N-heterocyclic carbene derived Nickel-Pincer complexes: Efficient and applicable catalysts for Suzuki-Miyaura coupling reactions of aryl/alkenyl tosylates and mesylates

Article abstract of DOI:10.1002/ejoc.200900067

Catalytic activities of NHC-derived nickel-pincer complexes for the Suzuki-Miyaura coupling reactions of aryl/alkenyl to- sylates and mesylates are described. In the presence of a catalytic amount of nickelacycle 1a, a wide array of tosylates and mesylates reacted with several aryl- and alkenylboronic acids to afford the coupling products, generally in high yields. Fine tuning of the reaction conditions for each class of electrophiles was achieved only by choosing the appropriate reaction medium (DME for tosylates, dioxane for mesylates).

Full text of DOI:10.1002/ejoc.200900067

FULL PAPER
DOI: 10.1002/ejoc.200900067
N-Heterocyclic Carbene Derived Nickel–Pincer Complexes: Efficient and
Applicable Catalysts for Suzuki–Miyaura Coupling Reactions of Aryl/Alkenyl
Tosylates and Mesylates
Jun-ichi Kuroda,[a] Kiyofumi Inamoto,*[a] Kou Hiroya,[a] and Takayuki Doi*[a]
Keywords: Carbene ligands / Pincer complexes / Cross-coupling / Nickel
Catalytic activities of NHC-derived nickel–pincer complexes
for the Suzuki–Miyaura coupling reactions of aryl/alkenyl to-
sylates and mesylates are described. In the presence of a
catalytic amount of nickelacycle 1a, a wide array of tosylates
and mesylates reacted with several aryl- and alkenylboronic
acids to afford the coupling products, generally in high
yields. Fine tuning of the reaction conditions for each class of
electrophiles was achieved only by choosing the appropriate
reaction medium (DME for tosylates, dioxane for mesylates).
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2009)
We recently reported the synthesis and evaluation of the
catalytic activities of N-heterocyclic carbene (NHC)-derived
nickel(II)–pincer complexes 1a–e (Figure 1), which turned
out to be excellent catalysts for C–C bond-forming coupling
reactions.[8,9] These nickel complexes, readily prepared from
inexpensive, commercially available materials, exhibit high
stability to both air and moisture, making them highly ap-
plicable catalysts. Herein, we disclose that our nickel–pincer
complexes efficiently catalyze the Suzuki–Miyaura coupling
processes of a range of aryl/alkenyl tosylates and mesylates
with aryl/alkenylboronic acids.[10]
Introduction
Palladium- and nickel-catalyzed cross-coupling reactions
are one of the most powerful methods for the assembly of
molecules such as natural products, pharmaceuticals, and
functional chemicals.[1] In this area, aryl/alkenyl triflates,
which are prepared from phenols or carbonyl compounds,
have often been employed as electrophiles in place of aryl/
alkenyl halides.[2] However, triflating reagents such as Tf2O
and PhNTf2 are relatively expensive, and triflates them-
selves are sometimes unstable in air and moisture. Aryl/alk-
enyl tosylates and mesylates have recently been regarded as
important alternatives to the above-mentioned traditional
electrophiles. They are easily prepared from inexpensive and
readily available starting materials, easier to handle crystal-
line solids, and more stable than the corresponding triflates.
Despite their considerably inert leaving-group activity, de-
velopment of the catalyst systems, which enable coupling
reactions of tosylates and mesylates to be performed, has
recently attracted much attention. Indeed, several examples
have realized their use in transition-metal-catalyzed C–C Figure 1. Nickel(II)–pincer complexes (Mes = mesityl, DIPP = 2,6-
and C–N bond-forming coupling reactions.[3–6] For exam-
diisopropylphenyl).
ple, Percec reported the Suzuki–Miyaura coupling reaction
of aryl mesylates in the presence of a NiCl2(dppe) cata-
lyst.[4b] The room temperature Suzuki–Miyaura coupling
Results and Discussion
reaction of aryl tosylates was also achieved by Hu by em-
ploying a Ni(cod)2/PCy3 catalyst system.[3c,3o] However,
there has been only a limited number of precedents for their
practical use in cross-coupling processes.[7]
Initial studies focused on the reaction of 4-(p-toluenesul-
fonyloxy)benzonitrile (2) with phenylboronic acid in the
presence of nickel–pincer complex 1a (5 mol-%) and K3PO4
(2 equiv.) to optimize the reaction conditions (Table 1).
Whereas solvents such as DMSO, DMF, dichloroethane,
and dioxane were not effective for this process (Table 1, En-
tries 1–4), the use of toluene, acetonitrile, and THF pro-
vided moderate to good yields (Table 1, Entries 5–7). DME
proved to be the best solvent for this reaction, producing
[a] Graduate School of Pharmaceutical Sciences, Tohoku Univer-
sity
6-3 Aoba, Aramaki, Aoba-ku, 980-8578 Sendai, Japan
Fax: +81-22-795-6864
E-mail: inamoto@mail.pharm.tohoku.ac.jp,
doi_taka@mail.pharm.tohoku.ac.jp
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J.-i. Kuroda, K. Inamoto, K. Hiroya, T. Doi
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coupling product 3 in excellent yield (95%; Table 1, En- enyl tosylates 37–41 were efficiently coupled with aryl-
try 8). K3PO4 was also crucial for efficient conversion.[11] boronic acids in the presence of a catalytic amount of 1a,
Decreasing either the reaction temperature or the catalyst and 4-arylated coumarins 42–48, 2-pyranones 49–51, and 2-
loading led to poorer results (Table 1, Entries 9 and 10). quinolones 52–54 were successfully obtained (Table 3).[12–14]
Complex 1b, which has two fused six-membered rings, sim-
ilar to 1a, also showed high performance for this process,
although a longer reaction time was necessary to reach
completion of the reaction (Table 1, Entry 11). Interest-
ingly, complexes 1c–e, possessing the five-membered metalla-
cycle backbone, were not as active as 1a and 1b. This result
is contrary to the previous observation[8a] in which reac-
tions of aryl halides proceeded faster in the presence of 1c
and 1d than in the presence of 1a and 1b, plausibly indicat-
ing that the rate-determining step during the catalytic cycle
would be different for the reactions of aryl tosylates than
for aryl halides. The precise reaction mechanism remains to
be elucidated.
Table 2. Coupling of various aryl tosylates with aryl/alkenylboronic
acids.[a]
Table 1. Optimization of reaction conditions for coupling of aryl
tosylate 2 with PhB(OH)2.[a]
Entry
1
Solvent
Yield [%][b,c]
1
2
3
4
5
6
7
8
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1b
1c
1d
1e
DMSO
DMF
ClCH2CH2Cl
dioxane
toluene
CH3CN
THF
11 (39)
37 (41)
43 (48)
40 (47)
58 (26)
63 (29)
69 (25)
95
70 (26)
59 (33)
84
37 (49)
37 (52)
33 (55)
DME
DME
DME
DME
DME
DME
DME
9[d]
10[e]
11[f]
12
13
14
[a] Reagents: 4-(p-toluenesulfonyloxy)benzonitrile (0.10 mmol),
PhB(OH)2 (0.30 mmol), 1 (0.0050 mmol), K3PO4 (0.20 mmol), and
solvent (1 mL) in a sealed tube. [b] Isolated yield. [c] Figure in pa-
rentheses is the recovery yield of 2. [d] 100 °C. [e] 1 mol-% of 1a
was used. [f] 48 h.
The substrate scope of this system was next examined by
using various aryl tosylates and boronic acids. Under the
optimal conditions identified, electron-poor aryl tosylates 2
and 4 were treated with a range of aryl- and alkenylboronic
acids in the presence of 1a (5 mol-%), and the correspond-
ing coupled products 11–20 were obtained in good to high
yields (Table 2, Entries 1–10). In contrast, electron-rich or
sterically hindered tosylates 5–7 remained as poorly reactive
substrates for this process (Table 2, Entries 11–13). The
combinations of aryl tosylates 8–10, derived from naphthols
and 3-hydroxypyridine, with boronic acids were also effec-
tive for the synthesis of biaryl and styrene compounds 24–
36 (Table 2, Entries 14–26).
Alkenyl tosylates turned out to be more reactive than
aryl tosylates in our catalytic system. Thus, activated alk-
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NHC-Derived Nickel–Pincer Complexes
Table 2. (Continued)
boronic acid was first carried out under the optimized reac-
tion conditions developed for aryl tosylates, resulting in a
low yield (Table 4, Entry 1). Subsequent screening of the
solvents revealed that the use of dioxane greatly enhanced
Table 3. Coupling of activated alkenyl tosylates with arylboronic
acids.[a]
[a] Reagents: aryl tosylate (0.10 mmol), RB(OH)2 (0.30 mmol), 1a
(0.0050 mmol), K3PO4 (0.30 mmol), and DME (1 mL) in a sealed
tube. [b] Isolated yield. [c] 48 h.
The capability of nickel–pincer complexes to participate
in for cross-coupling reactions of aryl/alkenyl tosylates en-
couraged us to use these catalysts in the reactions of aryl
mesylates, which are less reactive but more atom-economi-
cal substrates. The reaction of mesylate 55 with phenyl-
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J.-i. Kuroda, K. Inamoto, K. Hiroya, T. Doi
FULL PAPER
Table 3. (Continued)
Table 5. Coupling of aryl mesylates with aryl/alkenylboronic ac-
ids.[a]
[a] Reagents: alkenyl tosylate (0.10 mmol), ArB(OH)2 (0.30 mmol),
1a (0.0050 mmol), K3PO4 (0.20 mmol), and DME (1 mL) in a
sealed tube. [b] ArB(OH)2; A: Ar = Ph, B: Ar = p-MeOC6H4, C:
Ar = p-NCC6H4. [c] Isolated yield. [d] 0.15 mmol of ArB(OH)2 was
used.
the yield, giving coupling product 3 in fairly good yield
(Table 4, Entry 8). Here again, complexes 1a and 1b exhib-
ited higher catalytic activity than complexes 1c, 1d, and 1e
(Table 4, Entries 8 and 9 vs. 10–12).
