrical biaryls were synthesized by oxidative coupling reactions between aromatic primary alcohols and arylboronic acids through the C-C bond cleavage of the primary alcohols chelated with a rhodium catalyst. The desired unsymmetrical biaryl products were obtained in good to excellent yields under the optimized reaction conditions. A wide variety of functionalities are compatible with the reaction under the optimized conditions. This new coupling strategy provides a favorable method to construct valuable biaryl compounds from aromatic primary alcohols which are cheap, environmentally friendly, and easily accessible substrates.

Full text of DOI:10.1021/acs.organomet.6b00238

Article
pubs.acs.org/Organometallics
Efficient Approach To Construct Unsymmetrical Biaryls through
Oxidative Coupling Reactions of Aromatic Primary Alcohols and
Arylboronic Acids with a Rhodium Catalyst
Xiaobo Yu,†,‡,§ Jingjing Wang,∥ Weijie Guo,†,‡ Yun Tian,*,† and Jianhui Wang*,†,‡
†Department of Chemistry, College of Science, Tianjin University, Tianjin 300072, People’s Republic of China
‡Collaborative Innovation center of Chemical Science and Engineering (Tianjin), Tianjin 300072, People’s Republic of China
§College of Materials Science and Engineering, Jilin Institute of Chemical Technology, Jilin City 132022, People’s Republic of China
∥College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, Henan 476000, People’s Republic of China
S
* Supporting Information
ABSTRACT: Unsymmetrical biaryls were synthesized by oxidative
coupling reactions between aromatic primary alcohols and
arylboronic acids through the C−C bond cleavage of the primary
alcohols chelated with a rhodium catalyst. The desired unsym-
metrical biaryl products were obtained in good to excellent yields
under the optimized reaction conditions. A wide variety of
functionalities are compatible with the reaction under the optimized
conditions. This new coupling strategy provides a favorable method
to construct valuable biaryl compounds from aromatic primary
alcohols which are cheap, environmentally friendly, and easily accessible substrates.
However, C−C bonds are not easily activated, because they
are kinetically inert and thermodynamically stable. Therefore,
C−C bonds often have to be activated by forming stable
metallacyclic intermediates via ring-opening reactions of
strained three- or four-membered rings.9m−o,10 Directing a
metal to a particular C−C bond using a chelating group is a
method to cleave unstrained carbon−carbon bonds.11,12
Recently, catalytic selective C−C bond cleavage has been
used to form stable organometallic intermediates by using
sterically congested tertiary alcohols. For example, Miura and
co-workers successfully coupled tertiary alcohols with aryl
halides11a−c and with internal alkynes12b using C−C activation
strategies. Yorimitsu and Oshima’s group have explored C−C
bond cleavage using tertiary alcohols with aryl halides,11d−g
aldehydes,12c,d and Boc-protected allyl alcohols.12e
In comparison, secondary alcohols for C−C bond cleavage
generally are not thermodynamically favorable. However,
secondary alcohols have been employed in C−C bond
activation reactions.9l,13,14 Chiba et al. reported the Pd(II)-
catalyzed ring expansion of cyclic 2-azido alcohols which
involved unprecedented C−C bond cleavages and C−N bond
formations.13 Wang and Kang demonstrated allylic esterifica-
tion of secondary homoallyl alcohols with acids using
palladium-catalyzed selective C−C bond cleavage.9l Shi and
co-workers reported several novel examples of coupling
reactions which used rhodium-catalyzed C−C bond cleavage
of secondary alcohols.14
INTRODUCTION
■
Biaryl compounds have always drawn the attention of synthetic
chemists due to their wide range of pharmaceutical, material,
and biological applications.1 Transition-metal-catalyzed cross-
coupling reactions are powerful and reliable methods for C−C
bond formation, especially for the synthesis of unsymmetrical
biaryls.2,3 The Suzuki−Miyaura reaction is one of the more
widely used cross-coupling reactions.3m,4 However, traditional
coupling reactions have some drawbacks associated with the
use of organohalides and organometallic reagents.
In the last two decades, scientists have been developing more
atom economical and greener coupling reactions. For example,
direct arylation reactions using C−H bond activation by
transition-metal catalysts have been developed, and impressive
progress has been made in this area.5,6 The direct arylation
method does not require prefunctionalization of the reactants,
which offers an attractive alternative to conventional cross-
coupling reactions.
In comparison to synthetic methods based on C−H bond
activation, the synthesis of complex molecules via C−C bond
activation using nontraditional retrosynthetic disconnections
can have higher efficiencies.7−9 Furthermore, coupling reactions
based on C−C bond activation often use commercially
available, cheap, nontoxic, and environmentally friendly
substrates, such as aldehydes, ketones, esters, and alcohols as
the coupling counterparts. This has greatly enriched the
diversity of coupling reactions and has provided chemists
with alternative coupling methods for the construction of biaryl
compounds.
Received: March 23, 2016
© XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.6b00238
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Directing a rhodium metal close to a particular C−C bond by
chelation with a N group to generate a thermodynamically
stable five-membered rhodacyclic intermediate is the key to
successful C−C bond cleavage in secondary alcohols (Scheme
1a). However, when this method was applied to primary
Table 1. Optimization of Reaction Conditions for the Cross-
Coupling Reaction of (Benzo[h]quinolin-10-yl)methanol (a
a
Primary Alcohol) and Phenylboronic Acid
Scheme 1. Rhodium-Catalyzed Coupling Reaction of
Alcohols through C−C Bond Cleavage: (a) Secondary
Alcohols; (b) Primary Alcohols
time
(h)
yield
e
b
entry
catalyst
additive
solvent
(%)
1
Pd(OAc)2
xylene
xylene
xylene
xylene
xylene
xylene
xylene
xylene
xylene
xylene
xylene
xylene
xylene
tolune
NMP
15
15
15
15
15
15
15
15
15
15
15
20
12
15
15
15
15
15
15
15
15
15
15
15
0
2
Pd(dba)2
0
3
Pd(PPh3)4
lrCl3·3H2O
lrCp*Cl
(PPh3)3RhCl
(PPh3)3RhCl
(PPh3)3RhCl
(PPh3)3RhCl
(PPh3)3RhCl
0
4
0
5
0
6
45
90
82
67
50
0
7
CuCl
Cul
8
9
CuCl2
10
11
12
13
14
15
Cu(OAc)2
CuCl
(PPh3)3RhCl
(PPh3)3RhCl
(PPh3)3RhCl
(PPh3)3RhCl
(PPh3)3RhCl
(PPh3)3RhCl
Rh2(COD)2Cl2
Rh2(COD)2Cl2
RhCl3·3H2O
RhCp*Cl
CuCl
89
85
78
0
CuCl
CuCl
alcohols, the desired coupling products were only obtained in
very low yields.14d Thus, the efficient cleavage of a C−C bond
in a primary alcohol remains a challenge.
CuCl
c
16
CuCl
DCE
0
c
17
CuCl
CH3CN
xylene
xylene
xylene
xylene
xylene
xylene
xylene
0
Our group has reported efficient rhodium-catalyzed coupling
reactions for quinoline and arylboronic acid C−C9e or C−O15
bond cleavages. Decarbonylation coupling reactions of ethyl
benzo[h]quinoline-10-carboxylate and arylboronic acids
through chelate-assisted sp2 C−COOEt bond activation have
been achieved.9e The DFT calculations of this bond activation
process indicated that a lower energy and more stable
rhodacyclic intermediate was generated by the rhodium-
catalyzed C−C bond cleavage of the benzoquinoline reactants
with the assistance of a N-containing directing group. From this
result, we envisioned that (benzo[h]quinolin-10-yl)methanol
could be applied to study rhodium-catalyzed C−C bond
activation, since the generation of a more stable rhodacyclic
intermediate might facilitate C−C bond cleavage by avoiding
the subtraction of the primary alcohol α-H. Thus, herein the
reaction of (benzo[h]quinolin-10-yl)methanols, primary alco-
hols, with arylboronic acids in the presence of metal catalysts
was investigated for C−C bond activation (Scheme 1b).
18
23
35
trace
trace
trace
0
d
19
PPh3
20
21
22
23
24
[Ru(COD)Cl2]n
RuCl3·nH2O
NiCl2(dppe)
0
a
Reaction conditions unless specified otherwise: 1aa (0.1 mmol), 2aa
(0.2 mmol), catalyst (7 mol %) in 1 mL of xylene in air at 130 °C.
b
c
d
Additive (0.1 mmol). Reaction temperature: 90 °C. Additive (0.01
e
mmol). Yields were determined by 1H NMR using trimethylphe-
nylsilane as the internal standard.
CuCl play an important role in achieving this transformation.
Increasing the reaction time to 20 h did not improve the
reaction yield when (PPh3)3RhCl and CuCl were both used at
130 °C (entry 12). However, when the reaction time was
shortened to 12 h, the yield of 3aa decreased to 85% (entry
13). Several other solvents, such as tolune, NMP, DCE, and
CH3CN, were tested at different temperatures with
(PPh3)3RhCl as the catalyst and CuCl as the additive (entires
14−17). None of these solvents gave results better than those
with xylene.
When the catalyst (PPh3)3RhCl was replaced by
Rh2(COD)2Cl2, the cross-coupling reaction proceeded slowly
(15 h) to give the desired 3aa in low yield (23%; Table 1, entry
18). Adding the additive PPh3 did not significantly improve the
product yield (entry 19). RhCl3·3H2O and RhCp*Cl were also
tested as catalysts, but both gave very low (<5%) yields (entries
20 and 21). Finally, Ru and Ni complexes were tested as the
catalyst under similar reaction conditions, but again no 3aa was
obtained (entries 22−24). On the basis of these results, the
optimized catalytic system for this transformation is 7 mol % of
(PPh3)3RhCl with 1 equiv of CuCl in xylene at 130 °C.
