Suzuki-Miyaura cross-coupling reaction of aryl chlorides with aryl boronic acids catalyzed by a palladium dichloride adduct of N-diphenylphosphanyl-2-aminopyridine

Article abstract of DOI:10.1016/j.tet.2017.04.034

One palladium dichloride adduct of a phosphine-pyridine ligand N-diphenylphosphanyl-2-aminopyridine (L₁) [(L₁)PdCl₂] (1) has been prepared and structurally characterized. Compound 1 can be used as an effective catalyst for the Suzuki-Miyaura cross-coupling reactions of unreactive aryl chlorides with aryl boronic acids, and worked much better than its mono- or bidentate phosphine ligands. The reactions with a wide scope of substrates proceeded to give desired products in good to excellent yields.

Full text of DOI:10.1016/j.tet.2017.04.034

Accepted Manuscript
Suzuki-Miyaura cross-coupling reaction of aryl chlorides with aryl boronic acids
catalyzed by a palladium dichloride adduct of N-diphenylphosphanyl-2-aminopyridine
Lin-Yan Xu, Chun-Yu Liu, Shi-Yuan Liu, Zhi-Gang Ren, David James Young, Jian-
Ping Lang
PII:
S0040-4020(17)30407-6
10.1016/j.tet.2017.04.034
TET 28635
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 7 March 2017
Revised Date: 10 April 2017
Accepted Date: 13 April 2017
Please cite this article as: Xu L-Y, Liu C-Y, Liu S-Y, Ren Z-G, Young DJ, Lang J-P, Suzuki-Miyaura
cross-coupling reaction of aryl chlorides with aryl boronic acids catalyzed by a palladium dichloride
adduct of N-diphenylphosphanyl-2-aminopyridine, Tetrahedron (2017), doi: 10.1016/j.tet.2017.04.034.
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Graphical Abstract
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Suzuki-Miyaura cross-coupling reaction of aryl
chlorides with aryl boronic acids catalyzed by a
palladium dichloride adduct of N-
Leave this area blank for abstract info.
diphenylphosphanyl-2-aminopyridine
Lin-Yan Xua, Chun-Yu Liua, Shi-Yuan Liua, Zhi-Gang Rena,b,*, David James Youngc,d*, Jian-Ping Langa,b,*
a College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R.
China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, Shanghai 210032, P. R. China
c School of Science, Monash University Malaysia, Jalan Lagoon Selatan, 47500 Bandar Sunway, Selangor Darul
Ehsan, Malaysia
d Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast, Maroochydore,
Queensland 4558, Australia
L1/PdCl2 = 1:1
Cl
B(OH)2
R
R'
R
R'
NH
PPh2
N
L1
1

ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Suzuki-Miyaura cross-coupling reaction of aryl chlorides with aryl boronic acids
catalyzed by a palladium dichloride adduct of N-diphenylphosphanyl-2-
aminopyridine
Lin-Yan Xua, Chun-Yu Liua, Shi-Yuan Liua, Zhi-Gang Rena,b*, David James Youngc,d*, Jian-Ping Langa,b*
a College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 210032, P. R. China
c School of Science, Monash University Malaysia, Jalan Lagoon Selatan, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
d Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast, Maroochydore, Queensland 4558, Australia.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
One palladium dichloride adduct of a phosphine-pyridine ligand N-diphenylphosphanyl-2-
aminopyridine (L1) [(L1)PdCl2] (1) has been prepared and structurally characterized.
Compound 1 can be used as an effective catalyst for the Suzuki-Miyaura cross-coupling
reactions of unreactive aryl chlorides with aryl boronic acids, and worked much better than its
mono- or bidentate phosphine ligands. The reactions with a wide scope of substrates proceeded
to give desired products in good to excellent yields.
Available online
Keywords:
Aryl chloride
2017 Elsevier Ltd. All rights reserved.
Aryl boronic acid
Suzuki-Miyaura coupling
P-N donor ligand
Palladium(II)
and other ligands17 capable of increasing the electron density at
palladium and thereby accelerating the oxidative addition step in
1. Introduction
the catalytic cycle.18
There have been major efforts in the past decades to develop
efficient catalysts for the Suzuki–Miyaura cross-coupling
reaction.1,2 The most important topic in this respect has been the
structure of the reactive palladium intermediates involved in the
key transmetalation step.3 Relative to aryl bromides and iodides
as substrates, aryl chlorides are less expensive, less toxic and less
wasteful. While aryl bromides and iodides in the Suzuki-Miyaura
coupling reactions work well, their chloride analogues generally
go less reactive and require harsher conditions and/or longer
reaction times to give the coupling products in lower yields. Thus
the development of catalysts that can efficiently activate aryl
chlorides remains a big challenge.4 Over years, researchers have
introduced electron-withdrawing groups into aryl chlorides to
achieve their reactivity. However, reports on examples of high
yields usually involve aryl chlorides with the strong electron-
withdrawing nitro and cyano groups.5 The activation of aryl
chlorides is still quite tough for those containing the electron-
neutral alkyl, medium electron-withdrawing acyl, aldehyde
groups and electron-neutral/-donating groups.6
Unlike these homo-donor chelate ligands, hetero-donor ligands
have a distinct trans effect which can play an pertinent role in
controlling activity and selectivity.19 The synthesis and catalytic
activity of complexes bearing hemi-labile ligands of the types
P,N20 and P,O21 have been widely reported. P- and N- donor
ligands bearing large groups are of interest because of their
ability to stabilize transition metal catalysts.22 Besides, the π-
acceptor ability of the phosphine can stabilize a metal center in a
low oxidation state, while the nitrogen σ-donor makes the metal
center more susceptible to oxidative addition reactions.23 Thus,
the hetero-bidentate P,N-donor ligands represent an important
class of ligands that have been explored in various catalytic
systems, but not extensively in the Suzuki–Miyaura reaction.24, 25
Since Gregory C. Fu first published a catalytic system for the
activation of aryl chlorides in Suzuki-Miyaura reaction in 1998,7
many research groups including Kwong,8 Buchwald,9 Sarkar,10
Hong,11 Lee,12 and Rajabi13 have developed various catalyst
candidates. Modifications on ligands include bulky or electron-
rich phosphines,14 nitrogen-donors,15 N-heterocyclic carbenes16
In our previous report,6i we successfully designed a N,P,P
ligand,
N,N-bis-(diphenylphosphanylmethyl)-2-aminopyridine
(bdppmapy), and prepared its PdCl2 adduct [(bdppmapy)PdCl2].