Table 4. Optimization of reaction conditions for the coupling of
aryl mesylate 55 with PhB(OH)2.[a]
Entry
1
Solvent
Yield [%][b,c]
1
2
3
4
5
6
7
8
1a
1a
1a
1a
1a
1a
1a
1a
1b
1c
1d
1e
DME
THF
DMSO
DMF
8 (86)
10 (75)
0 (79)
trace (82)
40 (44)
16 (73)
38 (56)
63 (23)
56 (24)
38 (46)
25 (55)
28 (58)
ClCH2CH2Cl
CH3CN
toluene
dioxane
dioxane
dioxane
dioxane
dioxane
[a] Reagents: an aryl tosylate (0.10 mmol), RB(OH)2 (0.30 mmol),
1a (0.0050 mmol), K3PO4 (0.30 mmol), and DME (1 mL) in a
sealed tube. [b] Isolated yield.
9
10
11
12
Conclusions
In summary, we developed a method for the Suzuki–
Miyaura coupling reactions of aryl/alkenyl tosylates and
mesylates by using NHC-derived nickel(II)–pincer com-
plexes. Suitable substrates include both aryl and alkenyl tos-
ylates with various substituents in this system. They are ef-
ficiently cross-coupled with an array of aryl/alkenylboronic
[a] Reagents: 4-(methanesulfonyloxy)benzonitrile (0.10 mmol),
PhB(OH)2 (0.30 mmol), 1 (0.0050 mmol), K3PO4 (0.20 mmol), and
solvent (1 mL) in a sealed tube. [b] Isolated yield. [c] Figure in pa-
rentheses is the recovery yield of 55.
Several aryl mesylates 55–59 were also treated with aryl/ acids, especially in the presence of catalyst 1a, producing
alkenylboronic acids in the presence of nickel–pincer com- the corresponding coupling products generally in high
plex 1a to furnish the corresponding coupling compounds yields. More importantly, reactions employing aryl mesyl-
in moderate to good yields (Table 5).
ates as electrophiles – a more challenging process – also
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NHC-Derived Nickel–Pincer Complexes
(100 MHz, CDCl3): δ = 21.7, 26.6, 122.5, 128.5, 129.9, 130.0, 132.2,
135.7, 145.7, 153.0, 196.6 ppm. MS (EI): m/z (%) = 290 (65) [M+],
275 (15), 155 (100), 91 (78). HRMS: calcd. for C15H14O4S
290.0613; found 290.0601.
successfully proceeded only by changing the solvent of the
optimized conditions developed for tosylates. High catalytic
activity of nickel–pincer complexes as well as their facile
preparation would make this methodology an attractive ad-
dition to the repertoire of strategies for the catalytic acti-
vation of tosylates and mesylates. Further studies involving
elucidation of the precise reaction mechanism and applica-
tion of the catalysts to a range of cross-coupling reactions
of aryl/alkenyl sulfonates are underway.
4-(p-Toluenesulfonyloxy)anisole (5): 92% (1.0 g) from 4-meth-
oxyphenol (0.50 g, 4.0 mmol). Colorless needles; m.p. 69–70 °C
(hexane/AcOEt, ref.[3c] 69–71 °C). IR (film): ν = 1094, 1196, 1371,
˜
1
1502, 1597 cm–1. H NMR (400 MHz, CDCl3): δ = 2.45 (s, 3 H),
3.76 (s, 3 H), 6.76 (d, J = 10.0 Hz, 2 H), 6.88 (dt, J = 10.0 Hz, 2
H), 7.30 (d, J = 8.4 Hz, 2 H), 7.69 (d, J = 8.4 Hz, 2 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 21.7, 55.5, 114.5, 123.3, 128.6, 129.7,
132.4, 143.1, 145.2, 158.2 ppm. MS (EI): m/z (%) = 278 (44) [M+],
155 (2), 123 (100), 91 (5). HRMS: calcd. for C14H14O4S 278.0613;
found 278.0596.
Experimental Section
General Methods: 1H NMR spectra were recorded with a JEOL
JNM-AL400 (400 MHz) spectrometer by using tetramethylsilane
(TMS) as an internal standard. Chemical shifts (δ) are given from
TMS (δ =0 ppm) and coupling constants are expressed in Hertz
[Hz]. The following abbreviations are used: s = singlet, d = doublet,
t = triplet, q = quartet, sext. = sextet, dd = doublet of doublets, dt
= doublet of triplets, td = triplet of doublets, ddd, = doublet of
doublets of doublets, and m = multiplet. 13C NMR spectra were
recorded with a JEOL JNM-AL400 (100 MHz) spectrometer and
chemical shifts (δ) are given from 13CDCl3 (δ =77.0 ppm). Mass
spectra and high-resolution mass spectra were measured with
JEOL JMS-DX303 and MS-AX500 instruments, respectively. IR
spectra were recorded with a Shimadzu FTIR-8400. Melting points
were measured with a Yazawa micro melting point apparatus and
are uncorrected. Suzuki–Miyaura coupling reactions were carried
out under an argon atmosphere. Nickel(II)–pincer complexes 1a–e
were prepared according to previously established procedure.[8a,8c]
K3PO4 was dried while heating at 150 °C. All other chemicals, in-
cluding anhydrous solvents, were purchased from commercial sup-
pliers and used as received.
2-(p-Toluenesulfonyloxy)benzonitrile (6): 68% (0.77 g) from 2-cya-
nophenol (0.50 g, 4.2 mmol). Colorless plates; m.p. 88–90 °C (hex-
ane/AcOEt, ref.[15] 88–89 °C). IR (film): ν = 1194, 1383, 1485, 1599,
˜
1
2235 cm–1. H NMR (400 MHz, CDCl3): δ = 2.46 (s, 3 H), 7.35–
7.39 (m, 3 H), 7.50 (dd, J = 8.6, 0.8 Hz, 1 H), 7.58 (dd, J = 7.8,
1.3 Hz, 1 H), 7.63 (ddd, J = 8.6, 7.8, 1.3 Hz, 1 H), 7.82 (d, J =
8.8 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.7, 107.7,
114.4, 123.7, 127.3, 128.7, 130.0, 131.5, 133.7, 134.2, 146.3,
150.2 ppm. MS (EI): m/z (%) = 273 (21) [M+], 155 (72), 91 (100).
HRMS: calcd. for C14H11NO3S 273.0460; found 273.0457.
2-(p-Toluenesulfonyloxy)acetophenone (7): 80% (0.85 g) from 2-ace-
tylphenol (0.50 g, 3.7 mmol). Colorless plates; m.p. 95–96 °C (hex-
ane/AcOEt, ref.[16] 97–98 °C). IR (film): ν = 1198, 1373, 1479, 1601,
˜
1693 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.46 (s, 3 H), 2.51 (s,
3 H), 7.10 (d, J = 8.4 Hz, 1 H), 7.31–7.35 (m, 3 H), 7.43 (ddd, J =
8.4, 8.0, 1.1 Hz, 1 H), 7.64 (dd, J = 8.4, 2.0 Hz, 1 H), 7.68 (d, J =
8.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.7, 30.4,
123.3, 127.2, 128.5, 129.9, 130.1, 132.0, 132.8, 133.8, 145.9, 147.1,
197.8 ppm. MS (EI): m/z (%) = 290 (2) [M+], 275 (6), 155 (56),
121 (49), 91 (100). HRMS: calcd. for C15H14O4S 290.0613; found
290.0617.
Typical Procedure for Sulfonylation of Phenols [4-(p-Toluene-
sulfonyloxy)benzonitrile (2)]: To
a solution of 4-cyanophenol
(0.50 g, 4.2 mmol) in CH2Cl2 (20 mL)/pyridine (5 mL) was added
TsCl (1.2 g, 6.3 mmol) at 0 °C. After warming to room temperature,
the mixture was stirred for 12–48 h. The reaction mixture was
treated with saturated aqueous NH4Cl (15 mL) followed by extrac-
tion with CHCl3 (15 mLϫ3). The combined extracts were washed
with 3  HCl aq. (15 mLϫ2) and saturated aqueous NaCl
(15 mLϫ2), and the solvent was removed under reduced pressure.
The residue was purified by silica gel column chromatography
using hexane/AcOEt (4:1) as an eluent to obtain a colorless solid
(1.0 g, 87%). The solid was recrystallized from hexane/AcOEt to
obtain colorless plates.
1-(p-Toluenesulfonyloxy)naphthalene (8): 94% (0.97 g) from 1-naph-
thol (0.50 g, 3.5 mmol). Colorless plates; m.p. 89–91 °C (hexane/
AcOEt, ref.[17] 90–92 °C). IR (film): ν = 1190, 1373, 1597 cm–1. 1H
˜
NMR (400 MHz, CDCl3): δ = 2.41 (s, 3 H), 7.21 (d, J = 8.0 Hz, 1
H), 7.27 (d, J = 8.4 Hz, 2 H), 7.36 (t, J = 8.0 Hz, 1 H), 7.40–7.48
(m, 2 H), 7.73 (d, J = 8.4 Hz, 1 H), 7.77–7.81 (m, 3 H), 7.90 (d, J
= 8.4 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.7, 118.4,
121.8, 125.1, 126.65, 126.68, 127.0, 127.3, 127.7, 128.5, 129.8,
132.9, 134.7, 145.4, 145.8 ppm. MS (EI): m/z (%) = 298 (100) [M+],
155 (23), 143 (96), 115 (21), 91 (15). HRMS: calcd. for C17H14O3S
298.0664; found 298.0649.
