N-Heterocyclic carbene-palladacyclic complexes: synthesis, characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

Article abstract of DOI:10.1016/j.tet.2018.07.052

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01 mol%).

Full text of DOI:10.1016/j.tet.2018.07.052

Accepted Manuscript
N-heterocyclic carbene-palladacyclic complexes: Synthesis, characterization and their
applications in the C-N coupling and α-arylation of ketones using aryl chlorides
Feng Liu, Yuan-Yuan Hu, Di Li, Quan Zhou, Jian-Mei Lu
PII:
S0040-4020(18)30918-9
10.1016/j.tet.2018.07.052
TET 29712
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 28 June 2018
Revised Date: 26 July 2018
Accepted Date: 27 July 2018
Please cite this article as: Liu F, Hu Y-Y, Li D, Zhou Q, Lu J-M, N-heterocyclic carbene-palladacyclic
complexes: Synthesis, characterization and their applications in the C-N coupling and α-arylation of
ketones using aryl chlorides, Tetrahedron (2018), doi: 10.1016/j.tet.2018.07.052.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical Abstract
N-Heterocyclic carbene-palladacyclic
Leave this area blank for abstract info.
complexes: synthesis, characterization and
their applications in the C-N coupling and α-
arylation of ketones using aryl chlorides
Feng Liu, Yuan-Yuan Hu, Di Li, Quan Zhou and Jian-Mei Lu*
College of Chemistry and Materials Engineering, Wenzhou University, Chashan University Town, Wenzhou,
Zhejiang Province 325035, People’s Republic of China.
R
R
N
N
N
N
N
K2CO3
Pd
Cl
Cl
+
+
PdCl2
THF, Temp., 18 h
N
2
R
R
1a: R = 2,6-iPr2
3a: 99% (R = 2,6-iPr2), T = 50 o
C
3b: 94% (R = 2,4,6-Me3), T = 90 o
C
1b: R = 2,4,6-Me3
Cl
complex 3a
(0.01-0.05 mol%)
KOtBu, toluene
110 oC, 24 h
R1
N
R2
R1
+
HN
R2
R
R
6
5
4
Cl
O
O
complex 3a
(1.0-2.0 mol%)
+
NaOtBu, toluene
80 oC, 3 h
R'
R'
R
7
4
8
R

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
N-Heterocyclic carbene-palladacyclic complexes: synthesis, characterization and their
applications in the C-N coupling and α-arylation of ketones using aryl chlorides
Feng Liu, Yuan-Yuan Hu, Di Li, Quan Zhou and Jian-Mei Lu
College of Chemistry and Materials Engineering, Wenzhou University, Chashan University Town, Wenzhou, Zhejiang Province 325035, People’s Republic of
China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot
procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray
single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-
arylation of ketones even at very low catalyst loadings (0.01 mol%).
Available online
2009 Elsevier Ltd. All rights reserved
.
Keywords:
N-heterocyclic carbene-palladacyclic complex
aryl chlorides
C-N coupling
α-arylation
synthetic methods
1. Introduction
found to be an active catalyst in the Buchwald-Hartwig
amination and α-arylation of ketones using aryl chlorides even at
very low catalyst loadings. Herein, we report these results in
detail.
Palladium-catalyzed cross-coupling reactions are the most
important methods in the modern organic synthesis for the
formation of carbon-carbon and carbon-heteroatom bonds.1
Among the organic electrophiles involved, aryl chlorides seem to
be the most important but challenging ones because they are
more available and cheaper but less active than aryl bromides and
iodides, which thus attract much attention.2 Consequently, a
series of tertiary phosphine ligands with high activity but air- and
moisture-sensitive has been developed for the efficient coupling
of aryl chlorides.3 In order to overcome the disadvantages of
phosphine ligands, lots of well-defined N-heterocyclic carbene
(NHC)-palladium complexes, which usually are air- and thermal-
stable, mainly developed by Nolan,4 Organ,5 Lavigne,6 Tu7 and
others,8 have shown efficiently catalytic activity in the cross-
coupling reactions of aryl chlorides. Among these NHC-Pd(II)
complexes, besides the bulky and strong donating NHC skeleton,
the ancillary ligands also play important role in the catalytic
activities. We were therefore interested in the development of
easily synthesized and highly reactive NHC-Pd(II) complexes by
trying different ancillary ligands. As a consequent, we also have
successfully developed a series of NHC-Pd(II) complexes and
found them to be efficient catalysts in the cross-coupling
reactions of aryl chlorides.9 To continue investigating the
influence of ancillary ligands, N-heterocyclic carbene-
2. Results and discussion
2.1. Synthesis of NHC-Pd(II) complexes 3.
First, by a slightly modified method according to our
previously reported procedure,9b N-heterocyclic carbene-
palladacyclic complexes 3 were easily obtained in 99% and 94%
yields from commercially available imidazolium salts 1, PdCl2
and benzo[h]quinoline 2 in a one-step process (Scheme 1).
Crystals of 3a were grown in the mixture of ethyl acetate and
dichloromethane, and its structure was unambiguously
determined by X-ray single crystal diffraction (Figure 1).11
palladacyclic complexes
3
were synthesized by using
imidazolium salts 1, PdCl2 and benzo[h]quinoline 2 in a one-pot
procedure.10 In addition, one of the complexes, complex 3a, was
Corresponding author. Tel.: +86-577-86689300; fax: +86-577-86689300; e-mail: ljm@wzu.edu.cn