2

This catalyst showed good activity toward thAe SCuCzuEki-PMTiyEauDra MANUSCRIPT
coupling reactions of aryl bromides and arylboronic acids in
494.02
ethanol, but showed poor performance in catalyzing the similar
reactions using aryl chlorides. As an extension of this project, we
deliberately selected two P,N type bidentate ligands N-
(a)
(b)
phenylphosphanylmethyl-2-aminopyridine
(L1)
and
N-
phenylphosphanylmethyl-2-amino-6-methylpyridine (L2), and
prepared one PdCl2 adduct [(L1)PdCl2] (1). Compound 1
exhibited good catalytic activity toward the Suzuki-Miyaura
cross-coupling reaction of aryl chlorides with aryl boronic acids.
Described below are its synthesis, structural characterization and
catalytic performance.
490 491 492 493 494 495 496 497 498
m/z
2. Results and discussion
Fig. 2. The positive-ion ESI mass spectrum (a) and the calculated isotope
patterns (b) of the [L1/PdCl·DMF]+ cation.
Treatment of PdCl2 with equimolar L1 in DMF followed by a
standard workup produced yellow crystals of [(L1)PdCl2] (1).
Compound 1 is relatively stable in air, and soluble in polar
solvents such as DMF, DEF, and DMSO, but only slightly
soluble in other common solvents such as CH2Cl2, EtOH and
H2O. Single-crystal X-ray analysis revealed that 1 crystallizes in
the monoclinic space group P21/c. The Pd(II) center is
coordinated by a P atom and a N atom from one L1 molecule and
two chlorides, forming a cis square-planar geometry (Fig. 1). The
mean Pd-Cl bond length of 1 are comparable to those of the
square planar-coordinated Pd(II) complexes.6a, 26 The powder X-
ray diffraction (PXRD) patterns of the bulky sample of 1 are
consistent with the simulated patterns generated from the single
crystal data of 1 (Fig. S1). The IR spectrum showed one
stretching vibration at 1435 cm-1 attributable to the C-P groups of
4-Chloroacetophenone (2a) and 4-methoxy phenylboronic acid
(3a) were chosen as model substrates. The positive-ion ESI mass
spectrum of 1 in DMF was examined and provided an insight
into its solution behavior. A major signal at m/z = 494.02 (Fig. S6)
could be assigned to the [(L1)PdCl·DMF]+ cation (Fig. 2). The
presence of this cation indicated that Pd2+ and L1 remain
coordinated in solution, while one Pd-Cl bond is likely to be
broken in solution, which is helpful in inserting the Pd atom into
the C-Cl bond of aryl chloride during the oxidative addition step
in the catalytic cycle.18
The effects of different phosphine ligands were initially
evaluated (Table 1). Reaction without any ligands for the cross-
coupling of 4-chloroacetophenone (2a) with 4-methoxy-
phenylboronic acid (3a) generated the coupled product (4aa) in
36% yield under these conditions (entry 1). The yield was
significantly decreased in the presence of monodentate
triphenylphosphine (entry 2). Similarly, addition of bidentate
phosphine ligands such as dppm, dppe, dppp in this system
reduced this yield with the exception of dppf and one POP ligand
Xantphos (entries 3-7). The participation of P,N ligand L1 led to
a higher yield (entry 8). In order to evaluate the influence of
steric effects in this catalytic system, we prepared another P,N
1
L1. The H NMR spectrum of 1 (Fig. S2) in DMSO-d6 showed
the signals for the –Ph groups (7.91–7.04 ppm) and pyridine ring
(10.13-9.03 ppm). One signal at 77.8 ppm was observed in the
31P{1H} NMR spectrum (Fig. S4). The TGA measurement (Fig.
S5) indicated that 1 is quite stable at 200 oC, which eliminates L1
molecule at 200–365 °C (59.6%, Calcd 59.0%) and two chlorides
at 365-650 °C (13.9%, Calcd 15.1%) to leave PdO as a residual
species (26.5%, Calcd 25.9%).
ligand
N-phenylphosphanylmethyl-2-amino-6-methylpyridine
(L2). Notably, the increasing hindrance at the 6-position of the
pyridine ring in L2 resulted in a significant decrease in activity
(entry 9). This result is contrary to those reported using P,N
palladium catalysts,27 but similar to that observed using other
pyridine-based ligands.28 The reason may be attributed to the
weak axial steric hindrance of pyridine and the reduced basicity
of the pyridine nitogen.29 Thus, these P,N-donor ligands possess
one weakly coordinating group that may yield an unsaturation at
the Pd(II) center via Cl dissociation.
Table 1 The effect of different phosphine ligands on the
Suzuki-Miyaura cross-coupling reaction.
Fig. 1. View of the crystal structure of 1. All H atoms are omitted for clarity.
Selected bond lengths (Å): Pd(1)-Cl(1) 2.3844(6), Pd(1)-Cl(2) 2.2801(6),
Pd(1)-N(1) 2.0543(18), Pd(1)-P(1) 2.1802(6).
Entry
Catalyst system
PdCl2
Yield (%)
1
2
3
4
36
9
PdCl2 / PPh3
PdCl2 / dppma
PdCl2 / dppeb
35
31
3

ACCEPTED MANUSCRIPT
5
6
7
8
9
PdCl2 / dpppc
PdCl2 / dppfd
PdCl2 / Xantphose
PdCl2 / L1
13
43
62
78
31
5
6
7
8
9
THF
DMF
DMF
DMF
DMF
65
60
6
34
51
55
52
80
100
PdCl2 / L2
120
Reaction conditions: 2a (1 mmol), 3a (1.5 mmol), K3PO4·3H2O (3 mmol),
DMF (5 mL), PdCl2/L = 1/1, catalyst loading (2 mol% Pd), 18 h, 100 °C,
analyzed by GC, average of two runs. adppm = bisdiphenylphosphinomethane;
Reaction conditions: 2a (1 mmol), 3a (1.5 mmol), Solvent (3mL),
K3PO4 3H2O (3 mmol), PdCl2/L1 = 1/1, catalyst loading (2 mol% Pd), 24 h,
analyzed by GC, average of two runs.