4-(p-Toluenesulfonyloxy)benzonitrile (2): 87% (1.0 g) from 4-cya-
nophenol (0.50 g, 4.2 mmol). Colorless plates; m.p. 88–89 °C (hex-
2-(p-Toluenesulfonyloxy)naphthalene (9): 65% (0.67 g) from 2-naph-
thol (0.50 g, 3.5 mmol). Colorless needles; m.p. 119–120 °C (hex-
ane/AcOEt, ref.[15] 90.4–90.9 °C). IR (film): ν = 1204, 1377, 1497,
˜
ane/AcOEt, ref.[3c] 122–124 °C). IR (film):
ν = 1190, 1377,
˜
1
1599, 2232 cm–1. H NMR (400 MHz, CDCl3): δ = 2.47 (s, 3 H),
1595 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.44 (s, 3 H), 7.10
(dd, J = 9.0, 2.2 Hz, 1 H), 7.30 (d, J = 8.4 Hz, 2 H), 7.47–7.50
(m, 3 H), 7.72–7.76 (m, 4 H), 7.80–7.82 (m, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 21.7, 119.9, 121.2, 126.3, 126.8, 127.7,
127.9, 128.6, 129.7, 129.8, 131.9, 132.5, 133.5, 145.3, 147.2 ppm.
MS (EI): m/z (%) = 298 (100) [M+], 155 (46), 143 (54), 115 (39), 91
(31). HRMS: calcd. for C17H14O3S 298.0664; found 298.0648.
7.14 (d, J = 8.6 Hz, 2 H), 7.35 (d, J = 8.2 Hz, 2 H), 7.61 (d, J =
8.6 Hz, 2 H), 7.72 (d, J = 8.2 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 21.7, 111.2, 117.7, 123.4, 128.4, 130.0, 131.8, 133.9,
146.1, 152.5 ppm. MS (EI): m/z (%) = 273 (24) [M+], 155 (100),
119 (2), 91 (75). HRMS: calcd. for C14H11NO3S 273.0460; found
273.0444.
4-(p-Toluenesulfonyloxy)acetophenone (4): 72% (0.56 g) from 4-ace-
tylphenol (0.50 g, 3.7 mmol). Colorless needles; m.p. 69–70 °C
3-(p-Toluenesulfonyloxy)pyridine (10): 43% (0.57 g) from 3-hy-
(hexane/AcOEt, ref.[3c] 67–69 °C). IR (film): ν = 1200, 1377, 1497, droxypyridine (0.50 g, 5.3 mmol). Colorless plates; m.p. 73–75 °C
˜
1597, 1686 cm–1. H NMR (400 MHz, CDCl3): δ = 2.45 (s, 3 H), (hexane/AcOEt, ref.[5n] 72–73 °C). IR (film): ν = 1200, 1367, 1475,
1
˜
2.57 (s, 3 H), 7.09 (d, J = 8.6 Hz, 2 H), 7.32 (d, J = 8.4 Hz, 2 H),
1593 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.45 (s, 3 H), 7.29
7.72 (d, J = 8.4 Hz, 2 H), 7.90 (d, J = 8.6 Hz, 2 H) ppm. 13C NMR (dd, J = 8.5, 4.8 Hz, 1 H), 7.34 (d, J = 8.2 Hz, 2 H), 7.46 (ddd, J
Eur. J. Org. Chem. 2009, 2251–2261
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= 8.5, 2.6, 1.6 Hz, 1 H), 7.71 (d, J = 8.2 Hz, 2 H), 8.16 (d, J =
1
1607, 1628, 1732 cm–1. H NMR (400 MHz, CDCl3): δ = 2.47 (s,
2.6 Hz, 1 H), 8.50 (dd, J = 4.8, 1.6 Hz, 1 H) ppm. 13C NMR 3 H), 6.31 (s, 1 H), 7.25–729 (m, 1 H), 7.31 (d, J = 8.0 Hz, 1 H),
(100 MHz, CDCl3): δ = 21.7, 124.1, 128.5, 130.0, 130.1, 131.7, 7.39 (d, J = 8.2 Hz, 2 H), 7.57 (t, J = 8.0 Hz, 1 H), 7.64 (d, J =
144.0, 146.0, 146.4, 148.2 ppm. MS (EI): m/z (%) = 249 (57) [M+],
155 (100), 91 (79). HRMS: calcd. for C12H11NO3S 249.0460; found
249.0442.
8.0 Hz, 1 H), 7.90 (d, J = 8.2 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 21.9, 103.6, 114.9, 116.9, 123.1, 124.5, 128.4, 130.3,
131.6, 133.2, 146.8, 153.4, 157.7, 160.6 ppm. MS (EI): m/z (%) =
316 (24) [M+], 252 (69), 155 (100), 132 (20), 91 (64). HRMS: calcd.
for C16H12O5S 316.0405; found 316.0387.
4-Methanesulfonyloxybenzonitrile (55): 96% (0.80 g) from 4-cya-
nophenol (0.50 g, 4.2 mmol). Colorless plates; m.p. 92–93 °C (hex-
ane/AcOEt, ref.[18] 89–90 °C). IR (film): ν = 1153, 1202, 1362, 1499,
6-Methyl-4-(p-toluenesulfonyloxy)coumarin (38): 70% (0.39 g) from
4-hydroxy-6-methylcoumarin (0.30 g, 1.7 mmol). Colorless prisms;
˜
1
1601, 2233 cm–1. H NMR (400 MHz, CDCl3): δ = 3.23 (s, 3 H),
7.42 (d, J = 9.2 Hz, 2 H), 7.75 (d, J = 9.2 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 38.2, 111.5, 117.6, 123.0, 134.2, 151.9 ppm.
MS (EI): m/z (%) = 197 (50) [M+], 119 (100), 79 (24). HRMS:
calcd. for C8H7NO3S 197.0146; found 197.0128.
˜
m.p. 149–151 °C (hexane/AcOEt). IR (film): ν = 1061, 1200, 1364,
1489, 1597, 1630, 1732 cm–1. 1H NMR (400 MHz, CDCl3): δ =
2.37 (s, 3 H), 2.47 (s, 3 H), 6.26 (s, 1 H), 7.19 (d, J = 8.4 Hz, 1 H),
7.35–7.41 (m, 4 H), 7.90 (d, J = 8.8 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 20.8, 21.7, 103.5, 114.6, 116.6, 122.7, 128.4,
130.3, 131.8, 134.2, 134.4, 146.8, 151.6, 157.8, 160.9 ppm. MS (EI):
m/z (%) = 330 (100) [M+], 266 (55), 212 (11), 176 (10), 155 (100),
132 (22), 91 (74). HRMS: calcd. for C17H14O5S 330.0562; found
330.0548.
4-Methanesulfonyloxyacetophenone (56): 97% (0.78 g) from 4-ace-
tylphenol (0.50 g, 3.7 mmol). Colorless plates; m.p. 68–69 °C (hex-
ane/AcOEt, ref.[18] 71–72 °C). IR (film): ν = 1157, 1175, 1205, 1375,
˜
1
1501, 1597, 1682 cm–1. H NMR (400 MHz, CDCl3): δ = 2.61 (s,
3 H), 3.20 (s, 3 H), 7.38 (d, J = 8.8 Hz, 2 H), 8.03 (d, J = 8.8 Hz,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 26.6, 37.9, 122.0,
130.4, 135.9, 152.4, 196.4 ppm. MS (EI): m/z (%) = 214 (47) [M+],
199 (100), 121 (57), 79 (4). HRMS: calcd. for C9H10O4S 214.0300;
found 214.0269.
7-Methoxy-4-(p-toluenesulfonyloxy)coumarin (39): Quantitative
yield (0.54 g) from 4-hydroxy-7-methoxycoumarin (0.30 g,
1.6 mmol). Colorless prisms; m.p. 95–97 °C (hexane/AcOEt). IR
(film): ν = 1067, 1192, 1211, 1379, 1510, 1618, 1728 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 2.47 (s, 3 H), 3.86 (s, 3 H), 6.12 (s, 1 H),
6.78 (d, J = 2.5 Hz, 1 H), 6.82 (dd, J = 8.9, 2.5 Hz, 1 H), 7.39 (d,
J = 8.2 Hz, 2 H), 7.53 (d, J = 8.9 Hz, 1 H), 7.89 (d, J = 8.2 Hz, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.8, 55.8, 100.6, 100.8,
108.2, 112.8, 124.3, 128.4, 130.3, 131.8, 146.7, 155.5, 158.2, 161.3,
163.9 ppm. MS (EI): m/z (%) = 346 (97) [M+], 282 (97), 155 (86),
132 (100), 91 (79). HRMS: calcd. for C17H14O6S 346.0511; found
346.0479.
1-Methanesulfonyloxynaphthalene (57): 92% (0.76 g) from 1-naph-
thol (0.50 g, 3.5 mmol). Colorless plates; m.p. 35–36 °C (hexane/
AcOEt). IR (film): ν = 1151, 1180, 1221, 1367, 1507, 1599 cm–1.
