Nickel/N-Heterocyclic Carbene-Catalyzed Suzuki-Miyaura Type Cross-Coupling of Aryl Carbamates

Article abstract of DOI:10.1021/acs.joc.6b01627

The utility of N-heterocyclic carbene ligands in nickel-catalyzed Suzuki-Miyaura cross-coupling of aryl esters and carbamates is investigated. Imidazol-2-ylidene bearing 2-adamantyl groups at its nitrogen atoms generates the most active nickel species among the ligands examined, allowing cross-coupling of a range of aryl carbamates and pivalates. Unlike the previously reported system using tricyclohexylphosphine, this protocol is suitable for the cross-coupling using arylboronic esters in addition to arylboronic acids.

Full text of DOI:10.1021/acs.joc.6b01627

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Note
Nickel/N-Heterocyclic Carbene-Catalyzed Suzuki-
Miyaura Type Cross-Coupling of Aryl Carbamates
Akimichi Ohtsuki, Kousuke Yanagisawa, Takayuki Furukawa, Mamoru Tobisu, and Naoto Chatani
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01627 • Publication Date (Web): 07 Sep 2016
Downloaded from http://pubs.acs.org on September 7, 2016
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Nickel/N-Heterocyclic Carbene-Catalyzed Suzuki-Miyaura Type Cross-Coupling of Aryl
Carbamates
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Akimichi Ohtsuki, Kousuke Yanagisawa, Takayuki Furukawa, Mamoru Tobisu,*,† and Naoto
Chatani*
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Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-
0871, Japan
†Center for Atomic and Molecular Technologies, Graduate School of Engineering, Osaka
University, Suita, Osaka 565-0871, Japan
tobisu@chem.eng.osaka-u.ac.jp; chatani@chem.eng.osaka-u.ac.jp
Abstract: The utility of N-heterocyclic carbene ligands in nickel-catalyzed Suzuki-Miyaura cross-
coupling of aryl esters and carbamates is investigated. Imidazol-2-ylidene bearing 2-adamantyl
groups at its nitrogen atoms generates the most active nickel species among the ligands examined,
allowing cross-coupling of a range of aryl carbamates and pivalates. Unlike the previously reported
system using tricyclohexylphosphine, this protocol is suitable for the cross-coupling using
arylboronic esters in addition to arylboronic acids.
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The Suzuki-Miyaura reaction has been recognized as a powerful carbon-carbon bond formation
method because of the favorable features of organoboron reagents, such as high functional group
compatibility and ease of handling.1 The Suzuki-Miyaura reaction is particularly useful for the
synthesis of (hetero)biaryls, in which various aryl halides and their equivalents are coupled with
arylboronic acid derivatives. Recent efforts have been directed toward the use of inert phenol
derivatives,2 such as aryl ethers, esters and carbamates, as aryl halide surrogates for Suzuki-
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Miyaura reactions. These efforts will not only provide cost-effective, halogen-free processes but
also lead to diverse synthetic strategies such as orthogonal cross-coupling and late-stage
functionalization. In this context, we have reported nickel-catalyzed Suzuki-Miyaura coupling of
methoxyarenes via the cleavage of C(aryl)-O bonds.3 Although we initially used
tricyclohexylphosphine (PCy3) as a suitable ligand for this cross-coupling,3a a subsequent study led
us to identify 1,3-dicyclohexylimidazol-2-ylidene (ICy) as a superior ligand with broadened scope
of methoxyarenes.3c The outstanding activity of the Ni/ICy system4 for C(aryl)-O bond activation
of methoxyarenes naturally encouraged us to consider whether this system is able to promote the C-
O bond activation of other inert phenol derivatives. Aryl esters and carbamates have attracted
substantial attention as a class of inert phenol derivatives for use in nickel-catalyzed cross-coupling
reactions.2 Although several groups have already revealed that the Ni/PCy3 system is able to
catalyze Suzuki-Miyaura type reactions of aryl esters5 and carbamates,6 the utility of an NHC
ligand in these processes has not been verified.7,8 Herein, we report Ni/NHC-catalyzed cross-
coupling of aryl esters and carbamates with arylboron reagents.
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Table 1. Reported Conditions for Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling of Aryl Esters
and Carbamates
Reliable catalytic conditions used for the cross-coupling of aryl esters and carbamates with
arylboron reagents are summarized in Table 1. Close inspection of the reported boron sources
employed indicates that these reactions apparently need precise control of the amount of water
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present in the reaction mixture. For example, Garg used arylboronic acid ArB(OH)2,5a,6a which
generates water by the reversible formation of arylboroxine (ArBO)3 at elevated temperature. Shi
used a mixture of (ArBO)3 and 0.88 equiv of H2O,5b,6c while Snieckus employed a 10:1 mixture of
ArB(OH)2 and (ArBO)3.6b Although an excess amount of water is thought to be detrimental to
Ni(0) catalysis,6e a suitable amount of water is essential, presumably to generate active Ni(0)
species by the reaction of NiCl2(PCy3)2 with ArB(OR)2. To avoid the potential complexity
associated with the effect of water during ligand screening experiments, we decided to use
anhydrous conditions with Ni(cod)2 as a catalyst and an arylboronic ester as a nucleophile. Thus, 2-
naphthyl carbamate (1a) was reacted with phenylboronic ester 2a in the presence of Ni(cod)2 and a
ligand using K3PO4 as a base at 120 °C (Table 2). When PCy3 was used as the ligand under these
conditions, cross-coupling product 3aa was formed in only 9% yield (entry 1).9 A series of NHC
ligands was then examined. N-Aryl substituted carbenes such as L1 (entry 2) and L2 (entry 3) were
found to be ineffective for this coupling. In contrast to our expectation, the use of L3, which
represents the most effective ligand for nickel-catalyzed Suzuki-Miyaura reaction of
methoxyarenes, afforded 3aa in only 11% yield (entry 4). NHC ligands bearing adamantyl groups
led to better results. Whereas 1-adamantyl derivative L4 provided a slight increase in the yield of
3aa to 27% (entry 5), isomeric 2-adamantyl ligand L54c,10 delivered 3aa in 88% yield (entry 6).