Next the optimized reaction conditions were used to
investigate the reaction of (benzo[h]quinolin-10-yl)methanol
RESULTS AND DISCUSSION
■
To achieve these reactions, (benzo[h]quinolin-10-yl)methanol
(1aa) and phenylboronic acid (2aa) were initially used as the
cross -coupling partners to optimize the reaction conditions in
the presence of different transition-metal catalysts. The results
are shown in Table 1. Several Pd and Ir complexes completely
failed to catalyze the transformation under various reaction
conditions (entries 1−5). However, when (PPh3)3RhCl was
used as the catalyst at 130 °C in xylene for 15 h, 10-
phenylbenzo[h]quinoline (3aa) was obtained in 45% yield
(entry 6). The use of an additive with (PPh3)3RhCl significantly
improved the reaction yield (i.e., the efficiency). Using CuCl as
an additive gave 3aa in 90% yield (entry 7), and CuI gave 3aa
in 82% yield (entry 8). However, the reaction yield did not
significantly improve using CuCl2 or Cu(OAc)2 as an additive
(entries 9 and 10). Notably, the cross-coupling reaction did not
proceed at all when CuCl was used without (PPh3)3RhCl
(entry 11). These results show that (PPh3)3RhCl together with
B
DOI: 10.1021/acs.organomet.6b00238
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
(1aa) with various arylboronic acids bearing electron-donating
or electron-withdrawing groups. The results are shown in
Scheme 2. When 1aa was reacted with phenylboronic acid, the
aryl rings, afforded the desired products 3an, ao in 73% and
68% yields, respectively.
(Naphthalen-2-yl)boronic acid also exhibited good reactivity
under the standard conditions to give 3ap in 89% yield.
Notably, (benzo[h]quinolin-10-yl)methanol (1a) reacted with
arylboronic acid bearing methyl groups at the two meta
positions to give 3aq in 95% yield. Di- and trisubstituted −F
and −CF3 also gave the corresponding products 3ar−at in 80−
85% yields.
Scheme 2. Arylative Coupling Reaction of
(Benzo[h]quinolin-10-yl)methanol and Various Arylboronic
a
Acids
To gain further insight into the scope of the reaction, various
aromatic primary alcohols were also surveyed (Scheme 3). A
Scheme 3. Arylative Coupling Reactions of Various Primary
a
Alcohols and Boronic Acid
a
Reaction conditions: 1aa (0.1 mmol), 2a (0.2 mmol), Rh(PPh3)3Cl
(7 mol %), CuCl (0.1 mmol) in 1 mL of xylene in air at 130 °C for 15
h. Yields were determined by 1H NMR using trimethylphenylsilane as
the internal standard.
desired product 3aa was obtained in 90% yield (Table 1, entry
7). Meta-substituted phenylboronic acids, including −Me,
−OMe, −OCF3, and −NO2, were well-tolerated and afforded
the corresponding products 3ab−ae in moderate to good yields
(80−92% yield). The phenylboronic acid with a methyl group
had the highest yield (92% of 3ab). However, the coupling
reaction between 1aa and phenylboronic acid containing a
methyl group at the ortho position produced a yield of 3af of
only 15%, indicating that the reaction is very sensitive to steric
hindrance in the arylboronic acid.
Next, various para-substituted phenylboronic acids were
subjected to the coupling reaction. Both 4-methyl- and 4-tert-
butylphenylboronic acids exhibited good reactivities, giving 3ag,
ah in 93% and 91% yields, respectively. The reaction of 1aa
with a phenylboronic acid bearing a methoxy group proceeded
smoothly to give 3ai in 87% yield. However, phenylboronic
acid with a −COOEt substituent gave the coupling product 3aj
in low yield (44%): The ester group may act as a directing
group to induce C−H activation, which would significantly
reduce the yield of the main reaction.
Not surprisingly, when (benzo[h]quinolin-10-yl)methanol
(1aa) was reacted with arylboronic acids bearing −F, −Cl, or
−Br groups under the standard reaction conditions, the
corresponding products 3ak−am were obtained in 70−77%
yields. The halide substituents on the substrates survived these
coupling reactions, and thus this offers possibilities for
additional functionalization reactions.2b,16 In addition, the
coupling reactions of 1aa with phenylboronic acids containing
other groups, such as −Ph or −CF3 on the phenylboronic acid
a
Reaction conditions: 1b (0,1 mmol), 2aa (0.2 mmol), Rh(PPh3)3Cl
(7 mol %), CuCl (0.1 mmol) in 1 mL of xylene in air at 130 °C for 15
h. Yields were determined by 1H NMR using trimethylphenylsilane as
the internal standard.
substrate with a methyl substituent at the 6-position of the
benzo[h]quinoline ring worked well in this catalytic system,
giving the desired product 3ba in 87% yield. Moreover, a −Ph
substituent at the 5-position also did not affect the reaction
with phenylboronic acid; the corresponding coupling product
3bb was obtained in 83% yield. However, the reaction of (5-
(naphthalen-2-yl)benzo[h]quinolin-10-yl)methanol and phe-
nylboronic acid under the standard conditions afforded the
product 3bc in a slightly lower yield of 80%. Reactions between
phenylboronic acid and (7-methoxybenzo[h]quinolin-10-yl)-
methanol with an electron-donating −OMe group at the 7-
position on the benzo[h]quinoline ring and (7-phenylbenzo-
[h]quinolin-10-yl)methanol with a −Ph group at the 7-position
proceeded smoothly to give the products 3bd, be in 81% and
90% yields, respectively. These results show that substitutions
on the benzo[h]quinoline ring have little effect on this reaction.
Finally (2-(pyridin-2-yl)phenyl)methanol was subjected to
the coupling reaction under the standard conditions. The
corresponding product 3bf was obtained in a yield of only 46%.
This indicates that the benzo[h]quinoline ring can generate a
stable rhodacyclic intermediate which facilitates the C−C bond
cleavage during the coupling reaction.
Initially, we theorized that this reaction proceeded directly
through a C−C bond cleavage mechanism in which the
C
DOI: 10.1021/acs.organomet.6b00238
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
rhodium metal center was directed close to the α C−C bond of
the primary alcohol via coordination with the alcohol N atom.
The C−C bond cleavage would then occur through the
oxidative addition of rhodium to the C−C bond. If this
hypothesis were true, the breakage of the C−C bond would not
be directly related to the hydroxyl group. In order to prove this,
the hydroxyl group on 1aa was replaced with an acetyl or
benzyl group to give (benzo[h]quinolin-10-yl)methyl acetate
(1c) and 10-(phenoxymethyl)benzo[h]quinoline (1d) respec-
tively. However, mixtures of 1c, d with phenylboronic acid did
not give the desired product 3aa under the standard reaction
conditions (Scheme 4). These results indicate that a free
Scheme 4. Rhodium-Catalyzed Reactions of
(Benzo[h]quinolin-10-yl)methyl Acetate and 10-
(Phenoxymethyl)benzo[h]quinoline with Phenylboronic
Acid
Figure 1. Proposed mechanism for the reaction of primary alcohols
and arylboronic acids catalyzed by (PPh3)3RhCl.
center close to the α C−C bond of the primary alcohol. The
oxidative addition of rhodium to that C−C bond causes it to
break and A is formed. The migration of the aldehyde H to the
Rh(III) metal center then produces intermediate B. The H
coordinated to the metal center is then oxidized to H2O,19
which gives intermediate C. The CO ligand in C is then
eliminated with the assistant of CuCl to give intermediate D.9e
The subsequent reductive elimination of E affords the desired
product and a rhodium(0) complex. Finally, the rhodium(0)
complex is oxidized to (PPh3)3RhCl in the presence of HCl and
O2, and it then re-enters another catalytic cycle.
hydroxyl group is crucial for the cross-coupling reaction. This
suggests that the cross-coupling does not proceed directly
through a C−C bond cleavage but rather that the reaction
proceeds via another reaction mechanism.
To further explore the reaction mechanism, 1aa was mixed
with (PPh3)3RhCl (7 mol %) and CuCl (1 equiv) in air under
the standard reaction conditions in the absence of phenyl-
boronic acid. The reaction was stopped after 3 h. The major
product was isolated from the reaction mixture and was
identified as benzo[h]quinoline-10-carbaldehyde (Scheme 5).
CONCLUSION
■
In summary, direct arylated coupling reactions between primary
alcohols and arylboronic acids can be performed through C−C
bond cleavage with the assistance of an N-containing directing
group in the presence of (PPh3)3RhCl and CuCl. Various
functionalities are tolerated under the standard reaction
conditions, and the reaction proceeds with high efficiency.
This catalytic system may also be applicable to other coupling
reactions. Further work on the applications of this reaction for
building aromatic compounds with biological activities is
currently underway in our laboratory.
Scheme 5. Rhodium-Catalyzed Reaction of
(Benzo[h]quinolin-10-yl)methanol with Phenylboronic Acid
To Obtain 10-Phenylbenzo[h]quinoline by Intermediate
Benzo[h]quinoline-10-carbaldehyde
EXPERIMENTAL SECTION
■
General Information. The starting materials were synthesized and
purified according to the literature procedures.20−23 Other chemicals
and reagents were obtained from commercial sources. All reactions
were monitored by analytical thin-layer chromatography on 0.20 mm
Yantai Huagong silica gel plates and spots were detected by UV
absorption. Silica gel (200−300 mesh) (from Yantai Huagong
Chemical Co. Ltd.) was used for flash chromatography.
This suggests that the oxidation of the primary alcohol to an
aldehyde may be the key step in this cross-coupling reaction.
Next, the isolated benzo[h]quinoline-10-carbaldehyde was
mixed with phenylboronic acid in the presence of (PPh3)3RhCl
and CuCl in air under the standard reaction conditions. This
produced 3aa as the only product in high yield (Scheme 5).
On the basis of the above findings and previous reports,9e,u
a
NMR spectra were obtained on a 400 MHz spectrometer with
CDCl3 as solvent. The chemical shifts are reported in ppm relative to
CDCl3 (δ 7.26) for 1H NMR and relative to the central CDCl3
resonance (δ 77.0) for 13C NMR. For 19F NMR, (trifluoromethyl)-
benzene was used as an external standard. Coupling constants (J) are
quoted in Hz for 1H. Multiplicities are reported as follows: singlet (s),
doublet (d), doublet of doublets (dd), triplet (t), quartet (q), and
multiplet (m). Conversions were obtained by 1H NMR analysis of the
plausible mechanism is proposed in Figure 1. First,
(PPh3)3RhCl dehydrogenates 1aa to 1aa′ in air.17 Subse-
quently, 1aa′ interacts with (PPh3)3RhCl with the help of
CuCl, known to cleave phosphines,9e,18 to give the five-
membered rhodacyclic intermediate A.9e This occurs when the
rhodium coordinates with the N atom, bringing the Rh metal
D
DOI: 10.1021/acs.organomet.6b00238
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
sample. NMR data of known compounds are in agreement with
literature values. Infrared spectra were recorded on an FT-IR
spectrophotometer. Elemental analyses were performed by the
Elemental Analysis Section of Tianjin University.