.
bdppe
bis(diphenylphosphino)
=
1,2-bis(diphenylphosphino)ethane;
propane;
ddppf
eXantphos
cdppp
=
1,3-
1,1'-
=
Interestingly the concentration of substrate can influence the
yields of the desired products. As listed in Table 4, the highest
yield of 83% was found at a concentration of 0.2 mol/L (entry 3)
for 4-chloroacetophenone (2a) when it was adjusted from 0.10 to
0.30 mol/L (entries 1-5). Enlarged reaction by doubling all
reactants and solvent to keep the concentration being 0.2 mol/L
gave a similar yield (entry 6). This result might be caused by a
balance between speeding up the main and side reactions at
higher concentrations and slowing down the reactions due to the
insolubility of excess inorganic base.
=
bis(diphenylphosphino)ferrocene;
dimethylbisdiphenylphosphinoxanthene
The influences of bases, solvents and temperatures on this
coupling reaction were then investigated (Table 2). Potassium
phosphate (2 mmol) had a better effect on the yield of the desired
product (entry 3) than KOH and K2CO3 (entries 1 and 2), and
exhibited a slight improvement with an increased amount (3
mmol, entry 4). The yields were surprisingly poor in toluene,
water, ethanol or THF as a solvent at each boiling point (EtOH
and THF) or as high as 100 oC (entries 1-5 in Table 3), but got
Table 4 The effect of substrate concentrations on the Suzuki-
Miyaura cross-coupling reaction.
o
increased in DMF at 60 C or above (entries 6-9). However,
reactions in DMF reached the best yield at 100 oC (entry 8), but
did not go well at higher temperature (entry 9). This phenomenon
was probably due to the partly decomposition of L1 after the
long-term reactions.30
Table 2 The effect of different bases on the Suzuki-Miyaura
cross-coupling reaction.
Entry
Ar-Cl (mol/L)
0.10
Yield (%)
1
2
60
63
83
60
55
82
0.15
3
0.20
Entry
Base / amount
KOH / 2 mmol
Yield (%)
4
0.25
1
2
3
4
23
22
41
52
5
0.30
K2CO3 / 2 mmol
6a
0.20
K3PO4·3H2O / 2 mmol
.
Reaction conditions: 2a (1 mmol), 3a (1.5 mmol), K3PO4 3H2O (3 mmol),
DMF (5 mL), PdCl2/L1 = 1/1, catalyst loading (1.5 mol% Pd), 100 °C, 15 h,
analyzed by GC, average of two runs. a aryl halide (2 mmol), arylboronic acid
(3 mmol), K3PO4·3H2O (6 mmol), DMF (10 mL), catalyst loading (3 mol%
Pd).
K3PO4·3H2O / 3 mmol
Reaction conditions: 2a (1 mmol), 3a (1.5 mmol), DMF (3 mL), PdCl2/L1 =
1/1, catalyst loading (2 mol% Pd), 120 °C, 24 h, analyzed by GC, average of
two runs.
Investigation on the lower limit of the catalyst loading and
reaction time revealed that the majority of electron-poor substrate
4-chloroacetophenone (2a) was converted into the desired
product using 2 mol% palladium catalyst for 24 h at 100 °C
(Table 5, entry 1), and no starting materials were detected.
Decreasing the catalyst loading and the reaction time to 1.5 mol%
and 18 h, respectively, made no difference (entry 2). Similarly, a
yield of 83% was still obtained in the presence of 1.5 mol%
catalyst after 15 h (entry 3), but reduced to 59% at a reaction time
of 12 h (entry 4). Returning the time to 15 h and reducing the
loading to 1 mol% improved the yield (74%) (entry 5). Thus, the
reaction conditions were optimized as follows: 5 mL DMF, 1
mmol aryl halides, 1.5 mmol arylboronic acid, 3 mmol
K3PO4·3H2O, PdCl2/L1 = 1/1 with 1.5 mol% Pd loading, 100 °C
and 15 h.
Table 3 The effect of solvents and temperatures on the
Suzuki-Miyaura cross-coupling reaction.
Entry
Solvent
Dioxane
Toluene
H2O
Temperature (°C)
Yield (%)
1
2
3
4
100
100
100
78
18
9
8
EtOH
7
Table 5 The effect of reaction time and catalyst loadings on
the Suzuki-Miyaura cross-coupling reaction.
4

catalytic system generally acquired comparable coupling
ACCEPTED MANUSCRIPT
efficiency.6b-d Nevertheless, our catalytic efficiency appears to
exhibit higher yields and wider scope of substrates than other
catalytic systems.6e-k, 24f
Entry
catalyst loading (mol% Pd)
Time (h)
Yield (%)
Table 6 Substrate scope of the Suzuki-Miyaura coupling of
aryl chlorides with arylboronic acids
1
2
3
4
5
2.0
1.5
1.5
1.5
1.0
24
18
15
12
15
81
82
83
59
74
Entry ArX
1
Ar’B(OH)2
Product
Yield
(%)
85
2
3
86
Reaction conditions: 2a (1 mmol), 3a (1.5 mmol), K3PO4·3H2O (3 mmol),
DMF (5 mL), PdCl2/L1 = 1/1, 100 °C, analyzed by GC, average of two runs.
Under the optimized conditions, the reactions of a wide range
of electronically diverse substrates were examined (Table 6).