Having optimized ligand L5 in hand, we next examined a less reactive substrate 1b11 using these
conditions, which resulted in a lower yield of the coupling product (entry 7). Further optimization
revealed that conducting the reaction at 150 °C with a lower catalyst loading (5 mol%) increased
the yield of 3ba to 71% (entry 8). These conditions were used to explore the scope of this reaction.
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Table 2. Nickel/NHC-Catalyzed Cross-Coupling of Carbamate 1 with Phenylboronic Ester 2aa
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aReaction conditions: 1 (0.30 mmol), 2a (0.45 mmol), Ni(cod)2 (0.030 mmol), NHC·HCl (0.12
mmol), NaOtBu (0.12 mmol) and K3PO4 (1.4 mmol) in toluene (1.0 mL) at 120 °C for 24 h.
bConducted in the absence of NaOtBu. cPerformed using Ni(cod)2 (0.015 mmol), L5 (0.045 mmol)
and NaOtBu (0.045 mmol) at 150 °C for 20 h.
The scope of the reaction with respect to the boronic ester component was examined using 1b as
the substrate (Scheme 1). Both electron-rich and -deficient aryl groups can be introduced with
comparable efficiency. Similar to the standard Suzuki-Miyaura reaction, functional groups such as
amines (3be), esters (3bf), fluorides (3bg) and acetals (3bi) were well tolerated. In addition,
heteroarylboronic esters including 2j and 2k successfully underwent the cross-coupling with 1b.
Scheme 1. Scope of Arylboron Reagentsa
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Ni(cod)2 (5 mol%)
L5
(15 mol%)
Ar
NaOtBu (15 mol%)
OCONEt2
+
Ar B(OR)2
K3PO4, toluene
150 °C, 20 h
2b-k (1.5 equiv)
3bb-3bk
1b
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O
O
R
B
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O
O
R = Me
R = tBu
70% (3bb)
68% (3bc)
76% (3bd)
77% (3be)
67% (3bf)
73% (3ag)b
B
R = Ph
R = NMe2
R = CO2Me
R = F
67% (3bh)
O
B
O
O
O
B
O
O
B
O
O
N
Me
N
75% (3bi)
76% (3bj)
68% (3bk)
aReaction conditions: 1b (0.30 mmol), arylboron reagent (0.45 mmol), Ni(cod)2 (0.015 mmol), L5
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(0.045 mmol) NaOtBu (0.045 mmol) and K3PO4 (1.4 mmol) in toluene (1.0 mL) at 150 °C for 20 h.
c
b1a was used as the substrate. Conducted using Ni(cod)2 (0.030 mmol), L5 (0.090 mmol) and
NaOtBu (0.090 mmol) at 160 °C.
The scope of aryl carbamates was next investigated using 2b as a coupling partner (Scheme 2).
Although the Ni/L5 system can catalyze the reactions of an electronically diverse set of aryl
carbamates, electron-rich substrates such as 1d required higher catalyst loading to obtain
satisfactory yields of the products. When ortho substituted derivative 1g was used as the substrate,
the yield was decreased markedly because of the formation of an undesired reduced product (i.e.,
biphenyl with ca. 75% yield). The yield of 3gb was improved by switching the ligand to L3 and
increasing the amount of boronic ester 2b. Carbamate is known as a versatile directing group for
ortho C-H functionalization reactions.12 Therefore, the compatibility of the ortho substituent allows
sequential carbamate-directed ortho functionalization/arylation of the carbamate directing group.13
Heteroaryl carbamates (i.e., 1i) and aryl pivalates (i.e., 1j) also underwent cross-coupling with 2b
under these conditions. Phenyl p-toluenesulfonate and p-tert-butylanisole were found to be much
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less reactive under these conditions (34% and 0% yield, respectively, for the reaction with 2b).
Moreover, arylation at the benzylic position is also possible, as demonstrated by the reaction of 1k.