NMR (100 MHz, CDCl3) δ 159.2, 148.0, 140.3, 139.8, 137.5, 131.1,
130.0, 129.3, 128.1, 123.8, 122.2, 64.6; IR (KBr) ν 3282, 2923, 2860,
1726, 1576, 1518, 1497, 1182, 1033, 948, 743, 694 cm−1. Anal. Found
(calcd) for C12H11NO: C, 77.83 (77.81); H, 5.98 (5.99); N, 7.58
(7.56).
(Benzo[h]quinolin-10-yl)methyl Acetate (1c). The product was
prepared according to the literature.20,21 Yellow solid (yield 56%): 1H
NMR (400 MHz, CDCl3) δ 9.01 (d, J = 3.6 Hz, 1H), 8.17 (d, J = 7.6
Hz, 1H), 7.91−7.82 (m, 3H), 7.71−7.68 (m, 2H), 7.51−7.48 (m, 1H),
6.38 (s, 2H), 2.22 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 171.0,
147.8, 147.5, 135.7, 135.3, 135.0, 128.9, 128.5, 128.3, 127.5, 127.3,
126.4, 125.7, 120.9, 68.0, 21.3.
(Benzo[h]quinolin-10-yl)methanol (1aa). The product was
prepared according to the literature.20,21 Yellow solid (yield 63%):
1H NMR (400 MHz, CDCl3) δ 8.90 (d, J = 4.0 Hz, 1H), 8.18 (d, J =
8.0 Hz, 1H), 7.97 (d, J = 7.2 Hz, 1H), 7.83 (d, J = 8.8 Hz, 1H), 7.74−
7.67 (m, 3H), 7.52 (dd, J = 4.4 Hz, 8.0 Hz, 1H), δ 4.60 (q, J = 7.2 Hz,
2H); 13C NMR (100 MHz, CDCl3) δ 147.5, 146.3, 139.5, 136.7,
135.3, 130.2, 129.6, 129.0, 128.8, 127.9, 127.6, 125.1, 121.0, 66.6; IR
(KBr) ν 3467, 2923, 1630, 1447, 1383, 1199, 1025, 752, 698 cm−1.
Anal. Found (calcd) for C14H11NO: C, 80.31 (80.36); H, 5.32 (5.30);
N, 6.71 (6.69).
10-(Benzyloxymethyl)benzo[h]quinoline (1d). The product
was prepared according to the literature.20,21 Yellow solid (yield
53%): 1H NMR (400 MHz, CDCl3) δ 9.03−9.01 (m, 1H), 8.29 (d, J =
7.6 Hz, 1H), 8.17−8.15 (m, 1H), 7.90−7.83 (m, 2H), 7.78−7.74 (m,
1H), 7.67 (d, J = 8.8 Hz, 1H), 7.56 (d, J = 7.2 Hz, 2H), 7.49−7.33 (m,
4H), 5.92 (s, 2H), 4.91 (s, 2H); 13C NMR (100 MHz, CDCl3) δ
148.3, 147.2, 139.2, 139.1, 135.2, 134.9, 128.7, 128.6, 128.3, 127.7,
127.6, 127.54, 127.48, 127.4, 125.7, 125.3, 120.6, 73.8, 72.9.
Benzo[h]quinoline-10-carbaldehyde (1aa′). (Benzo[h]-
quinoline-10-yl)methanol (20.9 mg, 0.1 mmol), (PPh3)3RhCl (6.5
mg, 0.007 mmol), and CuCl (9.9 mg, 0.1 mmol) were added to 1 mL
of xylene. Then the mixture was stirred at 130 °C for 7 h in air, and the
product was purified by column chromatography to provide a pale
(6-Methylbenzo[h]quinolin-10-yl)methanol (1ba). The prod-
uct was prepared according to the literature.20,21 Yellow solid (yield
1
65%): H NMR (400 MHz, CDCl3) δ 8.93 (d, J = 2.0 Hz, 1H), 8.16
(d, J = 5.2 Hz, 1H), 8.07 (dd, J = 1.6 Hz, 4.8 Hz, 1H), 7.70 (d, J = 4.8
Hz, 2H), 7.53−7.52 (m, 2H), 5.20 (s, 2H), 2.75 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 146.9, 146.1, 140.0, 136.0, 135.4, 134.8, 130.4,
130.0, 128.0, 127.7, 125.4, 124.8, 121.3, 67.0, 29.7; IR (KBr) ν 3424,
2925, 1723, 1425, 1383, 1263, 1026, 797, 732 cm−1. Anal. Found
(calcd) for C15H13NO: C, 80.65 (80.69); H, 5.91 (5.87); N, 6.29
(6.27).
(5-Phenylbenzo[h]quinolin-10-yl)methanol (1bb). The prod-
uct was prepared according to the literature.20−23 Yellow solid (yield
60%): 1H NMR (400 MHz, CDCl3) δ 9.06−9.03 (m, 1H), 8.37−8.33
(m, 1H), 7.92 (d, J = 4.8 Hz, 1H), 7.77−7.63 (m, 2H), 7.55−7.41 (m,
6H), 7.17−7.13 (m, 1H), 5.28−5.25 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 147.6, 141.2, 139.2, 137.2, 135.3, 135.2, 130.5, 130.2, 130.0,
129.8, 129.1, 128.6, 128.5, 128.4, 127.7, 127.4, 127.0, 121.3, 121.1,
66.9; IR (KBr) ν 3323, 3055, 2925, 1923, 1725, 1493, 1265, 1175,
1032, 756, 702 cm−1. Anal. Found (calcd) for C20H15NO: C, 84.14
(84.19); H, 5.32 (5.30); N, 4.89 (4.91).
(5-(Naphthalen-2-yl)benzo[h]quinolin-10-yl)methanol (1bc).
The product was prepared according to the literature.20−23 Yellow
solid (yield 58%): 1H NMR (400 MHz, CDCl3) δ 9.05−9.04 (m, 1H),
8.40−8.38 (m, 1H), 8.02−7.92 (m, 6H), 7.74−7.68 (m, 2H), 7.64−
7.52 (m, 4H), 5.26 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 147.6,
147.0, 139.8, 137.4, 136.6, 135.4, 135.0, 133.4, 132.8, 130.6, 129.8,
129.5, 129.1, 128.9, 128.5, 128.11, 128.06, 128.0, 127.8, 127.4, 126.6,
126.5, 121.1, 66.9; IR (KBr) ν 3320, 2926, 2780, 1923, 1723, 1522,
1195, 1042, 763, 709 cm−1. Anal. Found (calcd) for C24H17NO: C,
85.88 (85.94); H, 5.13 (5.11); N, 4.18 (4.18).
(7-Methoxybenzo[h]quinolin-10-yl)methanol (1bd). The
product was prepared according to the literature.20,21 Yellow solid
(yield 63%): 1H NMR (400 MHz, CDCl3) δ 8.98 (dd, J = 1.6 Hz, 4.0
Hz, 1H), 8.40 (d, J = 9.2 Hz, 1H), 8.25 (dd, J = 1.6 Hz, 6.4 Hz, 1H),
7.69 (d, J = 8.8 Hz, 1H), 7.61 (d, J = 8.0 Hz, 1H), 7.57−7.54 (m, 1H),
7.05−7.00 (m, 1H), 5.14 (d, J = 7.6 Hz, 2H), 4.03 (S, 3H); 13C NMR
(100 MHz, CDCl3) δ 155.3, 147.7, 146.4, 136.8, 131.8, 130.8, 130.7,
128.0, 126.5, 124.5, 122.5, 121.3, 107.0, 66.6, 55.8; IR (KBr) ν 3415,
2928, 1734, 1427, 1396, 1241, 1023, 765, 713 cm−1. Anal. Found
(calcd) for C15H13NO2: C, 75.34 (75.30); H, 5.46 (5.48); N, 5.85
(5.85).
1
yellow solid (20.3 mg, yield 98%): H NMR (CDCl3, 400 MHz) δ
11.26 (s, 1H), 9.02−9.01 (m, 1H), 8.24 (dd, J = 0.8 Hz, 5.2 Hz, 1H),
8.07 (d, J = 5.2 Hz, 1H), 7.93 (d, J = 4.8 Hz, 1H), 7.88 (d, J = 6.0 Hz,
1H), 7.78−7.76 (m, 2H), 7.57−7.55 (m, 1H); 13C NMR (CDCl3, 100
MHz) δ 194.7, 148.6, 145.9, 138.0, 135.8, 134.1, 131.6, 129.8, 127.9,
127.8, 127.6, 127.3, 126.1, 121.9. IR (KBr) ν 3449, 2925, 2854, 1637,
1384, 1121, 836, 710 cm−1. Anal. Found (calcd) for C14H9NO: C,
81.10 (81.14); H, 4.41 (4.38); N, 6.75 (6.76).
Experimental Procedure for Rhodium-Catalyzed Direct
Arylation with Organoboron Compounds via Primary Alco-
hols. In an oven-dried screw-top vial were placed the primary alchohol
(0.1 mmol), substituted phenylboronic acid (0.2 mmol), copper(I)
chloride (9.9 mg, 0.1 mmol), Rh(PPh3)3Cl (6.5 mg, 0.007 mmol), and
xylene (1 mL) in an air atmosphere. The mixture was vigorously
stirred at 130 °C to the end of the reaction. Organic solvents were
removed in vacuo, and then the residue was purified by silica gel
column chromatography to give the desired product.