Aryl chlorides with electron-withdrawing substituents including
4-chloroacetophenone (2a), 3-chloroacetophenone (2b), 2-
chloroacetophenone (2c), p-chlorotrifluoromethylbenzene (2d),
m-chlorotrifluoromethylbenzene (2e), p-chlorobenzyl cyanide
(2f), p-chlorobenzaldehyde (2g) and p-chloronitrobenzene (2h)
underwent coupling with 4-methoxyphenylboronic acid (3a) to
afford the desired biaryls in good yields (82-98%, entries 1-8).
Substituted aryl chlorides exerted steric effect on the desired
products. The meta-substituted aryl chlorides 2b and 2e (entries 3
and 5) gave similar yields to those obtained from the para-
substituted ones 2a and 2d (entries 1 and 4), while ortho-
substituted one 2c produced a slightly lower yield (entry 3). On
the other hand, by comparing the para-substituted aryl chlorides,
it seems that the electron-withdrawing capacity of substituents
was positive correlated to the yields in the following order –
NO2 > –CF3 > –CN > –CHO ≈ –COCH3 (entries 8, 4, 6, 7 and 1,
respectively). This phenomenon was consistent with that reported
in other Suzuki-Miyaura reactions.4a In contrary, the reactions of
the electron-neutral chlorobenzene (2i) and 2-chloropyridine (2j)
(entries 9 and 10) and the electron-donating p-chloroanisole (2k)
(entry 11) afforded the related products in less yields (10-53%).
The reactions between p-chloroanisole (2k) and electron-
neutral/donating phenylboronic acids produced trace or no
product (entries 12 and 13). Steric effects of the phenylboronic
acids did not work well in this system (entries 14, 15, 18 and 19).
Strong electron-withdrawing p-chloronitrobenzene (2e) showed
excellent reactivity (85-98% yields) despite the boronic acids
were substituted by electron-donating (entries 8, 14 and 15),
electron-neutral (entry 16) and even electron-withdrawing (entry
17) groups. Therefore we selected the medium electron-
withdrawing p-chloroacetophenone (2a) to intensively explore
the electron effects of the boronic acids. The yields of the
corresponding products were acceptable in the cases of electron-
donating (entries 1, 18, 19) and electron-neutral (entries 20 and
21) phenylbronic acids, but gradually dropped when introducing
a series of electron-withdrawing –F, –CF3 and –NO2 groups
(entries 22-24). The reactions also gave good yields for the
naphtylboronic acid and benzoheteroaromatic boronic acids
(entries 25-27), but went inactive when using single
heteroaromatic boronic acids (entries 28-29) and 4-
ethylphenylboronic acid pinacol ester (entry 30). However, as
chloride is electron-donating, double arylation using p-
dichlorobenzene (2i) with 4-methoxyphenylboronic acid (3a)
resulted the 4,4''-dimethoxy-1,1':4',1''-terphenyl (4ia) in relatively
low but reasonable yield (46%, entry 31). Compared to the
reported results using N-heterocyclic carbene as ligand, this
82
4
5
95
96
6
93
7
8
9
86
98
10a
10
11
12
13
14
23
53
trace
NR
92
O
B(OH)2
3d
15
96
16
17
18
95
85
77
O
B(OH)2
3d
5

19
81
GC analyses were performed on an Agilent 7820A Gas
Chromatograph with an Agilent HP-5 chromatographic column
ACCEPTED MANUSCRIPT
and N2 as mobile phase. Thermogravimetric analysis (TGA) was
performed on a TASDT Q600 System (heating rate of 10 °C
min−1, under an air stream of 100 mL min−1). The LC-MS
20
21
22
23
24
25
81
80
78
56
37
63
analyses were recorded in
a
Rapid Resolution HT-3
chromatographic column on an Agilent 1260 Infinity Liquid
Chromatograph with 6120 Quadrupole Mass Spectrometer and
MeCN as the mobile phase. 1H and 13C NMR spectra were
recorded at ambient temperature on Varian UNITYplus-300, 400
and 600 spectrometers with chemical shifts referenced to residual
solvent signal. The powder X-ray diffraction (PXRD)
measurements were carried out on a PANalytical X’Pert PRO
MPD system (PW3040/60). Electrospray ion mass spectra (ESI-
MS) were performed on micrOTOF-Q III mass spectrometer.
4.2. Synthesis of compound 1
PdCl2 (0.0089 g, 0.05 mmol) and L1 (0.0139 g, 0.05 mmol)
were added to a Schlenk tube containing a magnetic stirrer bar,
and then DMF (5 mL) was added. The mixture was stirred for 12
h at room temperature to provide a yellow solution. Some yellow
block crystals of 1 were obtained by volatilization from the
yellow solution at room temperature after several days, which
were collected by filtration, washed with Et2O and dried in vacuo.
Yield: 0.0171 g, 75%. Anal. Calcd. for C17H15Cl2N2PPd (%): C,
44.81; H, 3.32; N, 6.15; Found (%): C, 44.77; H, 3.56; N, 6.16.
IR (KBr disk, cm-1): 3462(m), 3078(m), 2919(w), 2839(w),
2768(w), 1610(vs), 1477(vs), 1466(vs), 1435(s), 1385(m),
1307(w), 1275(w), 1234(w), 1157(m), 1105(s), 1023(w), 998(w),
902(s), 880(w), 783(m), 745(m), 705(s), 687(s), 625(w), 534(s),
488(s), 479(s). 1H NMR (400 MHz, DMSO-d6, ppm): δ 10.13 (s,
1H), 9.04 (d, J = 5.9 Hz, 1H), 7.88 (dd, J = 13.3, 7.7 Hz, 5H),
7.68 (dd, J = 28.6, 6.1 Hz, 6H), 7.15 (d, J = 8.3 Hz, 1H), 7.05 (t,
J = 6.6 Hz, 1H). 13C NMR (151 MHz, DMSO-d6, ppm): 161.9,
161.8, 149.0, 142.1, 133.4, 133.0, 132.9, 129.6, 129.5, 116.7,
111.7, 111.6. 31P{1H} NMR (243 MHz, DMSO-d6, ppm): δ 77.8.