Scheme 2. Scope of Aryl Carbamatesa
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Ni(cod)2 (5 mol%)
L5 (15 mol%)
NaOtBu (15 mol%)
Ar OCOR'
+
Ar
Me
2b
K3PO4, toluene
150 °C, 20 h
(1.5 equiv)
1c-1k
3cb-3kb
R
OCONEt2
OCONEt2
Me
OCONEt2
R = p-CO2Et
R = p-NMe2
66% (3cb)
45% (3db)
60% (3db)b
65% (3eb)
75% (3he)d
16% (3gb)
59% (3gb)c
R = m-CF3
R = m-CO2Et 71% (3fb)
OCOtBu
OCONEt2
N
OCONEt2
70% (3ib)
61% (3jb)
3kb
83% (
)
aReaction conditions: substrate (0.30 mmol), 2b (0.45 mmol), Ni(cod)2 (0.015 mmol), L5 (0.045
mmol), NaOtBu (0.045 mmol) and K3PO4 (1.4 mmol) in toluene (1.0 mL) at 150 °C for 20 h.
bConducted using Ni(cod)2 (0.030 mmol), L5 (0.090 mmol) and NaOtBu (0.090 mmol) at 160 °C.
cPerformed using 2b (1.8 mmol), Ni(cod)2 (0.030 mmol), L3 (0.090 mmol) and NaOtBu (0.090
d
mmol) at 160 °C. Performed using 2e (1.8 mmol), Ni(cod)2 (0.030 mmol), L3 (0.090 mmol) and
NaOtBu (0.090 mmol) at 160 °C.
One advantage of using an NHC ligand over PCy3 in the nickel-catalyzed Suzuki-Miyaura reaction
is its tolerance of a protecting group of the boronic acid component (Table 3). When the Ni/L5
system was used, neopentylglycolate 2b, pinacolate 2b’ and free boronic acid 2b” were all
successfully coupled with aryl carbamate 1b (entries 1,3 and 5, respectively). In stark contrast,
boronic esters 2b’ and 2b” did not form an appreciable amount of 3bb under the conditions using
PCy3 (entries 2 and 4, respectively). The use of boronic esters is preferred over the parent boronic
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acids when boronic acids are unstable14 or the boron compounds are prepared by C-H borylation.15
In such a situation, our catalytic system should offer a useful protocol for the arylation of aryl esters
and carbamates.16 ArBF3K was unreactive under theses nickel/L5-catalyzed conditions.
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Table 3. Effect of Ligands on the Reactivity of Boron Reagentsa
aReaction conditions: 1b (0.30 mmol), organoboron reagent (0.45 mmol), Ni(cod)2 (0.015 mmol),
L5 (0.045 mmol), NaOtBu (0.045 mmol) and K3PO4 (1.4 mmol) in toluene (1.0 mL) at 150 °C for
b
20 h. Conducted using Ni(cod)2 (0.030 mmol), L5 (0.090 mmol) and NaOtBu (0.045 mmol) at
160 °C.
In conclusion, we revealed that 2-adamantyl-substituted NHC ligand L5 serves as an active ligand
for nickel-catalyzed Suzuki-Miyaura cross-coupling of aryl esters and carbamates. Use of L5 as the
ligand allows boronic esters to participate in the cross-coupling reaction, which is in sharp contrast
to the previously reported catalytic system using PCy3, in which boronic acids are essential.
Although the Ni/PCy3 system dominates in catalytic transformations involving the activation of
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inert phenol derivatives,2 we anticipate that this work will stimulate the application of NHC ligands
to such reactions.
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Experimental
General Information. H NMR and 13C NMR spectra were recorded at 400 and 100 MHz,
1
respectively, in CDCl3 with tetramethylsilane as an internal reference standard. High resolution
mass spectra (HRMS) were recorded by EI using a double-focusing mass spectrometer. Column
chromatography was performed with SiO2 (230-400 mesh). Unless otherwise noted, all of the
reagents used in this study were obtained from commercial suppliers and used as received without
further purification. Aryl carbamates used in this study are all known compounds and were
prepared by the reaction of the corresponding phenols with ClCONEt2. Arylboronic esters used in
this study are also known compounds and were prepared by the reaction of the corresponding
arylboronic acids with 2,2-dimethylpropane-1,3-diol. Ni(cod)2, NaOtBu, K3PO4, L1 and L2 were
purchased from the commercial suppliers and used as received. L3,17 L418 and L54c were prepared
according to the literature procedure.
4-(Dimethylamino)phenyl diethylcarbamate (1d). In a dried round-bottom flask, NaH (60%
dispersion in mineral oil, 230 mg, 5.8 mmol) was dissolved in DME (20 mL) and then the mixture
was cooled to 0 °C. 4-(Dimethylamino)phenol (660 mg, 4.8 mmol) was added portionwise. After
the mixture was stirred at 0 °C for 10 min, diethylcarbamoyl chloride (781 mg, 5.8 mmol) was
added dropwise. The mixture was warmed to rt and then stirred for another 1.5 h. The resulting
mixture was quenched with H2O and an aqueous solution of NaOH (1.0 M) was added. The
resulting mixture was extracted with Et2O. The organic phase was washed with brine, dried over
MgSO4 and concentrated in vacuo. The crude mixture was purified by flash column
chromatography over silica gel (eluted with hexane/AcOEt = 3/1) to give the target product as a
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white solid (916 mg, 81%); Rf 0.20 (hexane/ AcOEt = 5/1); Mp: 37.5-38.0 °C; 1H NMR (400 MHz,
CDCl3)1.15-1.25 (m, 6H), 2.91 (s, 6H), 3.45-3.55 (m, 4H), 6.72 (dt, J = 8.8, 2.2 Hz, 2H), 6.98(dt,
J = 8.8, 2.2 Hz, 2H); 13C NMR (100 MHz, CDCl3)13.6, 14.4, 41.4, 41.9, 42.3, 113.6, 122.3,
142.8, 148.5, 155.1; IR(ATR): 3431 m, 2968 m, 2940 w, 2889 w, 2254 m, 1650 m, 1460 m, 1416 s,
1303 m, 1224 m, 1088 s, 1048 s, 907 s, 857 m, 805 w. HRMS (EI+) m/z [M]+ calcd for
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+
C13H20N2O2 236.1525, Found 236.1527.