The compounds 3aa−ag,ai−at,ba−bf are known, and the 1H NMR
and the 13C NMR spectra of these compounds are in agreement with
previous reports.9e,24
10-Phenylbenzo[h]quinoline (3aa). Pale yellow solid (23.0 mg,
1
yield 90%): H NMR (CDCl3, 400 MHz) δ 8.42 (dd, J = 4.4 Hz, 1.6
Hz, 1H), 8.09 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H),
7.86 (d, J = 8.8 Hz, 1H), 7.71−7.67 (m, 2H), 7.55 (d, J = 7.2 Hz, 1H),
7.40−7.33 (m, 6H); 13C NMR (CDCl3, 100 MHz) δ 146.8, 146.4,
141.8, 135.1, 135.0, 131.4, 129.0, 128.7, 128.2, 127.9, 127.3, 127.2,
127.0, 125.9, 125.6, 121.0. IR (KBr) ν 3051, 1584, 1511, 1441, 1420,
816, 757, 701, 621 cm−1. Anal. Found (calcd) for C19H13N: C, 89.32
(89.38); H, 5.14 (5.13); N, 5.51 (5.49).
10-m-Tolylbenzo[h]quinoline (3ab). Pale yellow solid (24.8 mg,
yield 92%): 1H NMR (CDCl3, 400 MHz) δ 8.45 (dd, J = 4.0, 1.2 Hz,
1H), 8.08 (d, J = 8.0 Hz, 1H), 7.91 (d, J = 8.0 Hz, 1H), 7.85 (d, J = 8.8
Hz, 1H), 7.70−7.66 (m, 2H), 7.55 (d, J = 7.2 Hz, 1H), 7.32−7.28 (m,
3H), 7.21−7.16 (m, 2H), 2.40 (s, 3H); 13C NMR (CDCl3, 100 MHz)
δ 146.9, 146.3, 141.9, 139.5, 135.1, 131.5, 129.3, 128.8, 128.3, 128.2,
127.8, 127.1, 127.0, 126.4, 126.0, 125.9, 121.0, 21.6; IR (KBr) ν 3030,
2942, 1555, 1367, 1258, 1022, 846, 767, 687 cm−1. Anal. Found
(calcd) for C20H15N: C, 89.13 (89.19); H, 5.63 (5.61); N, 5.23 (5.20).
10-(3-Methoxyphenyl)benzo[h]quinoline (3ac). Pale yellow solid
(23.4 mg, yield 82%): 1H NMR (CDCl3, 400 MHz) δ 8.47 (dd, J = 4.0
Hz, 1.6 Hz, 1H), 8.09 (dd, J = 8.0 Hz, 1.2 Hz,1H), 7.93 (d, J = 7.6 Hz,
1H), 7.86 (d, J = 8.8 Hz, 1H), 7.71−7.66 (m, 2H), 7.57 (d, J = 7.2 Hz,
1H), 7.36−7.30 (m, 2H), 6.97−6.91 (m, 3H), 3.80 (s, 3H); 13C NMR
(CDCl3, 100 MHz) δ 158.0, 147.0, 146.9, 141.4, 138.9, 135.2, 135.1,
131.7, 129.8, 129.2, 128.3, 127.7, 127.2, 127.0, 125.9, 121.0, 112.8,
(7-Phenylbenzo[h]quinolin-10-yl)methanol (1be). The prod-
uct was prepared according to the literature.20,21 Yellow solid (yield
1
60%): H NMR (400 MHz, CDCl3) δ 9.05 (d, J = 4.4 Hz, 1H), 8.28
(d, J = 8.0 Hz, 1H), 7.95 (d, J = 9.2 Hz, 1H), 7.75 (d, J = 7.6 Hz,
1H),7.65−7.61 (m, 2H), 7.52−7.46 (m, 6H), 5.25 (s, 2H); 13C NMR
(100 MHz, CDCl3) δ 147.9, 146.8, 141.2, 140.9, 139.2, 136.8, 133.5,
130.4, 130.2, 130.1, 129.4, 128.4, 127.6, 127.5, 127.1, 125.1, 121.5,
67.1; IR (KBr) ν 3326, 2923, 2860, 1726, 1576, 1518, 1497, 1182,
1033, 948, 743, 694 cm−1. Anal. Found (calcd) for C20H15NO: C,
84.16 (84.19); H, 5.33 (5.30); N, 4.89 (4.91)
(2-(Pyridin-2-yl)phenyl)methanol (1bf). The product was
prepared according to the literature.21 Yellow solid (yield 66%): H
1
NMR (400 MHz, CDCl3) δ 8.63 (d, J = 2.4 Hz, 1H), 7.85−7.83 (m,
1H), 7.62 (d, J = 5.2 Hz, 1H), 7.54 (d, J = 7.2 Hz, 1H), 7.53−7.48 (m,
1H), 7.42 (d, J = 2.4 Hz, 2H), 7.41−7.32 (m, 1H), 4.47 (s, 2H); 13C
E
DOI: 10.1021/acs.organomet.6b00238
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
55.3; IR (KBr) ν 3044, 2923, 1564, 1224, 1036, 829, 793, 725, 608
cm−1. Anal. Found (calcd) for C20H15NO: C, 84.17 (84.19); H, 5.27
(5.30); N, 4.92 (4.91).
(100 MHz, CDCl3) δ 166.3, 151.5, 146.9, 144.3, 135.2, 134.9, 130.9,
130.1, 130.0, 128.7, 128.4, 128.2, 127.2, 127.1, 127.0, 126.0, 121.2,
61.0, 14.3; IR (KBr): 3046, 2950, 2915, 2862, 1711, 1606, 1398, 1271,
1174, 1021, 832, 758, 731, 705 cm−1. Anal. Found (calcd) for
C22H17NO2: C, 80.68 (80.71); H, 5.24 (5.23); N, 4.30 (4.28).
10-(4-Fluorophenyl)benzo[h]quinoline (3ak). Pale yellow solid
(19.1 mg, yield 70%): 1H NMR (CDCl3, 400 MHz) δ 8.45 (dd, J = 4.0
Hz, 1.6 Hz, 1H), 8.09 (dd, J = 8.0 Hz, 1.2 Hz, 1H), 7.93 (d, J = 8.4 Hz,
1H), 7.86 (d, J = 8.8 Hz, 1H), 7.71−7.66 (m, 2H), 7.52 (d, J = 7.2 Hz,
1H), 7.37−7.28 (m, 3H), 7.08 (t, J = 8.8 Hz, 2H); 13C NMR (CDCl3,
100 MHz) δ 161.5 (d, 1JC−F = 241.7 Hz), 146.8, 146.7, 142.2 (d, 3JC−F
= 3.3 Hz), 140.7, 135.2, 135.0, 131.5, 130.1 (d, 3JC−F = 7.7 Hz), 129.1,
10-(3-(Trifluoromethoxy)phenyl)benzo[h]quinoline (3ad). Yellow
solid (28.8 mg, yield 85%): 1H NMR (400 MHz, CDCl3) δ 8.42 (dd, J
= 4.4 Hz, 1.6 Hz, 1H), 8.10 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 7.96 (d, J =
7.6 Hz, 1H), 7.87 (d, J = 8.4 Hz, 1H), 7.73−7.68 (m, 2H), 7.53 (d, J =
7.2 Hz, 1H), 7.43 (t, J = 8.0 Hz, 1H), 7.36−7.32 (m, 2H), 7.22 (d, J =
8.4 Hz, 2H); 13C NMR (CDCl3, 100 MHz) δ 148.6, 148.3, 147.0,
146.5, 140.0, 135.2, 135.0, 131.2, 128.9, 128.7, 128.5, 128.2, 127.3,
127.0, 126.9, 126.1, 122.1, 122.0, 121.2, 119.4 (q, JC−F = 254.7 Hz),
118.3; 19F NMR (376 MHz, CDCl3) δ −57.6 (s, 3F); IR (KBr) ν
3045, 2921, 1578, 1418, 1221, 1155, 913, 832, 695, 613 cm−1. Anal.
Found (calcd) for C20H12F3NO: C, 70.83 (70.79); H, 3.58 (3.56); N,
4.10 (4.13).
128.3, 128.1, 127.2, 127.0, 126.0, 121.1, 114.2 (d, 2JC−F = 21.3 Hz); 19
F
NMR (376 MHz, CDCl3) δ −118.1 (m, 1F); IR (KBr) ν 3045, 1594,
1423, 1213, 1157, 834, 756, 729 cm−1. Anal. Found (calcd) for
C19H12FN: C, 83.53 (83.50); H, 4.41 (4.43); N, 5.11 (5.12).
10-(4-Chlorophenyl)benzo[h]quinoline (3al). Pale yellow solid
(21.7 mg, yield 75%): 1H NMR (400 MHz, CDCl3) δ 8.49 (d, J = 2.8
Hz, 1H), 8.10 (d, J = 8.0 Hz, 1H), 7.95 (d, J = 7.6 Hz, 1H), 7.87 (d, J
= 8.8 Hz, 1H), 7.72−7.68 (m, 2H), 7.52 (d, J = 7.2 Hz, 1H),7.41−7.30
(m, 5H); 13C NMR (CDCl3, 100 MHz) δ 146.9, 146.8, 146.5, 144.9,
140.3, 135.2, 135.0, 131.5, 131.3, 130.1, 130.0, 128.9, 128.2, 127.4,
127.2, 127.1, 127.0, 126.0, 121.1; IR (KBr) ν 3045, 2926, 1510, 1421,
1395, 1086, 840, 822, 728 cm−1. Anal. Found (calcd) for C19H12ClN:
C, 78.72 (78.76); H, 4.16 (4.17); N, 4.81 (4.83).
10-(4-Bromophenyl)benzo[h]quinoline (3am). Pale yellow solid
(25.6 mg, yield 77%): 1H NMR (400 MHz, CDCl3) δ 8.47 (d, J = 2.8
Hz, 1H), 8.10 (d, J = 8.0 Hz, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.86 (d, J
= 8.8 Hz, 1H), 7.72−7.66 (m, 2H), 7.53−7.49 (m, 3H), 7.35 (dd, J =
8.0, 4.0 Hz, 1H), 7.23 (d, J = 8.4 Hz, 2H); 13C NMR (CDCl3, 100
MHz) δ 146.9, 146.6, 145.4, 140.4, 135.3, 135.0, 131.2, 130.5, 130.4,
128.8, 128.3, 128.2, 127.2, 127.0, 126.0, 121.2, 119.6; IR (KBr) ν 3045,
1592, 1487, 1422, 1394, 1015, 920, 816, 730 cm−1. Anal. Found
(calcd) for C19H12BrN: C, 68.32 (68.28); H, 3.61 (3.62); N, 4.17
(4.19).