26
27
80
81
28
29
trace
trace
30
NR
46
31b
4.3. X-ray structure determination
Reaction conditions: aryl chlorides (1 mmol), arylboronic acid (1.5 mmol),
K3PO4·3H2O (3 mmol), DMF (5 mL), PdCl2/L1 = 1/1, catalyst loading (1.5
mol% Pd), 100 °C, 15 h, isolated yield, average of two runs. a GC yield. b aryl
halides (1 mmol), arylboronic acid (3 mmol), K3PO4·3H2O (6 mmol), DMF
(10 mL), catalyst loading (3 mol% Pd).
Single crystals suitable for X-ray analysis were obtained from
the above preparation and mounted in a capillary. Diffraction
intensities were collected on a Bruker D8-Quest using graphite
monochromated Mo-Kα (λ = 0.71073 Å) radiation. The program
APEX2 v2012.4-3 (Bruker, AXS) was used for the refinement of
cell parameters and the reduction of collected data, while
absorption corrections (multi-scan) were applied. The crystal
structure of 1 was solved by direct methods and refined on F2 by
full-matrix least-squares methods with the SHELXL-2013
program package.32 All non-H atoms were refined anisotropically.
All H atoms were placed in geometrically idealized positions. A
summary of key crystallographic information is given in Table 7.
3. Conclusions
In summary, we have synthesized one mononuclear complex 1
from reaction of PdCl2 with a P,N bidentate ligand L1 and
employed 1 as a catalyst for the Suzuki-Miyaura cross-coupling
reaction of aryl chlorides and aryl boronic acids. This catalytic
system is suitable for a wide scope of substrates and remarkably
better than mono- and bi-dentate phosphines under the same
conditions. Relative to the similar catalytic system using the
bulky analogue L2, complex 1 proved very effective for the
coupling reactions of the relatively unreactive aryl chlorides
containing strong and medium electron-withdrawing groups. The
results demonstrate the importance of ligand design for
stabilizing low-valence Pd intermediates and the advantage in
incorporating both a π-acceptor P and σ-donor N into the
chelating ligands.
Table 7 Crystal data and structure refinement parameters for
compound 1
Formula
Formula weight
Crystal system
Space group
a/Å
C17H15Cl2N2PPd
455.58
Monoclinic
P21/c
4. Experimental
12.6676(15)
11.6312(14)
24.346(3)
103.503(3)
4.1. General procedures
b/Å
All manipulations were carried out using standard Schlenk
techniques. The ligands L1 and L2 were prepared according to
literature procedures.31 The substrates and other chemicals used
for the experiments were purchased from commercial suppliers.
c/Å
β/°
6

V/Å3
3488.0(7)
1.735
8
127.8, 126.9, 125.8 (d, JCF = 3.7 Hz), 124.5 (d, JCF = 271.8 Hz),
114.5, 55.5.
ACCEPTED MANUSCRIPT
Dc/g.cm−3
4.4.5. 3-trifluoromethyl-4'-methoxy-1,1'-biphenyl (4ea).37
Z
1
White solid, H NMR (400 MHz, CDCl3, ppm): δ 7.78 (s, 1H),
ꢀ(Mo-Kα)/mm−1
F(000)
1.461
1808
7.71 (d, J = 7.1 Hz, 1H), 7.61 – 7.46 (m, 4H), 6.99 (d, J = 8.3 Hz,
2H), 3.85 (s, 3H). 13C NMR (151 MHz, CDCl3, ppm): δ 159.8,
141.7, 132.3, 131.2 (d, JCF = 32.0 Hz), 130.0, 129.3, 128.4, 125.3,
123.5 (m, JCF = 3.7 Hz), 114.5, 55.5.
4.4.6. 4-cyano-4'-methoxy-1,1'-biphenyl (4fa).34 White solid,
1H NMR (400 MHz, DMSO-d6, ppm): δ 7.86 (q, J = 8.3 Hz, 4H),
7.72 (d, J = 8.5 Hz, 2H), 7.06 (d, J = 8.5 Hz, 2H), 3.81 (s, 3H).
13C NMR (151 MHz, CDCl3, ppm): δ 160.3, 145.3, 132.6, 131.6,
128.4, 127.2, 119.1, 114.6, 110.2, 55.5.
Total Reflections
Unique Reflections
No. observations
No. parameters
Rint
85023
8681
6607
415
0.0359
0.0259
0.0636
1.067
4.4.7. 4'-methoxy-[1,1'-biphenyl]-4-carbaldehyde (4ga).35
Ra
1
White solid, H NMR (400 MHz, CDCl3, ppm): δ 10.03 (s, 1H),
7.92 (d, J = 8.1 Hz, 2H), 7.71 (d, J = 8.1 Hz, 2H), 7.59 (d, J = 8.6
Hz, 2H), 7.01 (d, J = 8.6 Hz, 2H), 3.87 (s, 3H). 13C NMR (100
MHz, CDCl3, ppm): δ 191.7, 160.0, 146.6, 134.5, 131.9, 130.2,
128.4, 126.9, 114.3, 55.3.
4.4.8. 4-methoxy-4'-nitro-1,1'-biphenyl (4ha).33 Yellow solid,
1H NMR (400 MHz, DMSO-d6, ppm) δ 8.26 (d, J = 8.6 Hz, 2H),
7.92 (d, J = 8.6 Hz, 2H), 7.76 (d, J = 8.6 Hz, 2H), 7.09 (d, J = 8.6
Hz, 2H), 3.82 (s, 3H).13C NMR (151 MHz, CDCl3, ppm): δ 160.5,
147.3, 146.6, 131.1, 128.6, 127.2, 124.2, 114.7, 55.5.
4.4.9. 2-(4-methoxyphenyl)-pyridine (4ja).33 White solid, 1H
NMR (400 MHz, CDCl3, ppm): δ 8.66 (s, 1H), 7.96 (s, 2H),
7.74–7.65 (m, 2H), 7.18 (d, J = 4.0 Hz, 1H), 7.00 (s, 2H), 3.87 (s,
3H). 13C NMR (151 MHz, CDCl3, ppm): δ 160.5, 157.2, 149.6,
136.7, 132.1, 128.2, 121.5, 119.9, 114.2, 55.4.
wRb
GOFc
aR = ||Fo|-|Fc|/|Fo|. bwR = {w(Fo -Fc2)2/w(Fo )2}1/2 cGOF= {w((Fo -Fc2)2)/(n-
.