Ethyl 3-((diethylcarbamoyl)oxy)benzoate (1f). In a dried round-bottom flask, NaH (60% dispersion
in mineral oil, 480 mg, 12 mmol) was dissolved in DME (25 mL) and then the mixture was cooled
to 0 °C. Ethyl 3-hydroxybenzoate (1.66 g, 10 mmol) was added portionwise. After the mixture was
stirred at 0 °C for 10 min, diethylcarbamoyl chloride (1.63 g, 12 mmol) was added dropwise. The
mixture was warmed to rt and then stirred for another 1.5 h. The resulting mixture was quenched
with H2O and an aqueous solution of NaOH (1.0 M) was added. The organic phase was washed
with brine, dried over MgSO4 and concentrated in vacuo. The crude mixture was purified by flash
column chromatography over silica gel (eluted with hexane/AcOEt = 3/1) to give the target product
as a clear oil (2.61 g, 98%); Rf 0.54 (hexane/ AcOEt = 1/1). 1H NMR (400 MHz, CDCl3)1.18-
1.28 (m, 6H), 1.39 (t, J = 7.2 Hz, 3H), 3.38-3.47 (m, 4H), 4.37 (q, J = 7.2 Hz, 2 H), 7.33-7.35 (m,
1H), 7.42 (t, J = 7.8 Hz, 1H), 7.73 (t, J = 1.8 Hz, 1H), 7.88 (dt, J = 8.0 Hz, 1.4 Hz, 1H); 13C NMR
(100 MHz, CDCl3)13.5, 14.38, 14.44, 42.1, 42.5, 61.3, 123.0, 126.4, 126.6, 129.2, 131.9, 151.6,
154.0, 166.0; IR(ATR): 2978w, 2936 w, 2904 w, 2874 w, 1713 s, 1589 w, 1473 w, 1455 w, 1445
w, 1415 m 1381 w, 1367 w, 1283 m, 1254 s, 1223 m, 1120 s, 1150 s, 1097 s, 1075 m, 1042 m,
1021 m, 965 m, 912 w, 866 w, 826 w, 784 w, 750 s, 684 m. HRMS (EI+) m/z [M]+ calcd for
C14H19NO4 265.1314, Found 265.1312.
Typical Procedure. Ni(cod)2 (4.2 mg, 0.015 mmol, 5 mol%), L5 (17 mg,0.045 mmol), NaOtBu
(4.3 mg, 0.045 mmol), and toluene (0.4 mL) were added to a 10 mL-sample vial with a Teflon-
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sealed screwcap in a glove box with N2-atomosphere. The resulting mixture was stirred at room
temperature for 5 min. K3PO4 (287 mg, 1.35 mmol), 1b (58 mg, 0.30 mmol), 2b (92 mg, 0.45
mmol), and toluene (0.6 mL) were added to the vial and the cap was closed. The contents of the
vial were stirred at 150 °C for 20 h. The reaction mixture was cooled to room temperature, and then
the crude mixture was filtered through a pad of silica gel, and analyzed by GC. The filtrate was
concentrated in vacuo to give a residue, which was purified by column chromatography over silica
gel (eluent: hexane/EtOAc =9/1) to give 3bb as a white solid (35 mg, 70% yield).
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2-Phenylnaphthalene (3aa).19 The general procedure was used, except that the reaction was
conducted at 120 °C for 24 h. The yield was only determined by GC since this is a model
compound used for optimization studies (88% GC yield); 1H NMR (400 MHz, CDCl3)  7.39-7.41
13
(m, 1H), 7.47-7.52 (m, 4H), 7.72-7.77 (m, 3H), 7.86-7.94 (m, 3H), 8.05 (s, 1H); C NMR (100
MHz, CDCl3) 125.7, 125.9, 126.1, 126.4, 127.5, 127.6, 127.8, 128.3, 128.6, 129.0, 132.8, 133.8,
138.7, 141.3. HRMS (EI+) m/z [M]+ calcd for C16H12 204.0939, Found 204.0937.
Biphenyl (3ba).20 The general procedure was used, except that the reaction was conducted at
120 °C for 24 h. The yield was only determined by GC since this is a model compound used for
optimization studies (71% GC yield); 1H NMR (400 MHz, CDCl3)  7.35-7.39 (m, 2H), 7.44-7.48
13
(m, 4H), 7.61-7.63 (m, 4H); C NMR (100 MHz, CDCl3) 127.3, 127.4, 128.9, 141.4. HRMS
(EI+) m/z [M]+ calcd for C12H10 154.0783, Found 154.0780.