10-(Biphenyl-4-yl)benzo[h]quinoline (3an). Pale yellow solid (24.2
mg, yield 73%): 1H NMR (CDCl3, 400 MHz) δ 8.46 (dd, J = 4.0 Hz,
1.6 Hz, 1H), 8.11 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 7.95 (d, J = 7.6 Hz,
1H), 7.88 (d, J = 8.8 Hz, 1H), 7.76−7.66 (m, 7H), 7.51−7.44 (m,
4H),7.39−7.33 (m, 2H); 13C NMR (CDCl3, 100 MHz) δ 146.9,
145.6, 141.5, 141.4, 138.4, 135.2, 135.1, 131.5, 129.2, 129.1, 128.7,
128.3, 128.0, 127.3, 127.0, 126.9, 126.0, 125.9, 121.1; IR (KBr) ν 3045,
2924, 1483, 1419, 835, 752, 711 cm−1. Anal. Found (calcd) for
C25H17N: C, 90.63 (90.60); H, 5.17 (5.17); N, 4.21 (4.23).
10-(3-Nitrophenyl)benzo[h]quinoline (3ae). Yellow solid (24.1
1
mg, yield 80%): H NMR (400 MHz, CDCl3) δ 8.37−8.24 (m, 3H),
8.12 (d, J = 8.0 Hz, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.89 (d, J = 8.8 Hz,
1H), 7.75−7.68 (m, 3H), 7.56−7.51 (m, 2H),7.34 (dd, J = 7.6 Hz, 4.4
Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 148.0, 147.8, 147.0, 146.2,
139.0, 135.4, 135.1, 135.0, 131.1, 129.0, 128.7, 128.2, 127.9, 127.4,
127.1, 126.3, 123.9, 121.4, 120.8; IR (KBr) ν 3047, 1526, 1345, 835,
805, 743, 676, 615 cm−1. Anal. Found (calcd) for C19H12N2O2: C,
76.04 (75.99); H, 4.05 (4.03); N, 9.31 (9.33).
10-o-Tolylbenzo[h]quinoline (3af). Yellow viscous oil (4.04 mg,
1
yield 15%): H NMR (CDCl3, 400 MHz) δ 8.41 (dd, J = 4.0, 1.6 Hz,
1H), 8.08 (dd, J = 8.0, 1.6 Hz, 1H), 7.95 (d, J = 7.6 Hz, 1H), 7.87 (d, J
= 8.8 Hz, 1H), 7.72−7.68 (m, 2H), 7.47 (d, J = 7.2 Hz, 1H), 7.32−
7.25 (m, 4H), 7.18−7.16 (m, 1H), 1.84 (s, 3H); 13C NMR (CDCl3,
100 MHz) δ 147.4, 147.1, 146.4, 141.1, 135.8, 135.0, 134.7, 130.7,
128.7, 128.4, 127.9, 127.8, 127.2, 127.0, 125.9, 125.8, 125.4, 125.1,
120.9, 20.1; IR (KBr) ν 3045, 2920, 1419, 1261, 1134, 925, 753, 734
cm−1. Anal. Found (calcd) for C20H15N: C, 89.21 (89.19); H, 5.59
(5.61); N, 5.22 (5.20).
10-p-Tolylbenzo[h]quinoline (3ag). Pale yellow solid (25.0 mg,
1
yield 93%): H NMR (CDCl3, 400 MHz) δ 8.44 (d, J = 2.4 Hz, 1H),
8.15 (d, J = 6.8 Hz, 1H), 7.92 (d, J = 7.6 Hz, 1H), 7.77 (d, J = 8.8 Hz,
1H), 7.70 (t, J = 8.0 Hz, 2H), 7.57 (d, J = 7.2 Hz, 1H), 7.33−7.20 (m,
5H), 2.47 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ 147.0, 146.8,
143.5, 141.8, 135.1, 135.0, 131.6, 129.1, 128.6, 128.3, 128.1, 127.8,
127.2, 127.0, 125.8, 121.0, 21.3; IR (KBr) ν 3044, 2918, 1603, 1555,
1442, 1419, 1326, 1261, 925, 813, 716, 663 cm−1. Anal. Found (calcd)
for C20H15N: C, 89.24 (89.19); H, 5.60 (5.61); N, 5.21 (5.20).
10-(4-tert-Butylphenyl)benzo[h]quinoline (3ah). Pale yellow solid
(28.3 mg, yield 91%):1H NMR (CDCl3, 400 MHz) δ 8.43 (dd, J = 4.0
Hz, 1.6 Hz, 1H), 8.08 (dd, J = 8.0 Hz, 1.2 Hz, 1H), 7.91 (d, J = 7.6 Hz,
1H), 7.86 (d, J = 8.8 Hz, 1H), 7.70−7.66 (m, 2H), 7.59 (d, J = 7.2 Hz,
1H), 7.43 (d, J = 8.4 Hz, 2H), 7.33−7.30 (m, 3H), 1.44 (s, 9H); 13C
NMR (CDCl3, 100 MHz) δ 148.4, 147.0, 146.8, 143.3, 141.8, 135.1,
135.0, 131.5, 129.2, 128.4, 128.3, 127.7, 127.2, 127.0, 125.8, 124.2,
121.0, 34.5, 31.6; IR (KBr) ν 3051, 2945, 1637, 1573, 1418, 1332, 927,
833, 813, 662 cm−1; HRMS (ESI) m/z 312.1734 [M + H+] (calcd
312.1752). Anal. Found (calcd) for C23H21N: C, 88.67 (88.71); H,
6.79 (6.80); N, 4.50 (4.50).
10-(4-Methoxyphenyl)benzo[h]quinoline (3ai). Pale yellow solid
(23.7 mg, yield 87%): 1H NMR (CDCl3, 400 MHz) δ 8.46 (dd, J = 4.0
Hz, 1.6 Hz, 1H), 8.10 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 7.94 (dd, J = 8.0
Hz,1.2 Hz, 1H), 7.86 (d, J = 8.8 Hz, 1H), 7.71−7.67(m, 2H), 7.54−
7.52 (m, 1H), 7.36−7.29 (m, 3H), 7.12−7.08 (m, 2H), 3.89 (s, 3H);
13C NMR (CDCl3, 100 MHz) δ 158.0, 147.0, 146.9, 139.0, 135.2,
135.1, 131.7, 129.8, 129.2, 128.3, 127.7, 127.2, 127.0, 125.9, 121.0,
112.8, 55.3; IR (KBr) ν 3028, 2920, 1513, 1242, 1172, 821, 736, 660
cm−1. Anal. Found (calcd) for C20H15NO: C, 84.22 (84.19); H, 5.29
(5.30); N, 4.92 (4.91).
10-(4-(Trifluoromethyl)phenyl)benzo[h]quinoline (3ao). Pale yel-
1
low solid (22.0 mg, yield 68%): H NMR (400 MHz, CDCl3) δ 8.40
(d, J = 2.8 Hz, 1H), 8.11 (d, J = 8.0 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H),
7.88 (d, J = 8.8 Hz, 1H), 7.74−7.64 (m, 4H), 7.52−7.45 (m, 3H),7.35
(dd, J = 8.0 Hz, 4.0 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 150.2,
146.9, 146.4, 140.3, 135.3, 135.0, 131.1, 129.0, 128.9, 128.5, 128.2,
128.0, 127.7 (q, JC−F = 31.8 Hz), 127.3, 127.1, 126.1, 124.8 (q, JC−F
=
273.6 Hz), 124.2 (q, JC−F = 3.7 Hz), 121.3; 19F NMR (376 MHz,
CDCl3) δ −62.0 (s, 3F); IR (KBr) ν 3043, 2928, 1523, 1402, 1162,
1075, 926, 742, 693, 607 cm−1. Anal. Found (calcd) for C20H12F3N: C,
74.32 (74.30); H, 3.75 (3.74); N, 4.34 (4.33).
10-(Naphthalen-2-yl)benzo[h]quinoline (3ap). Yellow solid (27.2
mg, yield 89%): 1H NMR (CDCl3, 400 MHz) δ 8.33 (dd, J = 4.0 Hz,
1.6 Hz, 1H), 8.10 (dd, J = 8.0, 1.6 Hz, 1H), 7.98 (d, J = 7.6 Hz, 1H),
7.94−7.89 (m, 4H), 7.79−7.72 (m, 3H), 7.66 (d, J = 6.4 Hz, 1H),
7.53−7.49 (m, 2H), 7.46 (dd, J = 8.4 Hz, 1.6 Hz, 1H),7.30 (dd, J = 8.0
Hz, 4.4 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 146.9, 146.7, 144.5,
141.5, 135.1, 135.0, 133.7, 132.1, 131.9, 129.4, 129.0, 128.3, 128.1,
128.0, 127.6, 127.2, 127.1, 125.9, 125.6, 125.5, 125.4, 125.1, 121.0; IR
(KBr) ν 3047, 1560, 1418, 1013, 831, 817, 749, 642 cm−1. Anal. Found
(calcd) for C23H15N: C, 90.42 (90.46); H, 4.96 (4.95); N, 4.57 (4.59).