2
2
2
p)}1/2, where n = number of reflections and p = total number of parameters
refined.
4.4. General procedure for the Suzuki-Miyaura cross-
coupling reaction of aryl chlorides with aryl boronic acids
In a 25 mL Schlenk tube containing a magnetic stirrer bar, 4-
chloroacetophenone (2a) (155 mg, 1 mmol) was mixed with 4-
methoxyphenylboronic acid (3a) (228 mg, 1.5 mmol). Then
trihydrate potassium phosphate (798 mg, 3 mmol) and DMF (5
mL) were added. The dissolved mixture of 1 (1.50 mL, 0.015
mmol) was transferred into the tube by a pipette. The tube was
◦
placed in a 100 C oil bath and stirred for 15 h. At the end of the
1
4.4.10. 4,4'-Dimethoxy-1,1'-biphenyl (4ka).33 White solid, H
reaction, the mixture was cooled to room temperature, added with
water (5 mL), and then extracted with ethyl acetate (3×5 mL).
The organic layer was dried over anhydrous Na2SO4. After
evaporation of the solvent, the residue was subjected to silica gel
column chromatography to give the cross-coupling product.
Finally, the resulting products were characterized using 1H NMR
and 13C NMR. See Supplementary data for full ESI-MS data of
the catalysts and characterization data for the isolated products.
4.4.1. 1-(4'-methoxy-[1,1'-biphenyl]-4-yl)ethanone (4aa).33
White solid, 1H NMR (400 MHz, CDCl3, ppm): δ 8.00 (d, J = 8.0
Hz, 2H), 7.64 (d, J = 8.0 Hz, 2H), 7.58 (d, J = 8.0 Hz, 2H), 7.00
(d, J = 8.0 Hz, 2H), 3.86 (s, 3H), 2.62 (s, 3H). 13C NMR (151
MHz, CDCl3, ppm): δ 197.8, 160.0, 145.5, 135.4, 132.4, 129.1,
128.4, 126.7, 114.5, 55.5, 26.7.
4.4.2. 1-(4'-methyl-[1,1'-biphenyl]-3-yl)ethan-1-one (4ba).34
Yellow solid, 1H NMR (400 MHz, CDCl3, ppm): δ 8.14 (s, 1H),
7.88 (d, J = 7.6 Hz, 1H), 7.75 (d, J = 7.6 Hz, 1H), 7.65 – 7.42 (m,
3H), 7.00 (d, J = 8.3 Hz, 2H), 3.86 (s, 3H), 2.65 (s, 3H). 13C
NMR (151 MHz, CDCl3, ppm): δ 198.3, 159.7, 141.4, 137.7,
132.8, 131.4, 129.1, 128.3, 126.7, 126.6, 114.5, 55.5, 26.9.
4.4.3. 1-(4'-methyl-[1,1'-biphenyl]-2-yl)ethan-1-one (4ca).34
Colorless oil, 1H NMR (400 MHz, CDCl3, ppm): δ 7.50 (dd, J =
15.9, 7.6 Hz, 2H), 7.38 (t, J = 7.2 Hz, 2H), 7.27 (d, J = 7.6 Hz,
2H), 6.96 (d, J = 8.3 Hz, 2H), 3.85 (s, 3H), 2.01 (s, 3H). 13C
NMR (151 MHz, CDCl3, ppm): 205.4, 159.7, 141.0, 140.2, 133.1,
130.8, 130.1, 127.9, 127.2, 114.3, 55.4, 30.5.
NMR (400 MHz, CDCl3, ppm): δ 7.47 (d, J = 8.6 Hz, 4H), 6.96
(d, J = 8.6 Hz, 4H), 3.84 (s, 6H). 13C NMR (100 MHz, CDCl3,
ppm): δ 159.1, 140.8, 133.8, 128.7, 128.1, 126.7, 126.6, 114.2,
55.3.
4.4.11. 3-methoxy-4'-nitro-1,1'-biphenyl (4hd).34 Yellow solid,
1H NMR (400 MHz, CDCl3, ppm): δ 8.29 (d, J = 8.6 Hz, 2H),
7.73 (d, J = 8.6 Hz, 2H), 7.41 (t, J = 7.9 Hz, 1H), 7.20 (d, J = 7.6
Hz, 1H), 7.14 (s, 1H), 6.99 (d, J = 6.8 Hz, 1H), 3.89 (s, 3H). 13C
NMR (151 MHz, CDCl3, ppm): 160.1, 147.5, 147.1, 140.2, 130.2,
127.8, 124.0, 119.8, 114.1, 113.2, 55.4.
4.4.12. 2-methoxy-4'-nitro-1,1'-biphenyl (4he).36 Yellow solid,
1H NMR (400 MHz, CDCl3, ppm): δ 8.25 (d, J = 8.4 Hz, 2H),
7.69 (d, J = 8.4 Hz, 2H), 7.40 (t, J = 7.8 Hz, 1H), 7.33 (d, J = 7.4
Hz, 1H), 7.01 – 7.09 (m, 2H), 3.84 (s, 3H). 13C NMR (151 MHz,
CDCl3, ppm): 156.4, 146.6, 145.4, 130.6, 130.3, 1301, 128.2,
123.2, 121.1, 111.4, 55.5.
1
4.4.13. 4-nitro-1,1'-biphenyl (4eb).5(b) Yellow solid, H NMR
(400 MHz, CDCl3, ppm):δ 8.30 (d, J = 8.6 Hz, 2H), 7.74 (d, J =
8.6 Hz, 2H), 7.63 (d, J = 7.4 Hz, 2H), 7.48 (dt, J = 14.4, 7.1 Hz,
3H). 13C NMR (151 MHz, CDCl3, ppm): δ 147.8, 147.2, 138.9,
129.3, 129.1, 128.0, 127.5, 124.3.