4-Methyl-1,1'-Biphenyl (3bb).21 The general procedure was used; white solid (35 mg, 70% yield);
1H NMR (400 MHz, CDCl3)  2.40 (s, 3H), 7.24-7.28 (m, 2H), 7.33 (t, J = 7.2 Hz, 1H), 7.43 (t, J =
13
7.8 Hz, 2H), 7.49 (dd, J = 6.4, 2.0 Hz, 2H), 7.58 (dd, J = 8.4, 1.2 Hz, 2H); C NMR (100 MHz,
CDCl3)  21.2, 127.1, 128.9, 129.6, 137.2, 138.5, 141.3. HRMS (EI+) m/z [M]+ calcd for C13H12
168.0939, Found 168.0935.
4-(1,1-Dimethylethyl)-1,1'-Biphenyl (3bc).22 The general procedure was used; white solid (43 mg,
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68% yield); 1H NMR (400 MHz, CDCl3)  1.37 (s, 9H), 7.33 (t, J = 7.4 Hz, 1H), 7.41-7.49 (m, 4H),
7.54 (d, J = 8.8 Hz, 2H), 7.59 (d, J = 7.2 Hz, 2H); 13C NMR (100 MHz, CDCl3)  31.5, 34.7, 125.9,
126.9, 127.1, 127.2, 128.8, 138.5, 141.2, 150.4. HRMS (EI+) m/z [M]+ calcd for C16H18 210.1409,
Found 210.1405.
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1,1':4',1''-Terphenyl (3bd).23 The general procedure was used; white solid (53 mg, 76% yield); H
NMR (400 MHz, CDCl3)  7.37 (dt, J = 7.6, 1.2 Hz, 2H), 7.49 (t, J = 7.8 Hz, 4H), 7.64-7.67 (m,
4H), 7.69 (s, 4H); 13C NMR (100 MHz, CDCl3) 127.2, 127.5, 127.6, 129.0, 140.3, 140.9. HRMS
(EI+) m/z [M]+ calcd for C18H14 230.1096, Found 230.1095.
N,N-Dimethyl-[1,1'-biphenyl]-4-amine (3be).24 The general procedure was used; white solid (46
1
mg, 77% yield); H NMR (400 MHz, CDCl3)  3.02 (s, 6H), 6.84 (d, J = 8.8 Hz, 2H), 7.28 (t, J =
7.6 Hz, 1H), 7.43 (t, J = 7.8 Hz, 2H), 7.54 (dd, J = 6.8, 2.4 Hz, 2H), 7.59 (dd, J = 7.2, 1.6 Hz, 2H);
13C NMR (100 MHz, CDCl3)  40.7, 112.9, 126.1, 126.4, 127.8, 128.8, 129.4, 141.4, 150.1. HRMS
(EI+) m/z [M]+ calcd for C14H15N 197.1204, Found 197.1200.
Methyl [1,1'-biphenyl]-4-carboxylate (3bf).25 The general procedure was used; white solid (43 mg,
67% yield); 1H NMR (400 MHz, CDCl3)  3.95 (s, 3H), 7.40 (tt, J = 7.4, 1.6 Hz, 1H) , 7.48 (tt, J =
7.4, 1.6 Hz, 2H) , 7.63 (dt, J = 8.4, 1.2 Hz, 2H) , 7.67 (dt, J = 8.2, 1.8 Hz, 2H), 8.11 (dt, J = 8.2, 1.8
Hz, 2H); 13C NMR (100 MHz, CDCl3) 52.3, 127.2, 127.4, 128.3, 129.1, 130.2, 140.2, 145.8,
167.2. HRMS (EI+) m/z [M]+ calcd for C14H12O2 212.0837, Found 212.0839.
2-(4-Fluorophenyl)-naphthalene (3ag).26 The general procedure was used except that 1a was used
as the substrate; white solid (36 mg, 53% yield); 1H NMR (400 MHz, CDCl3) 7.16-7.21 (m, 2H),
7.51-7.56 (m, 2H), 7.67-7.72 (m, 3H), 7.89-7.93 (m, 3H), 8.00-8.02 (m, 1H); 13C NMR (100 MHz,
CDCl3) 115.8 (d, J = 22.0 Hz), 125.5, 125.8, 126.1, 126.5, 127.8, 128.3, 128.7, 129.1 (d, J = 7.67
Hz), 132.7, 133.8, 137.4 (d, J = 2.88 Hz), 137.7, 162.7 (d, J = 246.3 Hz). HRMS (EI+) m/z [M]+
calcd for C16H11F 222.0845, Found 222.0844.
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1-Phenylnaphthalene (3bh).27 The general procedure was followed used; white solid (41 mg, 67%
yield); 1H NMR (400 MHz, CDCl3)  7.56-7.44 (m, 9H) ,7.86-7.93 (m, 3H); 13C NMR (100 MHz,
CDCl3)  125.5, 125.9, 126.2, 127.1, 127.4, 127.8, 128.4, 130.2, 131.7, 133.9, 140.4, 140.9. HRMS
(EI+) m/z [M]+ calcd for C16H12 204.0939, Found 204.0938.
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5-Phenylbenzo[d][1,3]dioxole (3bi).28 The general procedure was used; white solid (45 mg, 75%
1
yield); H NMR (400 MHz, CDCl3)  6.00 (s, 2H), 6.89 (dd, J = 8.0, 0.8 Hz, 1H), 7.08-7.05 (m,
2H), 7.32 (tt, J = 7.2, 1.4 Hz, 1H), 7.42 (t, J = 7.6 Hz, 2H), 7.52 (dd, J = 7.6, 1.0 Hz, 2H); 13C NMR
(100 MHz, CDCl3)  101.3, 107.8, 108.7, 120.8, 127.0, 127.1, 128.9, 135.8, 141.1, 147.2, 148.3.