˜
1H NMR (400 MHz, CDCl3): δ = 3.20 (s, 3 H), 7.46 (t, J = 8.0 Hz,
1 H), 7.51–7.61 (m, 3 H), 7.80 (d, J = 8.4 Hz, 1 H), 7.88 (d, J =
8.0 Hz, 1 H), 8.13 (d, J = 8.0 Hz, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 37.9, 118.3, 121.4, 125.3, 126.9, 127.0, 127.2, 127.3,
128.0, 134.9, 145.3 ppm. MS (EI): m/z (%) = 222 (31) [M+], 143
(71), 115 (100). HRMS: calcd. for C11H10O3S 222.0351; found
222.0340.
6-Methyl-4-(p-toluenesulfonyloxy)-2-pyranone (40): 94% (1.0 g)
from 4-hydroxy-6-methyl-2-pyranone (0.50 g, 4.0 mmol). Colorless
prisms; m.p. 100–102 °C (hexane/AcOEt, ref.[21] 101.2–102.0 °C).
2-Methanesulfonyloxynaphthalene (58): 74% (0.61 g) from 2-naph-
thol (0.50 g, 3.5 mmol). Colorless prisms; m.p. 101–102 °C (hexane/
1
IR (film): ν = 1180, 1194, 1387, 1570, 1641, 1740 cm–1. H NMR
˜
(400 MHz, CDCl3): δ = 2.24 (s, 3 H), 2.48 (s, 3 H), 5.81 (s, 1 H),
6.00 (s, 1 H), 7.39 (d, J = 8.3 Hz, 2 H), 7.82 (d, J = 8.3 Hz, 2 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 20.1, 21.8, 100.68, 100.73,
128.4, 130.3, 131.7, 146.7, 161.9, 162.8, 164.2 ppm. MS (EI): m/z
(%) = 280 (34) [M+], 167 (16), 155 (100), 132 (96), 91 (87). HRMS:
calcd. for C13H12O5S 280.0405; found 280.0399.
AcOEt, ref.[19] 103.5–104.5 °C). IR (film): ν = 1177, 1209, 1364,
˜
1508 cm–1. 1H NMR (400 MHz, CDCl3): δ = 3.13 (s, 3 H), 7.41
(dd, J = 9.0, 2.6 Hz, 1 H), 7.50–7.57 (m, 2 H), 7.76 (d, J = 2.0 Hz,
1 H), 7.84–7.91 (m, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
37.4, 119.4, 120.8, 126.6, 127.1, 127.8, 127.9, 130.3, 132.1, 133.6,
146.8 ppm. MS (EI): m/z (%) = 222 (32) [M+], 143 (40), 115 (100).
HRMS: calcd. for C11H10O3S 222.0351; found 222.0341.
1-Methyl-4-(p-toluenesulfonyloxy)-2-quinolone (41): 91% (0.85 g)
from 4-hydroxy-1-methyl-2-quinolone (0.50 g, 2.9 mmol). Colorless
plates; m.p. 153–155 °C (hexane/AcOEt, ref.[22] 156 °C). IR (film):
3-Methanesulfonyloxypyridine (59): 51% (0.46 g) from 3-hydroxy-
pyridine (0.50 g, 5.3 mmol). Colorless needles; m.p. 57–58 °C (hex-
ν = 1080, 1178, 1377, 1456, 1499, 1595, 1661 cm–1. 1H NMR
˜
ane/AcOEt, ref.[20] 60 °C). IR (film): ν = 1178, 1202, 1377, 1479,
˜
(400 MHz, CDCl3): δ = 2.45 (s, 3 H), 3.66 (s, 3 H), 6.42 (s, 1 H),
7.22–7.26 (m, 1 H), 7.34–7.37 (m, 3 H), 7.60 (ddd, J = 8.3, 7.3,
1.4 Hz, 1 H), 7.81 (dd, J = 8.3, 1.4 Hz, 1 H), 7.87 (d, J = 8.3 Hz,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.6, 29.4, 110.5,
114.2, 116.1, 122.3, 123.6, 128.3, 130.1, 132.0, 132.1, 139.9, 146.2,
154.1, 162.0 ppm. MS (EI): m/z (%) = 329 (100) [M+], 279 (22),
265 (44), 217 (13), 174 (57), 167 (33), 91 (34). HRMS: calcd. for
C17H15NO4S 329.0722; found 329.0743.
1
1576, 1587, 3421 cm–1. H NMR (400 MHz, CDCl3): δ = 3.22 (s,
3 H), 7.40 (dd, J = 8.5, 4.8 Hz, 1 H), 7.68 (dt, J = 8.5, 1.4 Hz, 1
H), 8.59–8.60 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
37.8, 124.4, 129.7, 143.6, 146.0, 148.5 ppm. MS (EI): m/z (%) = 173
(88) [M+]. HRMS: calcd. for C6H7NO3S 173.0147; found 173.0110.
Typical Procedure for Tosylation of Enols [4-(p-Toluenesulfonyloxy)-
coumarin (37)]:
A
mixture of 4-hydroxycoumarin (0.50 g,
3.1 mmol), TsCl (0.70 g, 3.7 mmol), Et3N (0.37 g, 3.7 mmol), and
CH2Cl2 (15 mL) was stirred for 0.5 h at room temperature. The
solvent was removed under reduced pressure, and the residue was
purified by silica gel column chromatography (hexane/AcOEt, 4:1)
to obtain a colorless solid (0.92 g, 94%). The solid was recrys-
tallized from hexane/AcOEt to obtain colorless plates.
Typical Procedure for Nickel(II)–Pincer Complex Catalyzed
Suzuki–Miyaura Coupling Reaction: A mixture of 2 (27.3 mg,
0.10 mmol), PhB(OH)2 (36.6 mg, 0.30 mmol), complex 1a (3.3 mg,
0.0050 mmol), K3PO4 (43.0 mg, 0.20 mmol), and DME (1 mL) in
a sealed tube was heated to 120 °C for 24 h. After cooling to room
temperature, the reaction mixture was treated with H2O (15 mL)
followed by extraction with AcOEt (3ϫ15 mL). The combined ex-
tracts were washed with saturated aqueous solution of NaCl
(3ϫ15 mL), and the solvent was removed under reduced pressure.
4-(p-Toluenesulfonyloxy)coumarin (37): 94% (0.92 g) from 4-hy-
droxycoumarin (0.50 g, 3.1 mmol). Colorless plates; m.p. 110–
111 °C (hexane/AcOEt). IR (film): ν = 1069, 1194, 1371, 1489,
˜
2256
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 2251–2261

NHC-Derived Nickel–Pincer Complexes
The residue was purified by silica gel column chromatography (hex-
ane/AcOEt, 19:1) to obtain a colorless solid (17.1 mg, 95%;
Table 1, Entry 8).
ref.[4b] 117–119 °C). IR (film): ν = 1680 cm–1. 1H NMR (400 MHz,
˜
CDCl3): δ = 2.64 (s, 3 H), 7.40 (t, J = 7.8 Hz, 1 H), 7.40 (t, J =
7.8 Hz, 2 H), 7.47 (t, J = 7.8 Hz, 2 H), 7.47 (d, J = 8.4 Hz, 2 H),
8.03 (d, J = 8.4 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 26.9, 127.26, 127.31, 128.3, 128.96, 129.00, 135.9, 139.9, 145.8,
197.7 ppm. MS (EI): m/z (%) = 196 (64) [M+], 181 (100). HRMS:
calcd. for C14H12O 196.0888; found 196.0884.
4-Cyanobiphenyl (3): 95% (17.1 mg) from 2 (27.3 mg, 0.10 mmol)
(Table 1, Entry 8); 63% (11.3 mg) from 55 (19.7 mg, 0.10 mmol)
(Table 4, Entry 8; Table 5, Entry 1). Colorless prisms; m.p. 85–
86 °C (hexane, ref.[4b] 84–86 °C). IR (film): ν = 2228 cm–1. 1H
˜
4-Acetyl-4Ј-methoxybiphenyl (17): 71% (16.0 mg) from 4 (29.0 mg,
0.10 mmol) (Table 2, Entry 7); 38% (8.6 mg) from 56 (21.4 mg,
0.10 mmol) (Table 5, Entry 4). Colorless plates; m.p. 152–153 °C
NMR (400 MHz, CDCl3): δ = 7.40–7.50 (m, 3 H), 7.58 (dd, J =
7.2, 1.2 Hz, 2 H), 7.66–7.73 (m, 4 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 110.8, 118.9, 127.1, 127.6, 128.6, 129.0, 132.5, 139.0,
145.5 ppm. MS (EI): m/z (%) = 179 (100) [M+]. HRMS: calcd. for
C13H9N 179.0735; found 179.0739.
(hexane/AcOEt, ref.[24] 154–155 °C). IR (film): ν = 1296, 1601,
˜
1674 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.63 (s, 3 H), 3.86 (s,
3 H), 7.00 (d, J = 8.8 Hz, 2 H), 7.57 (d, J = 8.8 Hz, 2 H), 7.64 (d,
J = 8.2 Hz, 2 H), 8.00 (d, J = 8.2 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 26.6, 55.4, 114.4, 126.6, 128.4, 128.9, 132.3,
135.3, 145.4, 159.9, 197.7 ppm. MS (EI): m/z (%) = 226 (94) [M+],
211 (100), 183 (14), 168 (10). HRMS: calcd. for C15H14O2 226.0994;
found 226.0983.