10-(3,5-Dimethylphenyl)benzo[h]quinoline (3aq). Pale yellow
Ethyl 4-(Benzo[h]quinolin-10-yl)benzoate (3aj). Yellow solid (14.4
1
mg, yield 44%): H NMR (400 MHz, CDCl3) δ 8.39−8.38 (m, 1H),
1
8.13 (d, J = 8.4 Hz, 1H), 8.09 (d, J = 8.0 Hz, 2H), 7.95 (d, J = 8.0 Hz,
1H), 7.86 (d, J = 8.8 Hz, 1H), 7.68 (d, J = 8.0 Hz, 2H), 7.50 (d, J = 7.2
Hz, 1H), 7.41 (d, J = 7.6 Hz, 2H), 7.32 (dd, J = 8.0 Hz, 4.0 Hz, 1H),
4.43 (dd, J = 11.6 Hz, 7.2 Hz, 2H), 1.44 (t, J = 7.2 Hz, 3H); 13C NMR
solid (26.9 mg, yield 95%): H NMR (CDCl3, 400 MHz) δ 8.48
(dd, J = 4.0, 1.6 Hz, 1H), 8.09 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 7.91 (d, J
= 7.2 Hz, 1H), 7.86 (d, J = 8.8 Hz, 1H), 7.70−7.66 (m, 2H), 7.56 (d, J
= 6.4 Hz, 1H), 7.34 (dd, J = 8.0 Hz, 4.4 Hz, 1H), 7.01 (s, 3H), 2.37 (s,
F
DOI: 10.1021/acs.organomet.6b00238
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
6H); 13C NMR (CDCl3, 100 MHz) δ 146.9, 146.8, 146.1, 141.9,
136.6, 135.1, 135.0, 131.5, 129.0, 128.3, 127.7, 127.3, 127.1, 127.0,
126.6, 125.8, 121.0, 21.4; IR (KBr) ν 3046, 2925, 1556, 1413, 1328,
905, 830, 733, 636 cm−1. Anal. Found (calcd) for C21H17N: C, 89.05
(89.01); H, 6.04 (6.05); N, 4.92 (4.94).
2H), 8.09 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 7.71 (d, J = 8.8 Hz, 1H), 7.49
(d, J = 8.0 Hz, 1H), 7.39−7.31 (m, 6H), 7.13 (d, J = 8.0 Hz, 1H), 4.10
(s, 3H); 13C NMR (100 MHz, CDCl3) δ 154.8, 146.7, 146.6, 146.5,
135.1, 133.9, 131.4, 130.0, 129.0, 127.4, 127.2, 125.7, 125.3, 125.1,
121.5, 121.1, 106.5, 55.8; IR (KBr) ν 3052, 1590, 1510, 1455, 1419,
1318, 1246, 1112, 1072, 1024, 834, 812, 764, 736, 699 cm−1. Anal.
Found (calcd) for C20H15NO: C, 84.24 (84.19); H, 5.30 (5.30); N,
4.92 (4.91).
10-(3,5-Bis(trifluoromethyl)phenyl)benzo[h]quinoline (3ar). Pale
1
yellow solid (33.2 mg, yield 85%): H NMR (400 MHz, CDCl3) δ
8.37 (d, J = 2.4 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 8.01 (d, J = 7.6 Hz,
1H), 7.85−7.72 (m, 6H), 7.53 (d, J = 6.8 Hz, 1H),7.37 (dd, J = 8.0 Hz,
4.0 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 148.1, 146.9, 146.0,
138.4, 135.5, 135.0, 131.2, 130.4, 129.2, 128.6, 127.3, 127.1, 126.4,
125.2, 122.5, 121.6, 119.5; 19F NMR (376 MHz, CDCl3) δ −62.6 (s,
6F); IR (KBr) ν 3043, 1640, 1516, 1375, 1278, 1167, 1127, 895, 836,
735, 626 cm−1. Anal. Found (calcd) for C21H11F6N: C, 64.50 (64.46);
H, 2.82 (2.83); N, 3.59 (3.58).
7,10-Diphenylbenzo[h]quinoline (3be). Pale yellow solid (29.8 mg,
1
yield 90%): H NMR (400 MHz, CDCl3) δ 8.44 (dd, J = 4.0 Hz, 1.6
Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H), 7.94 (d, J = 8.8 Hz, 1H), 7.66−7.55
(m, 7H), 7.50−7.47 (m, 1H), 7.43−7.37 (m, 5H),7.33 (dd, J = 8.0 Hz,
4.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 146.9, 146.8, 146.8,
141.2, 141.0, 140.1, 134.9, 132.8, 130.8, 130.3, 129.5, 128.7, 128.6,
128.4, 127.4, 127.3, 126.9, 125.9, 125.7, 125.6, 121.2; IR (KBr) ν 3053,
1574, 1523, 1496, 1394, 1146, 1035, 812, 766, 735, 708 cm−1. Anal.
Found (calcd) for C25H17N: C, 90.65 (90.60); H, 5.17 (5.17); N, 4.21
(4.23).
2-(Biphenyl-2-yl)pyridine (3bf). White solid (10.6 mg, yield 46%):
1H NMR (400 MHz, CDCl3) δ 8.66 (d, J = 3.6 Hz, 1H), 7.75−7.73
(m, 1H), 7.51−7.48 (m, 3H), 7.41−7.38 (m, 1H), 7.52−7.19 (m, 5H),
7.13−7.10 (m, 1H), 6.91 (d, J = 8.0 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 159.2, 149.3, 141.3, 140.6, 139.4, 135.2, 130.4, 129.7, 128.5,
128.0, 127.6, 126.6, 125.4, 121.3; IR (KBr) ν 3053, 1572, 1521, 1491,
1394, 1146, 1035, 812, 761, 735, 709 cm−1. Anal. Found (calcd) for
C17H13N, 88.27 (88.28); H, 5.68 (5.67); N, 6.04 (6.06).
10-(3,4-Difluorophenyl)benzo[h]quinoline (3as). Pale yellow solid
(23.3 mg, yield 80%): 1H NMR (400 MHz, CDCl3) δ 8.48 (dd, J = 4.0
Hz, 1.6 Hz, 1H), 8.11 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 7.95 (d, J = 7.2 Hz,
1H), 7.87 (d, J = 8.8 Hz, 1H), 7.73−7.66 (m, 2H), 7.52−7.49 (m,
1H), 7.36 (dd, J = 8.0 Hz, 4.0 Hz, 1H), 7.21−7.12 (m, 2H), 7.06−7.03
(m, 1H); 13C NMR (CDCl3, 100 MHz) δ 149.7 (dd, 1JC−F = 244.2 Hz,
1
12.6 Hz), 149.0 (dd, JC−F = 243.6 Hz, 12.6 Hz), 146.9, 146.4, 143.1
3
(dd, JC−F = 6.5 Hz, 4.2 Hz), 139.4, 135.3, 134.9, 131.2, 128.8, 128.5,
3
128.2, 127.3, 126.9, 126.1, 124.5 (dd, JC−F = 5.7 Hz, 3.4 Hz), 121.2,
117.9 (d, 2JC−F = 17.3 Hz), 116.0 (d, 2JC−F = 16.9 Hz); 19F NMR (376
MHz, CDCl3) δ −140.3 (m, 1F), −143.0 (m, 1F); IR (KBr) ν 3052,
2926, 1665, 1519, 1423, 1257, 1123, 837, 816, 772, 733, 628 cm−1.
Anal. Found (calcd) for C19H11F2N: C, 78.37 (78.34); H, 3.80 (3.81);
N, 4.83 (4.81).
ASSOCIATED CONTENT
* Supporting Information
■
S
10-(3,4,5-Trifluorophenyl)benzo[h]quinoline (3at). Pale yellow
solid (26.3 mg, yield 85%): 1H NMR (CDCl3, 400 MHz) δ 8.51
(dd, J = 4.0 Hz, 1.6 Hz, 1H), 8.12 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 7.97
(d, J = 7.6 Hz, 1H), 7.87 (d, J = 8.8 Hz, 1H), 7.74−7.66 (m, 2H), 7.48
(d, J = 7.2 Hz, 1H), 7.38 (dd, J = 8.0 Hz, 4.4 Hz, 1H), 6.96−6.92 (m,
2H); 13C NMR (CDCl3, 100 MHz) δ 151.8, 149.4, 147.1, 146.2,
142.3, 139.5, 138.5, 135.4, 134.9, 130.8, 128.9, 128.7, 128.1, 127.4,
127.0, 126.3, 121.4, 112.9, 112.8; 19F NMR (376 MHz, CDCl3) δ
−137.3 (m, 1F), −165.8 (m, 2F); IR (KBr) ν 3052, 1611, 1527, 1423,
1244, 1031, 833, 732, 659, 631 cm−1. Anal. Found (calcd) for
C19H10F3N: C, 73.75 (73.78); H, 3.28 (3.26); N, 4.51 (4.53).
6-Methyl-10-phenylbenzo[h]quinoline (3ba). Pale yellow solid
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.6b00238.
NMR spectra of materials and products (PDF)
AUTHOR INFORMATION
Corresponding Authors
*E-mail for Y.T.: yuntian@hust.edu.cn.
*E-mail for J.W.: wjh@tju.edu.cn.
■
1
Notes
(23.4 mg, yield 87%): H NMR (400 MHz, CDCl3) δ 8.37−8.36 (m,
The authors declare no competing financial interest.
1H), 8.11 (d, J = 8.4 Hz, 1H), 8.00 (dd, J = 8.0 Hz, 1.2 Hz, 1H), 7.75
(t, J = 7.6 Hz, 1H), 7.60−7.55 (m, 2H), 7.44−7.40 (m, 2H), 7.38−
7.36 (m, 3H), 7.28 (dd, J = 8.0 Hz, 4.0 Hz, 1H), 2.82 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ 146.9, 146.3, 146.0, 142.1, 134.8, 134.3,
133.6, 131.2, 128.6, 127.4, 127.1, 126.9, 125.8, 125.5, 123.8, 121.1,
20.5; IR (KBr) ν 3052, 1587, 1573, 1442, 1424, 1382, 1021, 871, 828,
786, 760, 732, 696 cm−1. Anal. Found (calcd) for C20H15N: C, 89.22
(89.19); H, 5.60 (5.61); N, 5.18 (5.20).
ACKNOWLEDGMENTS
This work was supported by grants from the NSFC (21572155,
21372175).
■
REFERENCES
■
(1) (a) Pu, L. Chem. Rev. 1998, 98, 2405−2494. (b) Lloyd-Williams,
P.; Giralt, E. Chem. Soc. Rev. 2001, 30, 145−157. (c) Khalafi-Nezhad,
A.; Panahi, F. J. Organomet. Chem. 2012, 717, 141−146. (d) Iranpoor,
N.; Panahi, F.; Jamedi, F. J. Organomet. Chem. 2015, 781, 6−10.
(2) (a) Miyaura, N. Topics in Current Chemistry; Springer-Verlag:
New York, 2002. (b) de Meijere, A.; Diederich, F. Metal-Catalyzed
Cross-Coupling Reactions, 2nd ed.; Wiley-VCH: Weinheim, Germany,
2004.