HRMS (EI+) m/z [M]+ calcd for C13H10O2 198.0681, Found 198.0682.
1-Methyl-5-phenyl-1H-indole (3bj).29 The general procedure was used; pale yellow solid (47mg,
1
76% yield); H NMR (400 MHz, CDCl3)  3.83 (s, 3H), 6.55 (d, J = 2.4 Hz, 1H), 7.09 (d, J = 3.2
Hz, 1H), 7.31 (t, J = 7.2 Hz, 1H), 7.36-7.53 (m, 4H), 7.66 (dd, J = 8.0, 0.8 Hz, 2H), 7.85 (d, J = 1.2
Hz, 1H); 13C NMR (100 MHz, CDCl3)  33.1, 101.5, 109.5, 119.6, 121.5, 126.4, 127.5, 128.8,
129.1, 129.6, 133.0, 136.4, 142.8. HRMS (EI+) m/z [M]+ calcd for C15H13N 207.1048, Found
207.1048.
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3-Phenylpyridine (3bk).30 The general procedure was used; white solid (32 mg, 68% yeild); H
NMR (400 MHz, CDCl3)  7.20 (dd, J = 7.6, 4.8 Hz, 1H), 7.29-7.31 (m, 1H), 7.33-7.38 (m, 2H),
7.44-7.47 (m, 2H), 7.71(dt, J = 8.0, 1.6 Hz, 1 H), 8.50 (dd, J = 4.8, 1.6 Hz, 1H), 8.78 (d, J = 2.4 Hz,
1H); 13C NMR (100 MHz, CDCl3)  123.2, 126.8, 127.8, 128.8, 133.9, 136.2, 137.4, 148.0, 148.2.
HRMS (EI+) m/z [M+H]+ calcd for C11H10N+ 156.0808, Found 156.0814.
Ethyl 4'-methyl-[1,1'-biphenyl]-4-carboxylate (3cb).31 The general procedure was used; white solid
(43 mg, 60% yield); 1H NMR (400 MHz, CDCl3)  1.42 (t, J = 7.4 Hz, 3H), 2.42 (s, 3H), 4.41 (q, J
= 7.0 Hz, 2H), 7.28 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 7.6 Hz, 2H), 7.65 (d, J = 8.4 Hz, 2H), 8.11 (d, J
13
= 8.2 Hz, 2H); C NMR (100 MHz, CDCl3)  14.5, 21.3, 61.1, 126.9, 127.2, 129.1, 129.8, 130.2,
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137.3, 138.2, 145.6, 166.7. HRMS (EI+) m/z [M]+ calcd for C16H16O2 240.1150, Found 240.1148.
N,N,4'-Trimethyl-[1,1'-biphenyl]-4-amine (3db).32 The general procedure was used, except that the
reaction was conducted at 160 °C using 10 mol% of Ni(cod)2, 30 mol% of L5 and NaOtBu; white
solid (38 mg, 60% yield); 1H NMR (400 MHz, CDCl3)  2.38 (s, 3H), 3.00 (s, 6H), 6.81 (d, J = 8.0
Hz, 2H), 7.22 (d, J = 8.4 Hz, 2H), 7.47 (d, J = 7.6 Hz, 2H), 7.50 (d, J = 8.0 Hz, 2H); 13C NMR (100
MHz, CDCl3)  21.2, 40.8, 113.0, 126.3, 127.0, 127.7, 129.5, 135.8, 138.5, 149.9. HRMS (EI+) m/z
[M]+ calcd for C15H17N 211.1361, Found 211.1360.
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4'-Methyl-3-(trifluoromethyl)-1,1'-biphenyl (3eb).33 The general procedure was used; white solid
(46 mg, 65% yeild); 1H NMR (400 MHz, CDCl3)  2.42 (s, 3H), 7.29 (d, J = 8.4 Hz, 2H), 7.49-7.59
(m, 4H), 7.76 (d, J = 7.2 Hz, 1H), 7.83 (s, 1H); 13C NMR (100 MHz, CDCl3)  21.3, 123.8 (q, J =
3.9 Hz), 124.4 (q, J = 271 Hz), 127.2, 129.3, 129.9, 130.3, 131.2 (q, J = 31.87 Hz), 137.0, 138.1,
142.1. HRMS (EI+) m/z [M]+ calcd for C14H11F3 236.0813, Found 236.0809.
Ethyl 4'-methyl-[1,1'-biphenyl]-3-carboxylate (3fb).34 The general procedure was used; white solid
(51 mg, 71%); 1H NMR (400 MHz, CDCl3)  1.34 (t, J = 7.4 Hz, 3H), 2.34 (s, 3H), 4.34 (q, J = 7.2
Hz, 2H), 7.20 (d, J = 8.4 Hz, 2H), 7.42 (t, J = 7.8 Hz, 1H), 7.46 (d, J = 8.0 Hz, 2H), 7.68 (dt, J =
13
7.8, 1.6 Hz, 1H), 7.92 (dt, J = 7.8, 1.4 Hz, 1H), 8.19 (t, J = 1.8 Hz, 1H); C NMR (100 MHz,
CDCl3)  14.5, 21.3, 61.2, 127.2, 128.2, 128.9, 129.7, 131.1, 131.4, 137.5, 137.7, 141.5, 166.8.