4-Cyano-4Ј-methoxybiphenyl (11): 55% (11.5 mg) from 2 (27.3 mg,
0.10 mmol) (Table 2, Entry 1); 24% (5.0 mg) from 55 (19.7 mg,
0.10 mmol) (Table 5, Entry 2). Colorless plates; m.p. 101–102 °C
(hexane/AcOEt, ref.[23] 103–104 °C). IR (film): ν = 1038, 1607,
˜
2224 cm–1. 1H NMR (400 MHz, CDCl3): δ = 3.86 (s, 3 H), 7.00 (d,
J = 8.8 Hz, 2 H), 7.53 (d, J = 8.8 Hz, 2 H), 7.63 (d, J = 8.0 Hz, 2
H), 7.69 (d, J = 8.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 55.4, 110.1, 114.6, 119.1, 127.1, 128.3, 131.5, 132.6, 145.2,
160.2 ppm. MS (EI): m/z (%) = 209 (100) [M+], 194 (29), 166 (20).
HRMS: calcd. for C14H11NO 209.0841; found 209.0826.
4-Acetyl-4Ј-cyanobiphenyl (18): 48% (10.6 mg) from 4 (29.0 mg,
0.10 mmol) (Table 2, Entry 8). Colorless prisms; m.p. 113–114 °C
(hexane/AcOEt, ref.[25] 115–116 °C). IR (film): ν = 1603, 1684,
˜
2226 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.65 (s, 3 H), 7.68 (d,
J = 8.2 Hz, 2 H), 7.72 (d, J = 8.2 Hz, 2 H), 7.76 (d, J = 8.2 Hz, 2
H), 8.07 (d, J = 8.2 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 26.8, 111.9, 118.5, 127.4, 127.8, 129.0, 132.6, 136.8, 143.4, 144.2,
197.3 ppm. MS (EI): m/z (%) = 221 (56) [M+], 206 (100), 178 (24).
HRMS: calcd. for C15H11NO 221.0841; found 221.0833.
4-Cyano-3Ј-methylbiphenyl (12): 59% (11.4 mg) from 2 (27.3 mg,
0.10 mmol) (Table 2, Entry 2). Colorless oil. IR (neat): ν = 1607,
˜
1
2226 cm–1. H NMR (400 MHz, CDCl3): δ = 2.43 (s, 3 H), 7.23–
7.25 (m, 1 H), 7.34–7.39 (m, 3 H), 7.67 (d, J = 8.2 Hz, 2 H), 7.71
(d, J = 8.2 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.6,
110.7, 118.9, 124.3, 127.6, 127.9, 128.9, 129.3, 132.4, 138.7, 139.1,
145.7 ppm. MS (EI): m/z (%) = 193 (100) [M+], 178 (9). HRMS:
calcd. for C14H11N 193.0892; found 193.0907.
4-Acetyl-3Ј-methylbiphenyl (19): 79% (16.6 mg) from 4 (29.0 mg,
0.10 mmol) (Table 2, Entry 9). Colorless oil. IR (neat): ν =
˜
1684 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.43 (s, 3 H), 2.63 (s,
3 H), 7.33–7.37 (m, 2 H), 7.41–7.43 (m, 2 H), 7.67 (d, J = 8.6 Hz,
2 H), 8.01 (d, J = 8.6 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 21.6, 26.7, 124.3, 127.1, 127.9, 128.8, 128.9, 131.8, 135.7, 138.5,
139.8, 145.8, 197.6 ppm. MS (EI): m/z (%) = 210 (84) [M+], 195
(100), 167 (12), 152 (10). HRMS: calcd. for C15H14O 210.1045;
found 210.1026.
4-Cyano-2Ј-methylbiphenyl (13): 52% (10.0 mg) from 2 (27.3 mg,
0.10 mmol) (Table 2, Entry 3). Colorless prisms; m.p. 54–56 °C
(hexane/AcOEt). IR (film): ν = 1609, 2226 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 2.25 (s, 3 H), 7.18 (d, J = 7.2 Hz, 1 H),
7.25–7.33 (m, 3 H), 7.43 (d, J = 7.6 Hz, 2 H), 7.70 (d, J = 7.6 Hz,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 20.4, 110.7, 118.9,
126.0, 128.2, 129.3, 129.9, 130.6, 131.9, 134.9, 139.9, 146.7 ppm.
MS (EI): m/z (%) = 193 (100) [M+], 178 (14). HRMS: calcd. for
C14H11N 193.0892; found 193.0904.
4-(E)-Pentenylacetophenone (20): 69% (13.0 mg) from 4 (29.0 mg,
0.10 mmol) (Table 2, Entry 10). Colorless oil. IR (neat): ν = 1603,
˜
1
1682 cm–1. H NMR (400 MHz, CDCl3): δ = 0.96 (t, J = 7.2 Hz,
3 H), 1.52 (sext., J = 7.2 Hz, 2 H), 2.22 (q, J = 7.2 Hz, 2 H), 2.58
(s, 3 H), 6.35–6.44 (m, 2 H), 7.41 (d, J = 8.4 Hz, 2 H), 7.88 (d, J
= 8.4 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 13.8, 22.4,
26.6, 35.3, 125.8, 128.7, 129.0, 134.2, 135.3, 142.6, 197.5 ppm. MS
(EI): m/z (%) = 188 (100) [M+], 173 (88), 146 (19), 131 (29), 43
(36). HRMS: calcd. for C13H16O 188.1200; found 188.1208.
4-Cyano-2Ј-methoxybiphenyl (14): 58% (12.1 mg) from 2 (27.3 mg,
0.10 mmol) (Table 2, Entry 4). Colorless prisms; m.p. 72–74 °C
(hexane/AcOEt). IR (film): ν = 1263, 1607, 2226 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 3.82 (s, 3 H), 6.96–7.07 (m, 2 H), 7.29 (dd,
J = 7.6, 1.1 Hz, 1 H), 7.38 (ddd, J = 8.3, 7.6, 1.1 Hz, 1 H), 7.63 (d,
J = 8.4 Hz, 2 H), 7.68 (d, J = 8.4 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 55.6, 110.4, 111.3, 119.1, 120.3, 121.0,
129.8, 130.1, 130.5, 131.7, 143.3, 156.2 ppm. MS (EI): m/z (%) =
209 (100) [M+], 194 (25), 166 (9). HRMS: calcd. for C14H11NO
209.0841; found 209.0818.
4-Methoxybiphenyl (21): 20% (3.7 mg) from 5 (27.8 mg, 0.10 mmol)
(Table 2, Entry 11). Colorless prisms; m.p. 86–87 °C (hexane, ref.[4b]
85–87 °C). IR (film): ν = 1036, 1609 cm–1. 1H NMR (400 MHz,
˜
CDCl3): δ = 3.83 (s, 3 H), 6.96 (d, J = 8.8 Hz, 2 H), 7.29 (t, J =
7.5 Hz, 1 H), 7.40 (t, J = 7.5 Hz, 2 H), 7.51–7.55 (m, 4 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 55.3, 114.1, 126.56, 126.64,
128.0, 128.6, 133.7, 140.7, 159.0 ppm. MS (EI): m/z (%) = 184 (100)
[M+], 169 (43), 141 (26). HRMS: calcd. for C13H12O 184.0888;
found 184.0886.
4-(E)-Pentenylbenzonitrile (15): 74% (12.7 mg) from 2 (27.3 mg,
0.10 mmol) (Table 2, Entry 5). Colorless oil. IR (neat): ν = 1651,
˜
1
2224 cm–1. H NMR (400 MHz, CDCl3): δ = 0.96 (t, J = 7.2 Hz,
3 H), 1.51 (sext., J = 7.2 Hz, 2 H), 2.20–2.25 (m, 2 H), 6.33–6.42
(m, 2 H), 7.40 (d, J = 8.4 Hz, 2 H), 7.56 (d, J = 8.4 Hz, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 13.8, 22.3, 35.2, 109.8, 119.1,
126.3, 128.5, 132.2, 135.2, 142.3 ppm. MS (EI): m/z (%) = 171 (60)
[M+], 142 (74), 129 (100), 115 (19). HRMS: calcd. for C12H13N
171.1047; found 171.1029.
2-Cyanobiphenyl (22): 17% (3.0 mg) from 6 (27.3 mg, 0.10 mmol)
(Table 2, Entry 12). Colorless oil. IR (neat): ν = 2224 cm–1. 1H
˜
NMR (400 MHz, CDCl3): δ = 7.39–7.50 (m, 5 H), 7.54–7.56 (m, 2
H), 7.62 (td, J = 7.8, 1.3 Hz, 1 H), 7.74 (dd, J = 7.8, 1.3 Hz, 1 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 111.1, 118.6, 127.4, 128.59,
128.61, 128.64, 130.0, 132.7, 133.6, 138.0, 145.4 ppm. MS (EI): m/z
(%) = 179 (100) [M+]. HRMS: calcd. for C13H9N 179.0735; found
179.0725.
4-Acetylbiphenyl (16): 78% (15.3 mg) from 4 (29.0 mg, 0.10 mmol)
(Table 2, Entry 6); 46% (9.0 mg) from 56 (21.4 mg, 0.10 mmol)
(Table 5, Entry 3). Colorless needles; m.p. 121–122 °C (hexane,
Eur. J. Org. Chem. 2009, 2251–2261
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2257

J.-i. Kuroda, K. Inamoto, K. Hiroya, T. Doi
FULL PAPER
2-Acetylbiphenyl (23): 9% (1.8 mg) from 7 (29.0 mg, 0.10 mmol)
(hexane, ref.[28] 100–101 °C). 1H NMR (400 MHz, CDCl3): δ = 7.37
(Table 2, Entry 13). Colorless oil. IR (neat): ν = 1688 cm–1. 1H (t, J = 7.4 Hz, 1 H), 7.43–7.51 (m, 4 H), 7.71–7.75 (m, 3 H), 7.85–
˜
NMR (400 MHz, CDCl3): δ = 2.00 (s, 3 H), 7.32–7.44 (m, 7 H), 7.91 (m, 3 H), 8.03 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ
7.50 (td, J = 7.5, 1.5 Hz, 1 H), 7.56 (dd, J = 7.5, 0.8 Hz, 1 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 30.5, 127.3, 127.76, 127.78,
128.6, 128.7, 130.1, 130.6, 140.4, 140.6, 140.8, 204.7 ppm. MS (EI):
m/z (%) = 196 (74) [M+], 181 (100). HRMS: calcd. for C14H12O
196.0888; found 196.0860.