5,10-Diphenylbenzo[h]quinoline (3bb). Yellow solid (27.5 mg,
1
yield 83%): H NMR (400 MHz, CDCl3) δ 8.43−8.42 (m, 1H), 8.15
(dd, J = 8.4, 1.2 Hz, 1H), 7.93 (d, J = 8.4 Hz, 1H), 7.83 (s, 1H), 7.71
(t, J = 7.6 Hz, 1H), 7.58−7.55 (m, 5H), 7.46−7.37 (m, 6H), 7.28−
7.25 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 146.5, 141.7, 139.5,
138.0, 134.4, 133.5, 131.4, 130.3, 130.0, 128.7, 128.6, 128.5, 128.3,
128.0, 127.7, 127.4, 127.3, 126.4, 125.9, 125.6, 120.8; IR (KBr) ν 3055,
3025, 1567, 1513, 1492, 1386, 806, 758, 735, 703 cm−1. Anal. Found
(calcd) for C25H17N: C, 90.64 (90.60); H, 5.20 (5.17); N, 4.21 (4.23).
5-(Naphthalen-2-yl)-10-phenylbenzo[h]quinoline (3bc). Yellow
(3) For selected reviews on cross-coupling reactions, see: (a) Hassan,
J.; Sevignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M. Chem. Rev. 2002,
́
1
solid (30.5 mg, yield 80%): H NMR (400 MHz, CDCl3) δ 8.32 (d,
102, 1359−1469. (b) Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed.
2002, 41, 4176−4211. (c) Fagnou, K.; Lautens, M. Chem. Rev. 2003,
103, 169−196. (d) Nicolaou, K. C.; Bulger, P. G.; Sarlah, D. Angew.
Chem., Int. Ed. 2005, 44, 4442−4489. (e) Corbet, J.-P.; Mignani, G.
Chem. Rev. 2006, 106, 2651−2710. (f) Negishi, E. Bull. Chem. Soc. Jpn.
2007, 80, 233−257. (g) Martin, R.; Buchwald, S. L. Acc. Chem. Res.
J = 7.6 Hz, 1H), 8.08−8.03 (m, 1H), 7.90−7.81 (m, 3H), 7.61−7.54
(m, 2H), 7.48−7.43 (m, 5H), 7.33−7.26 (m, 6H), 7.16−7.14 (m, 1H);
13C NMR (100 MHz, CDCl3) δ 147.1, 147.0, 146.6, 146.5, 141.7,
141.6, 137.9, 134.4, 133.5, 131.5, 131.4, 130.0, 128.8, 128.7, 128.5,
128.1, 128.0, 127.8, 127.7, 127.4, 127.3, 125.6, 120.8, 119.1; IR (KBr)
ν 3051, 1597, 1513, 1412, 1383, 804, 738, 709 cm−1. Anal. Found
(calcd) for C29H19N: C, 91.27 (91.31); H, 5.01 (5.02); N, 3.68 (3.67).
7-Methoxy-10-phenylbenzo[h]quinoline (3bd). Pale yellow solid
2008, 41, 1461−1473. (h) Wurtz, S.; Glorius, F. Acc. Chem. Res. 2008,
̈
41, 1523−1533. (i) Yu, D.-G.; Li, B.-J.; Shi, Z.-J. Acc. Chem. Res. 2010,
43, 1486−1495. (j) Jana, R.; Pathak, T. P.; Sigman, M. S. Chem. Rev.
2011, 111, 1417−1492. (k) Liu, C.; Zhang, H.; Shi, W.; Lei, A. Chem.
1
(23.1 mg, yield 81%): H NMR (400 MHz, CDCl3) δ 8.43−8.40 (m,
G
DOI: 10.1021/acs.organomet.6b00238
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Rev. 2011, 111, 1780−1824. (l) Shi, W.; Liu, C.; Lei, A. Chem. Soc. Rev.
2011, 40, 2761−2776. (m) Han, F.-S. Chem. Soc. Rev. 2013, 42, 5270−
5298. (n) Bedford, R. B. Acc. Chem. Res. 2015, 48, 1485−1493.
(o) Tobisu, M.; Chatani, N. Acc. Chem. Res. 2015, 48, 1717−1726.
(p) Tollefson, E. J.; Hanna, L. E.; Jarvo, E. R. Acc. Chem. Res. 2015, 48,
2344−2353. (q) Cherney, A. H.; Kadunce, N. T.; Reisman, S. E. Chem.
Rev. 2015, 115, 9587−9652. (r) Abdoli, M.; Mirjafary, Z.; Saeidian, H.;
Kakanejadifard, A. RSC Adv. 2015, 5, 44371−44389. (s) Zhang, H.;
Zhang, X.-Y.; Dong, D.-Q.; Wang, Z.-L. RSC Adv. 2015, 5, 52824−
52831. (t) Wang, C.-Y.; Derosa, J.; Biscoe, M. R. Chem. Sci. 2015, 6,
5105−5113.
Xu, Z. J. Org. Chem. 2014, 79, 4799−4808. (l) Wang, Y.; Kang, Q. Org.
́
Lett. 2014, 16, 4190−4193. (m) Aïssa, C.; Crepin, D.; Tetlow, D. J.;
Ho, K. Y. T. Org. Lett. 2013, 15, 1322−1325. (n) Ishida, N.; Ikemoto,
W.; Murakami, M. J. Am. Chem. Soc. 2014, 136, 5912−5915. (o) Xia,
Y.; Liu, Z.; Liu, Z.; Ge, R.; Ye, F.; Hossain, M.; Zhang, Y.; Wang, J. J.
Am. Chem. Soc. 2014, 136, 3013−3015. (p) Souillart, L.; Parker, E.;
Cramer, N. Angew. Chem., Int. Ed. 2014, 53, 3001−3005. (q) Yu, H.;
Wang, C.; Yang, Y.; Dang, Z.-M. Chem. - Eur. J. 2014, 20, 3839−3848.
(r) Xu, T.; Dong, G. Angew. Chem., Int. Ed. 2014, 53, 10733−10736.
(s) Parker, E.; Cramer, N. Organometallics 2014, 33, 780−787.
(t) Souillart, L.; Cramer, N. Angew. Chem., Int. Ed. 2014, 53, 9640−
9644. (u) Lei, Z.-Q.; Li, H.; Li, Y.; Zhang, X.-S.; Chen, K.; Wang, X.;
Sun, J.; Shi, Z.-J. Angew. Chem., Int. Ed. 2012, 51, 2690−2694. (v) Wu,
J.-Q.; Qiu, Z.-P.; Zhang, S.-S.; Liu, J.-G.; Lao, Y.-X.; Gu, L.-Q.; Huang,
Z.-S.; Li, J.; Wang, H. Chem. Commun. 2015, 51, 77−80. (w) Shaw, M.
H.; McCreanor, N. G.; Whittingham, W. G.; Bower, J. F. J. Am. Chem.
Soc. 2015, 137, 463−468. (x) Zeng, R.; Dong, G. J. Am. Chem. Soc.
(4) For selected reviews on Suzuki−Miyaura cross-coupling
reactions, see: (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95,
2457−2483. (b) Martin, R.; Buchwald, S. L. Acc. Chem. Res. 2008, 41,
1461−1473. (c) So, C. M.; Kwong, F. Y. Chem. Soc. Rev. 2011, 40,
4963−4972. (d) Lennox, A. J. J.; Lloyd-Jones, G. C. Chem. Soc. Rev.
2014, 43, 412−443. (e) Cornella, J.; Zarate, C.; Martin, R. Chem. Soc.
Rev. 2014, 43, 8081−8097. (f) Chen, M.-L.; Yin, B.-S.; Song, J.-X. Prog.
Chem. 2015, 27, 641−654.
2015, 137, 1408−1411. (y) Heath, R.; Muller-Bunz, H.; Albrecht, M.
̈
Chem. Commun. 2015, 51, 8699−8701. (z) Masarwa, A.; Weber, M.;
Sarpong, R. J. Am. Chem. Soc. 2015, 137, 6327−6334.
(5) Yu, J.-Q.; Shi, Z.-J. Topics in Current Chemistry; Springer-Verlag,
New York, 2010.
(10) (a) Nishimura, T.; Ohe, K.; Uemura, S. J. Am. Chem. Soc. 1999,
121, 2645−2646. (b) Nishimura, T.; Ohe, K.; Uemura, S. J. Org. Chem.
2001, 66, 1455−1465. (c) Matsumura, S.; Maeda, Y.; Nishimura, T.;
Uemura, S. J. Am. Chem. Soc. 2003, 125, 8862−8869. (d) Nishimura,
T.; Yoshinaka, T.; Nishiguchi, Y.; Maeda, Y.; Uemura, S. Org. Lett.
2005, 7, 2425−2427. (e) Matsuda, T.; Makino, M.; Murakami, M.
Angew. Chem., Int. Ed. 2005, 44, 4608−4611. (f) Matsuda, T.; Shigeno,
M.; Makino, M.; Murakami, M. Org. Lett. 2006, 8, 3379−3381.
(g) Murakami, M.; Ashida, S.; Matsuda, T. J. Am. Chem. Soc. 2006,
128, 2166−2167. (h) Matsuda, T.; Shigeno, M.; Murakami, M. J. Am.
(6) For selected reviews on C−H activation reactions, see: (a) Jia, C.;
Kitamura, T.; Fujiwara, Y. Acc. Chem. Res. 2001, 34, 633−639.
(b) Lewis, J. C.; Bergman, R. G.; Ellman, J. A. Acc. Chem. Res. 2008,
41, 1013−1025. (c) Colby, D. A.; Bergman, R. G.; Ellman, J. A. Chem.
Rev. 2010, 110, 624−655. (d) Cho, S. H.; Kim, J. Y.; Kwak, J.; Chang,
S. Chem. Soc. Rev. 2011, 40, 5068−5083. (e) Wencel-Delord, J.; Droge,
̈
T.; Liu, F.; Glorius, F. Chem. Soc. Rev. 2011, 40, 4740−4761. (f) Song,
G.; Wang, F.; Li, X. Chem. Soc. Rev. 2012, 41, 3651−3678.
(g) Hashiguchi, B. G.; Bischof, S. M.; Konnick, M. M.; Periana, R.