HRMS (EI+) m/z [M]+ calcd for C16H16O2 240.1150, Found 240.1153.
4-Methyl-1,1':2',1''-terphenyl (3gb).35 The general procedure was used, except that the reaction was
conducted at 160 °C using Ni(cod)2 (10 mol%), L3 (30 mol%), NaOtBu (30 mol%) and 2b (6.0
equiv); colorless oil (43 mg, 59%). 1H NMR (400 MHz, CDCl3)  2.32 (s, 3H), 6.94-7.05 (m, 4H),
7.18-7.15 (m, 2H), 7.26-7.22 (m, 3H), 7.41-7.43 (m, 4H); 13C NMR (100 MHz, CDCl3)  21.2,
126.5, 127.4, 127.6, 128.0, 128.7, 129.9, 130.0, 130.8, 136.2, 138.7, 140.7, 141.8. HRMS (EI+) m/z
[M]+ calcd for C19H16 244.1252, Found 244.1251.
N,N,2'-Trimethyl[1,1'-biphenyl]-4-amine (3he).36 The general procedure was used, except that the
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reaction was conducted at 160 °C using Ni(cod)2 (10 mol%), L3 (30 mol%), NaOtBu (30 mol%)
and 2e (6.0 equiv); colorless oil (47 mg, 75%). 1H NMR (400 MHz, CDCl3)  2.33 (s, 3H), 3.00 (S,
6H), 6.79-6.81 (m, 2H), 7.21-7.26 (m, 6H); 13C NMR (100 MHz, CDCl3)  20.8, 40.8, 112.3, 125.9,
126.7, 130.06, 130.08, 130.4, 135.6, 142.1, 149.4. HRMS (EI+) m/z [M]+ calcd for C15H17N+
211.1361, Found 211.1357.
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2-(p-Tolyl)pyridine (3ib).37 The general procedure was used; white solid (36 mg, 70%); H NMR
(400 MHz, CDCl3)  2.41 (s, 3H), 7.20 (ddd, J = 6.4, 4.8, 1.8 Hz, 1H), 7.29 (d, J = 8.2 Hz, 2H),
7.68-7.78 (m, 2H), 7.90 (d, J = 8.4 Hz, 2H), 8.68 (d, J = 5.2 Hz, 1H); 13C NMR (100 MHz, CDCl3)
 21.4, 120.4, 121.9, 126.9, 129.6, 136.8, 139.1, 149.7, 157.6. HRMS (EI+) m/z [M]+ calcd for
C12H11N 169.0891, Found 169.0880.
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2-(p-Tolyl)naphthalene (3jb).38 The general procedure was used; white solid (40 mg, 61%); H
NMR (400 MHz, CDCl3)  2.42 (s, 3H), 7.30 (d, J = 7.8 Hz, 2H), 7.56-7.42 (m, 2H), 7.63 (d, J =
8.2 Hz, 2H), 7.74 (dd, J = 8.7, 1.8 Hz, 1H), 7.79-7.97 (m, 3H), 8.02 (d, J = 1.4 Hz, 1H); 13C NMR
(100 MHz, CDCl3)  21.2, 125.5, 125.6, 125.8, 126.3, 127.3, 127.7, 128.2, 128.4, 129.7, 132.6,
133.8, 137.2, 138.3, 138.6. HRMS (EI+) m/z [M]+ calcd for C17H14 218.1096, Found 218.1097.
2-(4-Methylbenzyl)naphthalene (3kb).39 The general procedure was used; pale-yellow oil (58 mg,
1
83%); H NMR (400 MHz, CDCl3)  2.36 (s, 3H), 4.14 (s, 2H), 7.07-7.25 (m, 4H), 7.35 (dd, J =
8.5, 1.6 Hz, 1H), 7.40-7.58 (m, 2H), 7.67 (s, 1H), 7.73-7.94 (m, 3H); 13C NMR (100 MHz, CDCl3)
 21.2, 41.8, 125.4, 126.1, 127.1, 127.68, 127.75, 127.77, 128.2, 129.0, 129.3, 132.2, 133.8, 135.8,
138.1, 139.0. HRMS (EI+) m/z [M]+ calcd for C18H16 232.1252, Found 232.1250.
Acknowledgements. This work was supported by ACT-C (J1210B2576) from JST, Japan and
Scientific Research on Innovative Area "Precisely Designed Catalysts with Customized
Scaffolding" (16H01022）from MEXT, Japan. We also thank the Instrumental Analysis Center,
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Faculty of Engineering, Osaka University, for their assistance with HRMS.
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Supporting Information Available: 1H and 13C NMR spectra for 1d, 1f and all the cross-coupling
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products is available free of charge via the Internet at http://pubs.acs.org.
References and Notes
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2011, 50, 6722.
(2) (a) Rosen, B. M.; Quasdorf, K. W.; Wilson, D. A.; Zhang, N.; Resmerita, A.-M.; Garg, N. K.;
Percec, V. Chem. Rev. 2011, 111, 1346-1416. (b) Li, B.-J.; Yu, D.-G.; Sun, C.-L. ; Shi, Z.-J. Chem.–
Eur. J. 2011, 17, 1728-1759. (c) Yamaguchi, J.; Muto, K.; Itami, K. Eur. J. Org. Chem. 2013, 2013,
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Chatani, N. Acc. Chem. Res. 2015, 48, 1717-1726.