= 125.6, 125.8, 125.9, 126.3, 127.3, 127.4, 127.6, 128.2, 128.4, 128.8,
132.6, 133.7, 138.6, 141.1 ppm. MS (EI): m/z (%) = 204 (100) [M+].
HRMS: calcd. for C16H12 204.0939; found 204.0923.
2-(4-Methoxyphenyl)naphthalene (30): 65% (15.2 mg) from
9
(29.8 mg, 0.10 mmol) (Table 2, Entry 20); 69% (16.1 mg) from 58
(22.2 mg, 0.10 mmol) (Table 5, Entry 9). Colorless plates; m.p. 130–
1-Phenylnaphthalene (24): 73% (14.9 mg) from
8 (29.8 mg,
0.10 mmol) (Table 2, Entry 14); 83% (16.9 mg) from 57 (22.2 mg,
132 °C (hexane/AcOEt, ref.[28] 131–133 °C). IR (film): ν = 1283,
˜
1
0.10 mmol) (Table 5, Entry 5). Colorless oil. H NMR (400 MHz,
1607 cm–1. 1H NMR (400 MHz, CDCl3): δ = 3.86 (s, 3 H), 7.02
CDCl3): δ = 7.39–7.53 (m, 9 H), 7.84–7.90 (m, 3 H) ppm. 13C NMR (dt, J = 8.9, 2.0 Hz, 2 H), 7.43–7.50 (m, 2 H), 7.66 (dt, J = 8.9,
(100 MHz, CDCl3): δ = 125.3, 125.7, 125.92, 125.94, 126.8, 127.1, 2.0 Hz, 2 H), 7.71 (dd, J = 8.6, 1.8 Hz, 1 H), 7.83–7.89 (m, 3 H),
127.5, 128.2 (2 C), 130.0, 131.5, 133.7, 140.2, 140.7 ppm. MS (EI):
m/z (%) = 204 (100) [M+]. HRMS: calcd. for C16H12 204.0939;
found 204.0921.
7.98 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 55.4, 114.3,
125.0, 125.4, 125.6, 126.2, 127.6, 128.0, 128.3, 128.4, 132.3, 133.6,
133.8, 138.2, 159.3 ppm. MS (EI): m/z (%) = 234 (100) [M+], 219
(31), 191 (10). HRMS: calcd. for C17H14O 234.1045; found
234.1026.
1-(4-Methoxyphenyl)naphthalene (25): 66% (15.4 mg) from
8
(29.8 mg, 0.10 mmol) (Table 2, Entry 15); 59% (13.8 mg) from 57
(22.2 mg, 0.10 mmol) (Table 5, Entry 6). Colorless prisms; m.p. 2-(4-Cyanophenyl)naphthalene (31): 51% (11.7 mg) from 9 (29.8 mg,
113–115 °C (hexane/AcOEt, ref.[26] 111–112 °C). IR (film): ν =
0.10 mmol) (Table 2, Entry 21). Colorless prisms; m.p. 148–150 °C
˜
1
1034, 1609 cm–1. H NMR (400 MHz, CDCl3): δ = 3.88 (s, 3 H), (hexane/AcOEt). IR (film): ν = 2224 cm–1. 1H NMR (400 MHz,
˜
7.02 (d, J = 8.2 Hz, 2 H), 7.39–7.52 (m, 6 H), 7.82 (d, J = 8.2 Hz, CDCl3): δ = 7.51–7.56 (m, 2 H), 7.70 (dd, J = 8.4, 1.6 Hz, 1 H),
1 H), 7.88–7.93 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 7.75 (d, J = 8.4 Hz, 2 H), 7.81 (d, J = 8.4 Hz, 2 H), 7.87–7.96 (m,
55.4, 113.7, 125.3, 125.6, 125.8, 126.0, 126.8, 127.2, 128.2, 131.0,
3 H), 8.05 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 110.9,
131.7, 133.0, 133.7, 139.8, 158.8 ppm. MS (EI): m/z (%) = 234 (100) 118.9, 124.8, 126.5, 126.67, 126.70, 127.6, 127.9, 128.3, 128.9,
[M+], 219 (31). HRMS: calcd. for C17H14O 234.1045; found
234.1028.
132.6, 133.1, 133.4, 136.3, 145.5 ppm. MS (EI): m/z (%) = 229 (100)
[M+]. HRMS: calcd. for C17H11N 229.0892; found 229.0886.
1-(4-Cyanophenyl)naphthalene (26): 91% (20.8 mg) from 8 (29.8 mg,
0.10 mmol) (Table 2, Entry 16); 30% (6.9 mg) from 57 (22.2 mg,
0.10 mmol) (Table 5, Entry 7). Colorless prisms; m.p. 79–81 °C
2-(2-Methylphenyl)naphthalene (32): 57% (12.4 mg) from
9
1
(29.8 mg, 0.10 mmol) (Table 2, Entry 22). Colorless oil. H NMR
(400 MHz, CDCl3): δ = 2.31 (s, 3 H), 7.27–7.33 (m, 4 H), 7.45–
7.51 (m, 3 H), 7.76 (s, 1 H), 7.84–7.88 (m, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 20.6, 125.7, 125.8, 126.1, 127.3, 127.4,
127.6, 127.65, 127.69, 127.9, 129.9, 130.3, 132.2, 133.2, 135.5,
139.4, 141.8 ppm. MS (EI): m/z (%) = 218 (100) [M+], 203 (30).
(hexane/AcOEt, ref.[27] 76–77 °C). IR (film): ν = 1607, 2228 cm–1.
˜
1H NMR (400 MHz, CDCl3): δ = 7.39 (dd, J = 7.0, 1.0 Hz, 1 H),
7.46 (t, J = 7.0 Hz, 1 H), 7.50–7.56 (m, 2 H), 7.60 (d, J = 8.4 Hz,
2 H), 7.75–7.79 (m, 3 H), 7.90–7.94 (m, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 111.1, 118.9, 125.1, 125.2, 126.1, 126.5, HRMS: calcd. for C17H14 229.1096; found 229.1079.
126.9, 128.4, 128.7, 130.7, 130.8, 132.0, 133.7, 138.1, 145.5 ppm.
2-(E)-Pentenylnaphthalene (33): 55% (10.8 mg) from 9 (29.8 mg,
MS (EI): m/z (%) = 229 (100) [M+]. HRMS: calcd. for C17H11N
0.10 mmol) (Table 2, Entry 23); 28% (5.5 mg) from 58 (22.2 mg,
229.0892; found 229.0896.
0.10 mmol) (Table 5, Entry 10). Colorless oil. 1H NMR (400 MHz,
1-(3-Methylphenyl)naphthalene (27): 72% (15.7 mg) from
(29.8 mg, 0.10 mmol) (Table 2, Entry 17). Colorless oil. H NMR
8
CDCl3): δ = 0.98 (t, J = 7.3 Hz, 3 H), 1.54 (sext., J = 7.3 Hz, 2 H),
2.24 (dt, J = 7.3, 7.1 Hz, 2 H), 6.35 (dt, J = 16.0, 7.3 Hz, 1 H),
1
(400 MHz, CDCl3): δ = 2.43 (s, 3 H), 7.23–7.24 (m, 1 H), 7.28– 6.54 (d, J = 16.0 Hz, 1 H), 7.37–7.45 (m, 2 H), 7.57 (d, J = 8.4 Hz,
7.32 (m, 2 H), 7.35–7.52 (m, 5 H), 7.84 (d, J = 8.0 Hz, 1 H), 7.88– 1 H), 7.66 (s, 1 H), 7.74–7.81 (m, 3 H) ppm. 13C NMR (100 MHz,
7.91 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.6, 125.3, CDCl3): δ = 13.9, 22.7, 35.3, 123.5, 125.2, 125.3, 126.1, 127.5,
125.6, 125.9, 126.0, 126.7, 127.1, 127.4, 127.9, 128.0, 128.1, 130.7,
127.7, 127.9, 129.9, 131.4, 132.5, 133.6, 135.3 ppm. MS (EI): m/z
131.6, 133.7, 137.7, 140.3, 140.6 ppm. MS (EI): m/z (%) = 218 (100) (%) = 196 (77) [M+], 167 (100), 141 (16), 128 (7). HRMS: calcd.
[M+], 203 (70). HRMS: calcd. for C17H14 218.1096; found
218.1078.
for C15H16 196.1252; found 196.1250.