A. Acc. Chem. Res. 2012, 45, 885−898. (h) Gaillard, S.; Cazin, C. S. J.;
Nolan, S. P. Acc. Chem. Res. 2012, 45, 778−187. (i) Arockiam, P. B.;
Bruneau, C.; Dixneuf, P. H. Chem. Rev. 2012, 112, 5879−5918.
(j) Johnson, K. R. D.; Hayes, P. G. Chem. Soc. Rev. 2013, 42, 1947−
1960. (k) Li, B.; Dixneuf, P. H. Chem. Soc. Rev. 2013, 42, 5744−5767.
(l) Baillie, R. A.; Legzdins, P. Acc. Chem. Res. 2014, 47, 330−340.
Chem. Soc. 2007, 129, 12086−12087. (i) Furstner, A.; Majima, K.;
̈
Martín, R.; Krause, H.; Kattnig, E.; Goddard, R.; Lehmann, C. W. J.
Am. Chem. Soc. 2008, 130, 1992−2004. (j) Matsuda, T.; Shigeno, M.;
Murakami, M. Org. Lett. 2008, 10, 5219−5221. (k) Seiser, T.; Cramer,
N. Org. Biomol. Chem. 2009, 7, 2835−2840. (l) Shigeno, M.;
Yamamoto, T.; Murakami, M. Chem. - Eur. J. 2009, 15, 12929−
12931. (m) Seiser, T.; Cramer, N. J. Am. Chem. Soc. 2010, 132, 5340−
5341. (n) Wang, J.; Zheng, N. Angew. Chem., Int. Ed. 2015, 54, 11424−
(m) Arnold, P. L.; McMullon, M. W.; Rieb, J.; Kuhn, F. E. Angew.
̈
Chem., Int. Ed. 2015, 54, 82−100. (n) Segawa, Y.; Maekawa, T.; Itami,
K. Angew. Chem., Int. Ed. 2015, 54, 66−81. (o) Lobana, T. S. RSC Adv.
2015, 5, 37231−37274. (p) Wu, X.-F. Chem. - Eur. J. 2015, 21,
12252−12265. (q) Topczewski, J. J.; Sanford, M. S. Chem. Sci. 2015, 6,
70−76.
́ ́
11427. (o) Julia-Hernandez, F.; Ziadi, A.; Nishimura, A.; Martin, R.
Angew. Chem., Int. Ed. 2015, 54, 9537−9541.
(11) (a) Terao, Y.; Wakui, H.; Satoh, T.; Miura, M.; Nomura, M. J.
Am. Chem. Soc. 2001, 123, 10407−10408. (b) Terao, Y.; Nomoto, M.;
Satoh, T.; Miura, M.; Nomura, M. J. Org. Chem. 2004, 69, 6942−6944.
(c) Nakano, M.; Satoh, T.; Miura, M. J. Org. Chem. 2006, 71, 8309−
8311. (d) Hayashi, S.; Hirano, K.; Yorimitsu, H.; Oshima, K. J. Am.
Chem. Soc. 2006, 128, 2210−2211. (e) Niwa, T.; Yorimitsu, H.;
Oshima, K. Angew. Chem., Int. Ed. 2007, 46, 2643−2645. (f) Iwasaki,
M.; Hayashi, S.; Hirano, K.; Yorimitsu, H.; Oshima, K. J. Am. Chem.
Soc. 2007, 129, 4463−4469. (g) Hayashi, S.; Hirano, K.; Yorimitsu, H.;
Oshima, K. J. Am. Chem. Soc. 2008, 130, 5048−5049. (h) Iwasaki, M.;
Iino, S.; Nishihara, Y. Org. Lett. 2013, 15, 5326−5329.
(7) Dong, G. Topics in Current Chemistry; Springer-Verlag: New
York, 2014.
(8) For reviews of C−C bond activation, see: (a) Crabtree, R. H.
Chem. Rev. 1985, 85, 245−269. (b) Jones, W. D. Nature 1993, 364,
676−677. (c) Rybtchinski, B.; Milstein, D. Angew. Chem., Int. Ed. 1999,
38, 870−883. (d) Murakami, M.; Ito, Y. Top. Organomet. Chem. 1999,
3, 97−129. (e) van der Boom, M. E.; Milstein, D. Chem. Rev. 2003,
103, 1759−1792. (f) Takahashi, T.; Kanno, K. Top. Organomet. Chem.
2004, 8, 217−236. (g) Jun, C.-H. Chem. Soc. Rev. 2004, 33, 610−618.
(h) Jun, C.-H.; Park, J.-W. Top. Organomet. Chem. 2007, 24, 117−143.
(i) Ruhland, K. Eur. J. Org. Chem. 2012, 2012, 2683−2706. (j) Souillart,
L.; Cramer, N. Chem. Rev. 2015, 115, 9410−9464.
(9) For selected recent reactions of C−C bond activation, see:
(a) Zhang, C.; Xu, Z.; Shen, T.; Wu, G.; Zhang, L.; Jiao, N. Org. Lett.
2012, 14, 2362−2365. (b) Xu, T.; Dong, G. Angew. Chem., Int. Ed.
2012, 51, 7567−7571. (c) Lutz, J. P.; Rathbun, C. M.; Stevenson, S.
M.; Powell, B. M.; Boman, T. S.; Baxter, C. E.; Zona, J. M.; Johnson, J.
B. J. Am. Chem. Soc. 2012, 134, 715−722. (d) Youn, S. W.; Kim, B. S.;
Jagdale, A. R. J. Am. Chem. Soc. 2012, 134, 11308−11311. (e) Wang, J.;
Liu, B.; Zhao, H.; Wang, J. Organometallics 2012, 31, 8598−8607.
(f) Gao, G.; Zhu, Y.; Lian, M.; Liu, M.; Yuan, J.; Yin, G.; Wu, A. J. Org.
Chem. 2012, 77, 9865−9870. (g) Zhang, C.; Feng, P.; Jiao, N. J. Am.
Chem. Soc. 2013, 135, 15257−15262. (h) Zhu, Y.; Yan, H.; Lu, L.; Liu,
D.; Rong, G.; Mao, J. J. Org. Chem. 2013, 78, 9898−9905. (i) Feng, P.;
Sun, X.; Su, Y.-J.; Li, X.-Y.; Zhang, L.-H.; Shi, X.-D.; Jiao, N. Org. Lett.
2014, 16, 3388−3391. (j) Gu, L.; Jin, C.; Zhang, H.; Zhang, L. J. Org.
Chem. 2014, 79, 8453−8456. (k) Zhang, J.; Wu, D.; Chen, X.; Liu, Y.;
(12) (a) Nishimura, T.; Araki, H.; Maeda, Y.; Uemura, S. Org. Lett.
2003, 5, 2997−2999. (b) Uto, T.; Shimizu, M.; Ueura, K.; Tsurugi, H.;
Satoh, T.; Miura, M. J. Org. Chem. 2008, 73, 298−300. (c) Takada, Y.;
Hayashi, S.; Hirano, K.; Yorimitsu, H.; Oshima, K. Org. Lett. 2006, 8,
2515−2517. (d) Sai, M.; Yorimitsu, H.; Oshima, K. Angew. Chem., Int.
Ed. 2011, 50, 3294−3298. (e) Sumida, Y.; Hayashi, S.; Hirano, K.;
Yorimitsu, H.; Oshima, K. Org. Lett. 2008, 10, 1629−1632.
(13) Chiba, S.; Xu, Y.-J.; Wang, Y.-F. J. Am. Chem. Soc. 2009, 131,
12886−12887.
(14) (a) Li, H.; Li, Y.; Zhang, X.-S.; Chen, K.; Wang, X.; Shi, Z.-J. J.
Am. Chem. Soc. 2011, 133, 15244−15247. (b) Zhang, X.-S.; Li, Y.; Li,
H.; Chen, K.; Lei, Z.-Q.; Shi, Z.-J. Chem. - Eur. J. 2012, 18, 16214−
16225. (c) Chen, K.; Li, H.; Lei, Z.-Q.; Li, Y.; Ye, W.-H.; Zhang, L.-S.;
Sun, J.; Shi, Z.-J. Angew. Chem., Int. Ed. 2012, 51, 9851−9855.
(d) Chen, K.; Li, H.; Li, Y.; Zhang, X.-S.; Lei, Z.-Q.; Shi, Z.-J. Chem.
Sci. 2012, 3, 1645−1649.
(15) (a) Wang, J.; Chen, W.; Zuo, S.; Liu, L.; Zhang, X.; Wang, J.
Angew. Chem., Int. Ed. 2012, 51, 12334−12338. (b) Wang, J.; Zuo, S.;
H
DOI: 10.1021/acs.organomet.6b00238
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Chen, W.; Zhang, X.; Tan, K.; Tian, Y.; Wang, J. J. Org. Chem. 2013,
78, 8217−8231.
(16) Yu, D.-G.; Li, B.-J.; Shi, Z.-J. Acc. Chem. Res. 2010, 43, 1486−
1495.
(17) Feng, C.; Liu, Y.; Peng, S.; Shuai, Q.; Deng, G.; Li, C.-J. Org.
Lett. 2010, 12, 4888−4891.
(18) Lipshutz, B. H.; Frieman, B.; Birkedal, H. Org. Lett. 2004, 6,
2305−2308.
(19) Karthikeyan, J.; Parthasarathy, K.; Cheng, C.-H. Chem. Commun.
2011, 47, 10461−10463.
(20) Hamada, Y.; Takeuchi, I. J. Org. Chem. 1977, 42, 4209−4213.
(21) Kochi, T.; Urano, S.; Seki, H.; Mizushima, E.; Sato, M.;
Kakiuchi, F. J. Am. Chem. Soc. 2009, 131, 2792−2793.
(22) Blanck, S.; Cruchter, T.; Vultur, A.; Riedel, R.; Harms, K.;
Herlyn, M.; Meggers, E. Organometallics 2011, 30, 4598−4606.
(23) Liu, C.; Yang, W. Chem. Commun. 2009, 6267−6269.
(24) Oi, S.; Fukita, S.; Hirata, N.; Watanuki, N.; Miyano, S.; Inoue, Y.
Org. Lett. 2001, 3, 2579−2581.
I
DOI: 10.1021/acs.organomet.6b00238
Organometallics XXXX, XXX, XXX−XXX