(3) (a) Tobisu, M.; Shimasaki, T.; Chatani, N. Angew. Chem., Int. Ed. 2008, 47, 4866. (b)
Shimasaki, T.; Konno, Y.; Tobisu, M.; Chatani, N. Org. Lett. 2009, 11, 4890. (c) Tobisu, M.;
Yasutome, A.; Kinuta, H.; Nakamura, K.; Chatani, N. Org. Lett. 2014, 16, 5572.
(4) Other catalytic transformations enabled by the Ni/ICy catalytic system: (a) Tobisu, M.;
Takahira, T.; Ohtsuki, A.; Chatani, N. Org. Lett. 2015, 17, 680. (b) Tobisu, M.; Takahira, T.;
Chatani, N. Org. Lett. 2015, 17, 4352. (c) Tobisu, M.; Morioka, T.; Ohtsuki, A.; Chatani, N. Chem.
Sci. 2015, 6, 3410. (d) Furukawa, T.; Tobisu, M.; Chatani, N. Chem. Commun. 2015, 51, 6508. (e)
Morioka, T.; Nishizawa, A.; Nakamura, K.; Tobisu, M.; Chatani, N. Chem. Lett. 2015, 44, 1729. (f)
Nakamura, K.; Tobisu, M.; Chatani, N. Org. Lett. 2015, 17, 6142. (g) Hu, J.; Sun, H.; Cai, W.; Pu,
X.; Zhang, Y.; Shi, Z. J. Org. Chem. 2016, 81, 14. (h) Basch, C. H.; Cobb, K. M.; Watson, M. P.
Org. Lett. 2016, 18, 136.
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(5) (a) Quasdorf, K. W.; Tian, X.; Garg, N. K. J. Am. Chem. Soc. 2008, 130, 14422. (b) Guan, B.-
T.; Wang, Y.; Li, B.-J.; Yu, D.-G.; Shi, Z.-J. J. Am. Chem. Soc. 2008, 130, 14468. (c) Molander, G.
A.; Beaumard, F. Org. Lett. 2010, 12, 4022. (d) Xu, M.; Li, X.; Sun, Z.; Tu, T. Chem. Commun.
2013, 49, 11539.
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(6) (a) Quasdorf, K. W.; Riener, M.; Petrova, K. V.; Garg, N. K. J. Am. Chem. Soc. 2009, 131,
17748. (b) Antoft-Finch, A.; Blackburn, T.; Snieckus, V. J. Am. Chem. Soc. 2009, 131, 17750. (c)
Xu, L.; Li, B.-J.; Wu, Z.-H.; Lu, X.-Y.; Guan, B.-T.; Wang, B.-Q.; Zhao, K.-Q.; Shi, Z.-J. Org.
Lett. 2010, 12, 884. (d) Baghbanzadeh, M.; Pilger, C.; Kappe, C. O. J. Org. Chem. 2011, 76, 1507.
(e) Quasdorf, K. W.; Antoft-Finch, A.; Liu, P.; Silberstein, A. L.; Komaromi, A.; Blackburn, T.;
Ramgren, S. D.; Houk, K. N.; Snieckus, V.; Garg, N. K. J. Am. Chem. Soc. 2011, 133, 6352.
(7) The use of NHC ligands in other nickel-catalyzed transformations of aryl esters and carbamates:
(a) Shimasaki, T.; Tobisu, M.; Chatani, N. Angew. Chem., Int. Ed. 2010, 49, 2929. (b) Mesganaw,
T.; Silberstein, A. L.; Ramgren, S. D.; Nathel, N. F. F.; Hong, X.; Liu, P.; Garg, N. K. Chem. Sci.
2011, 2, 1766. (c) Hie, L.; Ramgren, S. D.; Mesganaw, T.; Garg, N. K. Org. Lett. 2012, 14, 4182.
(8) During the preparation of this manuscript, nickel/NHC-catalyzed cross-coupling of aryl
pivalates with alkyl(9-BBN) was reported: Guo, L.; Hsiao, C.-C.; Yue, H.; Liu, X.; Rueping, M.
ACS Catal. 2016, 6, 4438.
(9) Lower reactivity of arylboronic etsers than the parpent arylboronic acids in nickel-catalyzed
Suzuki-Miyaura cross-coupling of phenol derivatives has been reproted: Leowanawat, P.; Zhang,
N.; Percec, V. J. Org. Chem. 2012, 77, 1018.
(10) Nakamura, K.; Yasui, K.; Tobisu, M.; Chatani, N. Tetrahedron 2015, 71, 4484.
(11) Phenol derivatives are less reactive than those of -extended phenols, such as naphthol, in
many nickel-catalyzed cross-coupling reactions. See ref 2e.
(12) Snieckus, V. Chem. Rev. 1990, 90, 879.
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(13) A review on convertible directing groups: Zhang, F.; Spring, D. R. Chem. Soc. Rev. 2014, 43,
6906.
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(14) (a) Yamamoto, Y.; Takizawa, M.; Yu, X.-Q.; Miyaura, N. Angew. Chem., Int. Ed. 2008, 47,
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