3-Phenylpyridine (34): 69% (10.7 mg) from 10 (24.9 mg, 0.10 mmol)
(Table 2, Entry 24); 36% (5.6 mg) from 59 (17.3 mg, 0.10 mmol)
1-(E)-Pentenylnaphthalene (28): 49% (9.6 mg) from 8 (29.8 mg,
0.10 mmol) (Table 2, Entry 18). Colorless oil. 1H NMR (400 MHz,
CDCl3): δ = 1.01 (t, J = 7.3 Hz, 3 H), 1.58 (sext., J = 7.3 Hz, 2 H),
2.31 (dt, J = 7.3, 7.1 Hz, 2 H), 6.23 (dt, J = 15.6, 7.1 Hz, 1 H),
(Table 5, Entry 11). Pale yellow oil. IR (neat): ν = 3396 cm–1. 1H
˜
NMR (400 MHz, CDCl3): δ = 7.35–7.43 (m, 2 H), 7.48 (t, J =
7.4 Hz, 2 H), 7.58 (d, J = 7.4 Hz, 2 H), 7.87 (dt, J = 7.8, 1.9 Hz, 1
7.11 (d, J = 15.6 Hz, 1 H), 7.40–7.52 (m, 3 H), 7.55 (d, J = 7.0 Hz, H), 8.59 (d, J = 4.0 Hz, 1 H), 8.85 (s, 1 H) ppm. 13C NMR
1 H), 7.73 (d, J = 7.8 Hz, 1 H), 7.82 (dd, J = 7.8, 2.4 Hz, 1 H),
(100 MHz, CDCl3): δ = 123.4, 127.1, 128.0, 129.0, 134.2, 136.5,
8.12 (d, J = 7.8 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 137.7, 148.2, 148.3 ppm. MS (EI): m/z (%) = 155 (100) [M+].
13.9, 22.7, 35.6, 123.4, 123.9, 125.5, 125.6, 125.7, 127.0, 127.1,
128.3, 131.0, 133.5, 134.2, 135.7 ppm. MS (EI): m/z (%) = 196 (69)
[M+], 167 (100), 153 (26), 128 (3). HRMS: calcd. for C15H16
196.1252; found 196.1237.
HRMS: calcd. for C11H9N 155.0735; found 155.0738.
3-(4-Methoxyphenyl)pyridine (35): 86% (15.9 mg) from 10 (24.9 mg,
0.10 mmol) (Table 2, Entry 25). Colorless prisms; m.p. 60–61 °C
(hexane/AcOEt, ref.[29] 60–61 °C). IR (film): ν = 1032, 1611,
˜
2-Phenylnaphthalene (29): 76% (15.5 mg) from
9
(29.8 mg,
3373 cm–1. 1H NMR (400 MHz, CDCl3): δ = 3.86 (s, 3 H), 7.01 (d,
J = 8.2 Hz, 2 H), 7.33 (dd, J = 7.7, 4.7 Hz, 1 H), 7.52 (d, J =
8.2 Hz, 2 H), 7.83 (d, J = 7.7 Hz, 1 H), 8.54 (d, J = 4.7 Hz, 1 H),
0.10 mmol) (Table 2, Entry 19); 73% (14.9 mg) from 58 (22.2 mg,
0.10 mmol) (Table 5, Entry 8). Colorless plates; m.p. 99–100 °C
2258
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 2251–2261

NHC-Derived Nickel–Pincer Complexes
8.81 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 55.4, 114.5, 107–109 °C (hexane/AcOEt, ref.[33] 110–111 °C). IR (film): ν =
˜
123.4, 128.1, 130.2, 133.7, 136.1, 147.8, 147.9, 159.6 ppm. MS (EI):
1150, 1281, 1508, 1609, 1726 cm–1. 1H NMR (400 MHz, CDCl3):
m/z (%) = 185 (100) [M+], 170 (43). HRMS: calcd. for C12H11NO δ = 3.88 (s, 3 H), 6.21 (s, 1 H), 6.79 (dd, J = 8.8, 2.6 Hz, 1 H), 6.89
185.0841; found 185.0851.
(d, J = 2.6 Hz, 1 H), 7.38 (d, J = 8.8 Hz, 1 H), 7.42–7.44 (m, 2 H),
7.49–7.52 (m, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 55.8,
101.1, 111.8, 112.3, 112.5, 127.9, 128.3, 128.7, 129.5, 135.5, 155.7,
155.9, 161.1, 162.7 ppm. MS (EI): m/z (%) = 252 (100) [M+], 224
(49), 209 (22). HRMS: calcd. for C16H12O3 252.0786; found
252.0820.
3-(4-Cyanophenyl)pyridine (36): 83% (14.9 mg) from 10 (24.9 mg,
0.10 mmol) (Table 2, Entry 26). Colorless prisms; m.p. 94–96 °C
(hexane/AcOEt, ref.[30] 95–96 °C). IR (film): ν = 2226, 3358 cm–1.
˜
1H NMR (400 MHz, CDCl3): δ = 7.42 (t, J = 6.7 Hz, 1 H), 7.69
(d, J = 8.2 Hz, 2 H), 7.78 (d, J = 8.2 Hz, 2 H), 7.89 (d, J = 6.7 Hz,
1 H), 8.67 (s, 1 H), 8.86 (s, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 111.9, 118.5, 123.7, 127.7, 132.8, 134.4, 134.7, 142.2,
148.1, 149.6 ppm. MS (EI): m/z (%) = 180 (100) [M+]. HRMS:
calcd. for C13H8N2 180.0687; found 180.0670.
7-Methoxy-4-(4-methoxyphenyl)coumarin (48): 76% (21.4 mg) from
39 (34.6 mg, 0.10 mmol) (Table 3, Entry 7). Colorless needles; m.p.
159–160 °C (hexane/AcOEt). IR (film): ν = 1150, 1248, 1512, 1611,
˜
1
1726 cm–1. H NMR (400 MHz, CDCl3): δ = 3.885 (s, 3 H), 3.887
(s, 3 H), 6.19 (s, 1 H), 6.80 (dd, J = 9.0, 2.6 Hz, 1 H), 6.89 (d, J =
2.6 Hz, 1 H), 7.03 (d, J = 8.6 Hz, 2 H), 7.40 (d, J = 8.6 Hz, 2 H),
7.45 (d, J = 9.0 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
55.4, 55.8, 101.1, 111.4, 112.2, 112.7, 114.3, 128.0, 128.4, 129.8,
130.3, 155.5, 156.1, 161.3, 162.7 ppm. MS (EI): m/z (%) = 282 (100)
[M+], 254 (80), 239 (30), 211 (8). HRMS: calcd. for C17H14O4
282.0892; found 282.0887.
4-Phenylcoumarin (42): 73% (16.2 mg) from 37 (31.6 mg,
0.10 mmol) (Table 3, Entry 1). Pale yellow oil. IR (neat): ν = 1180,
˜
1
1604, 1724 cm–1. H NMR (400 MHz, CDCl3): δ = 6.38 (s, 1 H),
7.23 (dd, J = 8.4, 7.2 Hz, 1 H), 7.40–7.57 (m, 8 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 115.2, 117.3, 119.0, 124.1, 126.9, 128.4,
128.8, 129.6, 131.8, 135.1, 154.1, 155.5, 160.6 ppm. MS (EI): m/z
(%) = 222 (100) [M+], 194 (58), 165 (19). HRMS: calcd. for
C15H10O2 222.0681; found 222.0665.
6-Methyl-4-phenyl-2-pyranone (49): 84% (15.6 mg) from 40
(28.0 mg, 0.10 mmol) (Table 3, Entry 8). Colorless plates; m.p. 89–
4-(4-Methoxyphenyl)coumarin (43): 90% (22.7 mg) from 37
90 °C (hexane/AcOEt, ref.[34] 89–91 °C). IR (film): ν = 1140, 1547,
(31.6 mg, 0.10 mmol) (Table 3, Entry 2). Colorless needles; m.p.
˜
130–131 °C (hexane/AcOEt, ref.[31] 119–120 °C). IR (film): ν =
1
1636, 1711 cm–1. H NMR (400 MHz, CDCl3): δ = 2.32 (s, 3 H),
˜
1180, 1248, 1510, 1605, 1726 cm–1. 1H NMR (400 MHz, CDCl3):
δ = 3.89 (s, 3 H), 6.34 (s, 1 H), 7.04 (d, J = 8.4 Hz, 2 H), 7.23 (t,
J = 7.6 Hz, 1 H), 7.37–7.41 (m, 3 H), 7.52–7.57 (m, 2 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 55.4, 114.2, 114.5, 117.2, 119.0,
123.9, 126.9, 127.3, 129.8, 131.6, 154.1, 155.1, 160.7 (2 C) ppm.
MS (EI): m/z (%) = 252 (100) [M+], 224 (47), 209 (19). HRMS:
calcd. for C16H12O3 252.0786; found 252.0785.
6.31 (s, 1 H), 6.35 (s, 1 H), 7.47–7.48 (m, 3 H), 7.56–7.57 (m, 2 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 20.1, 103.4, 108.1, 126.6,
129.1, 130.5, 135.8, 155.5, 162.1, 163.4 ppm. MS (EI): m/z (%) =
186 (78) [M+], 158 (100), 129 (20), 115 (19). HRMS: calcd. for
C12H10O2 186.0681; found 186.0684.
4-(4-Methoxyphenyl)-6-methyl-2-pyranone (50): 87% (18.8 mg)
from 40 (28.0 mg, 0.10 mmol) (Table 3, Entry 9). Colorless needles;
4-(4-Cyanophenyl)coumarin (44): 44% (10.9 mg) from 37 (31.6 mg,
0.10 mmol) (Table 3, Entry 3). Colorless needles; m.p. 250–251 °C
m.p. 109–111 °C (hexane/AcOEt, ref.[35] 114–115 °C). IR (film): ν
˜
= 1186, 1254, 1545, 1607, 1638, 1705 cm–1. 1H NMR (400 MHz,
CDCl3): δ = 2.31 (s, 3 H), 3.86 (s, 3 H), 6.29 (s, 1 H), 6.30 (s, 1 H),
6.98 (d, J = 9.0 Hz, 2 H), 7.54 (d, J = 9.0 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 20.1, 55.4, 103.1, 106.4, 114.6, 127.8, 128.1,
154.7, 161.7, 161.8, 163.6 ppm. MS (EI): m/z (%) = 216 (95) [M+],
188 (100), 173 (31), 145 (14). HRMS: calcd. for C13H12O3 216.0786;
found 216.0748.