4.4.14. 4-trifluoromethyl-4'-nitro-1,1'-biphenyl (4hf).37 Yellow
1
solid, H NMR (400 MHz, CDCl3, ppm): δ 8.34 (d, J = 8.6 Hz,
2H), 7.75 (dd, J = 11.2, 7.6 Hz, 6H). 13C NMR (151 MHz,
DMSO-d6, ppm): δ 147.7, 146.0, 142.2, 128.1, 127.8, 126.1 (d,
JCF = 3.6 Hz), 124.2, 123.9 (d, JCF = 273.3 Hz).
4.4.4. 4-trifluoromethyl-4'-methoxy-1,1'-biphenyl (4da).37
White solid, H NMR (400 MHz, CDCl3, ppm): δ 7.65 (s, 4H),
1
4.4.15. 1-(3'-methoxy-[1,1'-biphenyl]-4-yl)ethanone (4ad).38
1
7.54 (d, J = 8.5 Hz, 2H), 7.00 (d, J = 8.5 Hz, 2H), 3.86 (s, 3H).
White solid, H NMR (400 MHz, CDCl3, ppm): δ 8.02 (d, J =
13C NMR (151 MHz, CDCl3, ppm): δ 159.9, 144.4, 132.3, 128.4,
7.9 Hz, 2H), 7.68 (d, J = 7.9 Hz, 2H), 7.39 (t, J = 7.8 Hz, 1H),
7.22 – 7.15 (m, 2H), 6.95 (d, J = 7.7 Hz, 1H), 3.88 (s, 3H), 2.64
7

(s, 3H). 13C NMR (151 MHz, CDCl3, ppm): δ 197.7, 160.0,
145.6, 141.3, 136.0, 130.0, 128.8, 127.2, 119.7, 113.5, 113.1,
Acknowledgments
ACCEPTED MANUSCRIPT
55.3, 26.6.
The authors thank the National Natural Science Foundation of
China (21271134, 21373142, 21531006 and 21671144) and State
Key Laboratory of Organometallic Chemistry, Shanghai Institute
of Organic Chemistry, Chinese Academy of Sciences (2015kf-
07) for financial support. J. P. Lang also highly appreciates the
financial support of the "Qing-Lan" Project of Jiangsu Province,
the Priority Academic Program Development of Jiangsu Higher
Education Institutions, and the “Soochow Scholar” Program of
Suzhou University.
4.4.16. 1-(2'-methoxy-[1,1'-biphenyl]-4-yl)ethanone (4ae).34
White solid, 1H NMR (400 MHz, CDCl3, ppm): δ 8.00 (d, J = 8.0
Hz, 2H), 7.63 (d, J = 8.0 Hz, 2H), 7.38-7.32 (q, 2H), 7.07-6.99
(m, 2H), 3.82 (s, 3H), 2.63 (s, 3H). 13C NMR (151 MHz, CDCl3,
ppm): δ 197.8, 156.4, 143.6, 135.5, 130.7, 129.7, 129.5, 128.0,
120.9, 111.3, 55.5, 26.6.
4.4.17. 1-([1,1'-Biphenyl]-4-yl)ethan-1-one (4ab).33 White
1
solid, H NMR (400 MHz, CDCl3, ppm): δ 8.03 (d, J = 8.1 Hz,
2H), 7.66 (dd, J = 23.0, 7.8 Hz, 4H), 7.47 (t, J = 7.4 Hz, 2H),
7.41 (d, J = 7.2 Hz, 1H), 2.64 (s, 3H). 13C NMR (151 MHz,
CDCl3, ppm): δ 197.8, 145.9, 140.0, 136.0, 129.1, 129.0, 127.4,
26.8.
Supplementary data
1
The H and 13C NMR spectra for the isolated products can be
found in online version at http://dx.doi.org/10.1016/*******。
4.4.18. 1-(4'-methyl-[1,1'-biphenyl]-4-yl)ethan-1-one (4ag).39
White solid, 1H NMR (400 MHz, DMSO-d6, ppm): δ 8.02 (d, J =
8.2 Hz, 2H), 7.79 (d, J = 8.2 Hz, 2H), 7.64 (d, J = 7.9 Hz, 2H),
7.31 (d, J = 7.8 Hz, 2H), 2.60 (s, 3H), 2.35 (s, 3H). 13C NMR
(151 MHz, CDCl3, ppm): δ 196.9, 144.9, 137.4, 136.1, 134.8,
128.8, 128.1, 126.2, 126.1, 25.8, 20.3.
CCDC **** contain the supplementary crystallographic data of
compound
www.ccdc.cam.ac.uk/data_request/cif,
1
can be obtained free of charge via
or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge CB2
1EZ, UK; fax: +44 1223 336033.
4.4.19. 1-(4'-fluoro-[1,1'-biphenyl]-4-yl)ethan-1-one (4ah).37
White solid, 1H NMR (400 MHz, CDCl3, ppm): δ 8.03 (d, J = 8.0
Hz, 2H), 7.66 – 7.57 (m, 4H), 7.16 (t, J = 8.5 Hz, 2H), 2.64 (s,
References and notes
1
(a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457; (b) Suzuki, A. J.
Organomet. Chem. 1999, 576, 147; (c) Hassan, J.; Sevignon, M.; Gozzi,
C.; Schulz, E.; Lemaire, M. Chem. Rev. 2002, 102, 1359; (d) Miyaura,
N. J. Organomet. Chem. 2002, 653, 54.; (e) Kotha, S.; Lahiri, K.;
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Canturk, B. Angew. Chem. 2009, 121, 9404; (g) Torborg, C.; Beller, M.
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Neumann, H.; Beller, M. Angew. Chem. 2010, 122, 9231; (i) Suzuki, A.;
Yamamoto, Y. Chem. Lett. 2011, 40, 894.
3H). 13C NMR (151 MHz, CDCl3, ppm): δ 197.7, 163.1 (d, JCF
248.1 Hz), 144.8, 136.1 (d, JCF = 3.1 Hz), 135.9, 129.1 (d, JCF
2.8 Hz), 127.2, 116.0 (d, JCF = 21.6 Hz), 26.7.
=
=
4.4.20. 1-(4'-(trifluoromethyl)-[1,1'-biphenyl]-4-yl)ethan-1-one
1
(4af).37 White solid, H NMR (400 MHz, DMSO-d6, ppm): δ
8.08 (d, J = 8.2 Hz, 2H), 7.97 (d, J = 8.0 Hz, 2H), 7.88 (dd, J =
16.7, 8.1 Hz, 4H), 2.63 (s, 3H). 13C NMR (101 MHz, DMSO-d6,
ppm): δ 197.5, 142.8, 136.4, 129.0, 127.9, 127.3, 125.9 (d, JCF
= 3.8 Hz), 124.2 (d, JCF = 272.0 Hz), 26.8.
2
(a) Wolfe, J. P.; Singer, R. A.; Yang, B. H.; Buchwald, S. L. J. Am.
Chem. Soc. 1999, 121, 9550; (b) Kataoka, N.; Shelby, Q.; Stambuli, J.
P.; Hartwig, J. F. J. Org. Chem. 2002, 67, 5553; (c) Martin, R.;
Buchwald, S. L. Acc. Chem. Res. 2008, 41, 1461; (d) Fleckenstein, C.
A.; Plenio, H. Chem. Soc. Rev. 2010, 39, 694; (e) Liu, D. X.; Gong, W.
J.; Li, H. X.; Gao, J.; Li, F. L.; Lang, J. P. Tetrahedron 2014, 70, 3385;
(f) Li, Q.; Zhang, L. M.; Bao, J. J.; Li, H. X.; Xie, J. B.; Lang, J. P. Appl.
Organometal. Chem. 2014, 28, 861.
4.4.21. 1-(4'-nitro-[1,1'-biphenyl]-4-yl)ethan-1-one (4ac).40
1
Yellow solid, H NMR (400 MHz, CDCl3, ppm):δ 8.34 (d, J =
7.3 Hz, 2H), 8.09 (d, J = 7.0 Hz, 2H), 7.76 (dd, J = 21.9, 7.3 Hz,
4H), 2.67 (s, 3H). 13C NMR (75 MHz, CDCl3, ppm): δ 197.9,
147.9, 146.5, 143.4, 137.3, 129.4, 128.4, 124.5, 116.0, 27.0.
4.4.22. 1-(4-(Naphthalen-1-yl)phenyl)ethan-1-one (4ai).41
White solid, 1H NMR (400 MHz, CDCl3, ppm): δ 8.08 (d, J = 8.7
Hz, 3H), 7.96–7.86 (m, 3H), 7.79 (dd, J = 22.8, 7.8 Hz, 3H), 7.52
(d, J = 3.6 Hz, 2H), 2.66 (s, 3H). 13C NMR (151 MHz, CDCl3,
ppm): δ 197.9, 145.8, 137.3, 136.0, 133.7, 133.1, 129.1, 128.8,
128.5, 127.8, 127.6, 126.7, 126.6, 126.5, 125.3, 26.8.
3
4
Thomas, A. A.; Denmark, S. E. Science. 2016, 352, 329.
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Organomet. Chem. 2012, 696, 4293; (c) Silarska, E.; Trzeciak, A. M.;
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2016, 18, 3186.
4.4.23. 1-(4-(Benzofuran-2-yl)phenyl)ethan-1-one (4aj).42
1
5
(a) Li, L.; Zhao, S. B.; Amruta, J. P.; Diane, M.; Biscoe, M. R. J. Am.
Chem. Soc. 2014, 136, 14027; (b) Shahnaz, N.; Puzari, A.; Paul, B.; Das,
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White solid, H NMR (400 MHz, CDCl3, ppm): δ 8.06–8.00 (m,
2H), 7.94 (t, J = 6.0 Hz, 2H), 7.66–7.50 (m, 2H), 7.38–7.22 (m,
2H), 7.17 (d, J = 5.2 Hz, 1H), 2.64 (d, J = 5.6 Hz, 3H). 13C NMR
(151 MHz, CDCl3, ppm): δ 197.4, 155.3, 154.6, 136.6, 134.7,
129.0, 125.3, 124.9, 123.4, 121.4, 111.5, 103.8, 26.7.
4.4.24.
1-(4-(Benzo[b]thiophen-2-yl)phenyl)ethan-1-one
1
6
(a) Shen, A.; Hu, Y. C.; Liu, T. T.; Ni, C.; Luo, Y.; Cao, Y. C.
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Marchenko, A.; Koidan, H.; Hurieva, A.; Vlasenko, Y.; Kostyuk, A.;
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(4ak).43 White solid, H NMR (400 MHz, CDCl3, ppm): δ 8.01
(d, J = 8.2 Hz, 2H), 7.83 (dd, J = 19.6, 7.9 Hz, 4H), 7.67 (s, 1H),
7.37 (t, J = 5.5 Hz, 2H), 2.64 (s, 3H). 13C NMR (151 MHz,
CDCl3, ppm): δ 197.3, 142.6, 140.4, 139.9, 138.7, 136.4, 129.0,
126.3, 125.0, 124.8, 124.0, 122.3, 121.2, 26.6.
4.4.25. 4,4''-dimethoxy-1,1':4',1''-terphenyl (4ia).44 White solid,
1H NMR (400 MHz, CDCl3, ppm): δ 7.61 (s, 4H), 7.57 (d, J = 8.0
Hz, 4H), 7.01-6.98 (d, J = 12.0 Hz, 4H), 3.86 (s, 6H). 13C NMR
(151 MHz, CDCl3, ppm): δ 159.1, 139.1, 133.3, 128.0, 127.0,
114.2, 55.4.
8

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ACCEPTED MANUSCRIPT
Research Highlights
► Compound 1 is a PdCl2 adduct of N-diphenylphosphanyl-2-aminopyridine.
► Compound 1 can catalyze the reactions of aryl chlorides with aryl boronic acids.
► This catalytic system is suitable for a wide scope of substrates.