(hexane/AcOEt). IR (film): ν = 1182, 1603, 1722, 2220 cm–1. 1H
˜
NMR (400 MHz, CDCl3): δ = 6.38 (s, 1 H), 7.24–7.27 (m, 1 H),
7.33 (d, J = 7.2 Hz, 1 H), 7.44 (d, J = 8.4 Hz, 1 H), 7.57–7.61 (m,
3 H), 7.84 (d, J = 8.4 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 113.7, 115.9, 117.6, 117.9, 118.1, 124.4, 126.2, 129.2, 132.4,
132.6, 139.6, 153.4, 154.1, 159.9 ppm. MS (EI): m/z (%) = 247 (100)
[M+], 219 (78), 190 (18). HRMS: calcd. for C16H9NO2 247.0633;
found 247.0629.
4-(4-Cyanophenyl)-6-methyl-2-pyranone (51): 86% (18.1 mg) from
40 (28.0 mg, 0.10 mmol) (Table 3, Entry 10). Colorless plates; m.p.
6-Methyl-4-phenylcoumarin (45): 62% (14.6 mg) from 38 (33.0 mg,
182–184 °C (hexane/AcOEt). IR (film): ν = 1545, 1638, 1719,
˜
0.10 mmol) (Table 3, Entry 4). Colorless oil. IR (neat): ν = 1180,
˜
2228 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.35 (s, 3 H), 6.26 (s,
1 H), 6.36 (s, 1 H), 7.67 (d, J = 8.4 Hz, 2 H), 7.78 (d, J = 8.4 Hz,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 20.2, 102.8, 109.7,
114.2, 117.9, 127.3, 132.9, 140.3, 153.4, 162.5, 163.1 ppm. MS (EI):
m/z (%) = 211 (55) [M+], 183 (100). HRMS: calcd. for C13H9NO2
211.0633; found 211.0620.
1
1616, 1724 cm–1. H NMR (400 MHz, CDCl3): δ = 2.33 (s, 3 H),
6.35 (s, 1 H), 7.24–7.25 (m, 1 H), 7.30 (d, J = 8.6 Hz, 1 H), 7.35
(dd, J = 8.6, 1.6 Hz, 1 H), 7.43–7.45 (m, 2 H), 7.52–7.54 (m, 3 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 21.0, 115.1, 117.0, 118.6,
126.6, 128.3, 128.8, 129.5, 132.8, 133.8, 135.3, 152.2, 155.5,
160.8 ppm. MS (EI): m/z (%) = 236 (100) [M+], 208 (41). HRMS:
calcd. for C16H12O2 236.0837; found 236.0831.
1-Methyl-4-phenyl-2-quinolone (52): 87% (20.4 mg) from 41
(32.9 mg, 0.10 mmol) (Table 3, Entry 11). Colorless plates; m.p.
4-(4-Methoxyphenyl)-6-methylcoumarin (46): 65% (17.3 mg) from
38 (33.0 mg, 0.10 mmol) (Table 3, Entry 5). Colorless prisms; m.p.
147–148 °C (hexane/AcOEt, ref.[13d] 146–148 °C). IR (film): ν =
˜
1379, 1452, 1587, 1647, 1653 cm–1. 1H NMR (400 MHz, CDCl3):
δ = 3.78 (s, 3 H), 6.69 (s, 1 H), 7.17 (t, J = 7.6 Hz, 1 H), 7.41–7.60
(m, 8 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 29.5, 114.4,
120.4, 121.1, 121.9, 127.6, 128.5, 128.6, 128.8, 130.6, 136.9, 140.1,
150.8, 161.8 ppm. MS (EI): m/z (%) = 235 (100) [M+], 207 (14).
HRMS: calcd. for C16H13NO2 235.0997; found 235.0998.
128–130 °C (hexane/ AcOEt, ref.[32] 132–134 °C). IR (film): ν =
˜
1178, 1248, 1512, 1607, 1724 cm–1. 1H NMR (400 MHz, CDCl3):
δ = 2.35 (s, 3 H), 3.90 (s, 3 H), 6.32 (s, 1 H), 7.05 (d, J = 8.6 Hz,
2 H), 7.26–7.36 (m, 3 H), 7.41 (d, J = 8.6 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 20.9, 55.4, 114.3, 114.7, 117.1, 118.9, 126.7,
127.6, 129.9, 132.8, 133.7, 152.4, 155.3, 160.8, 161.1 ppm. MS (EI):
m/z (%) = 266 (100) [M+], 238 (50), 223 (21), 195 (5), 160 (15), 132
(6). HRMS: calcd. for C17H14O3 266.0943; found 266.0948.
4-(4-Methoxyphenyl)-1-methyl-2-quinolone (53): 77% (20.4 mg)
from 41 (32.9 mg, 0.10 mmol) (Table 3, Entry 12). Colorless need-
7-Methoxy-4-phenylcoumarin (47): 52% (13.1 mg) from 39
les; m.p. 116–117 °C (hexane/AcOEt). IR (film): ν = 1178, 1250,
˜
(34.6 mg, 0.10 mmol) (Table 3, Entry 6). Colorless prisms; m.p. 1379, 1454, 1512, 1587, 1587, 1607, 1645, 1657, 3368 cm–1. 1H
Eur. J. Org. Chem. 2009, 2251–2261
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2259

J.-i. Kuroda, K. Inamoto, K. Hiroya, T. Doi
FULL PAPER
Q. Zhu, L. Wang, R. Fathi, Z. Yang, J. Org. Chem. 2003, 68,
670–673; q) J. Wu, L. Wang, R. Fathi, Z. Yang, Tetrahedron
Lett. 2002, 43, 4395–4397.
NMR (400 MHz, CDCl3): δ = 3.78 (s, 3 H), 3.89 (s, 3 H), 6.67 (s,
1 H), 7.02 (d, J = 8.8 Hz, 2 H), 7.18 (dd, J = 8.0, 7.6 Hz, 1 H),
7.37 (d, J = 8.8 Hz, 2 H), 7.43 (d, J = 8.4 Hz, 1 H), 7.56–7.63 (m,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 29.4, 55.4, 114.0,
114.4, 120.7, 121.0, 121.8, 127.7, 129.4, 130.2, 130.6, 140.4, 150.7,
160.0, 162.1 ppm. MS (EI): m/z (%) = 265 (100) [M+], 222 (16).
HRMS: calcd. for C17H15NO2 265.1103; found 265.1091.
[4]
[5]
For reports on Suzuki–Miyaura coupling reaction of aryl mes-
ylates, see: a) C. M. So, C. P. Lau, F. Y. Kwon, Angew. Chem.
Int. Ed. 2008, 47, 8059–8063; b) V. Percec, G. M. Golding, J.
Smidrkal, O. Weichold, J. Org. Chem. 2004, 69, 3447–3452; c)
M. Ueda, A. Saitoh, S. Oh-tani, N. Miyaura, Tetrahedron 1998,
54, 13079–13086; d) Y. Kobayashi, R. Mizojiri, Tetrahedron
Lett. 1996, 37, 8531–8534; e) V. Percec, J.-Y. Bae, M. Zhao,
D. H. Hill, J. Org. Chem. 1995, 60, 1060–1065.
4-(4-Cyanophenyl)-1-methyl-2-quinolone (54): 86% (22.4 mg) from
41 (32.9 mg, 0.10 mmol) (Table 3, Entry 13). Colorless needles;
m.p. 185–186 °C (hexane/AcOEt). IR (film): ν = 1379, 1454, 1587,
˜
For other coupling reactions of tosylates and mesylates, see
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Recently, other electrophiles derived from phenols were also
employed for nickel-catalyzed Suzuki–Miyaura coupling reac-
tions, see aryl methyl ethers: a) M. Tobisu, T. Shimasaki, N.
Chatani, Angew. Chem. Int. Ed. 2008, 47, 4866–4869; aryl car-
boxylates: b) B.-T. Guan, Y. Wang, B.-J. Li, D.-G. Yu, Z.-J. Shi,
J. Am. Chem. Soc. 2008, 130, 14468–14470; c) K. W. Quasdorf,
X. Tian, N. K. Garg, J. Am. Chem. Soc. 2008, 130, 14422–
14423.
1
1605, 1659, 2230 cm–1. H NMR (400 MHz, CDCl3): δ = 3.79 (s,
3 H), 6.66 (s, 1 H), 7.20 (dd, J = 7.8, 7.4 Hz, 1 H), 7.39 (d, J =
7.8 Hz, 1 H), 7.47 (d, J = 8.7 Hz, 1 H), 7.55 (d, J = 8.0 Hz, 2 H),
7.62 (dd, J = 8.7, 7.4 Hz, 1 H), 7.81 (d, J = 8.0 Hz, 2 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 29.5, 112.7, 114.7, 118.2, 119.5,
121.6, 122.2, 127.0, 129.7, 131.1, 132.4, 140.3, 141.7, 148.9,
161.4 ppm. MS (EI): m/z (%) = 260 (100) [M+], 232 (47), 190 (23).
HRMS: calcd. for C17H12N2O 260.0950; found 260.0951.
Acknowledgments
This work was supported in part by a Grant-in-Aid for JSPS
Fellows from the Japan Society for the Promotion of Science
(JSPS).
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© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 2251–2261

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Received: January 22, 2009
Published Online: March 19, 2009
Eur. J. Org. Chem. 2009, 2251–2261
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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