2
Tetrahedron
ACCEPTED MANUSCRIPT
2
NaOtBu
LiOtBu
K2CO3
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
toluene
toluene
toluene
THF
<5
NR
NR
85
56
5
3a
3
4
3a
3a
3a
3a
3a
3b
3a
3a
3a
5
6
dioxane
DMF
7
8
toluene
toluene
toluene
toluene
9
9c
10d
11e
79
96
55
Figure 1. Molecular structure of 3a. Hydrogens have been
omitted for clarity. Selected bond lengths (Å) and angles (deg):
Pd(1)-C(1) = 1.990(3); Pd(1)-C(38) = 1.988(5); Pd(1)-N(3) =
a
Otherwise specified, all reactions were carried out using
chlorobenzene 4a (0.5 mmol), morpholine 5a (0.6 mmol), base
(1.3 equiv) and 3 (0.1 mol%) in solvent (1.0 mL) at 90 oC for 3 h.
b Isolated yields.
2.086(4); Pd(1)-Cl(1)
=
2.3864(12); C(1)-Pd(1)-N(3)
=
176.36(15); C(1)-Pd(1)-Cl(1) = 90.70(10); N(3)-Pd(1)-Cl(1) =
90.89(16); C(38)-Pd(1)-C(1) = 96.25(18); C(38)-Pd(1)-N(3) =
82.1 (2).
c 3a (0.05 mol%), 90 oC, 24 h.
d 3a (0.04 mol%), 110 oC, 24 h.
e 3a (0.03 mol%), 110 oC, 24 h.
2.2. Buchwald-Hartwig amination of aryl chlorides
Using complex 3a as the catalyst, a series of aryl chlorides and
amines were used as the substrates to test the generality and
limitation of the reactions. As shown in Table 2, all reactions
proceeded smoothly to give the corresponding coupling products
6 in good to excellent yields. The relative position of the same
substituents on the phenyl ring of aryl chlorides has some effect
on the coupling reactions. For example, when 2-chlorotoluene 4f
was used as the substrate, more catalyst loading (0.05 mol%) was
necessary to achieve similarly high yields (6h, 6l, 6o and 6p)
(entries 7, 11, 14 and 15). For 3-chlorotoluene 4c, only 0.015
mol% 3a was necessary and the aminated product 6e was formed
in 89% yield (entry 4). For electron-deficient substrates such as
3-chlorofluorobenzene 4d and 4-chlorofluorobenzene 4e, the
reactions took place smoothly to give the desired products 6f, 6g,
6j, 6k and 6n in good to high yields in the presence of 0.025
mol% 3a (entries 5, 6, 9, 10 and 13). The reaction of sterically
hindered substrates 2-chloro-1,3-diisopropylbenzene 4h with
2,4,6-trimethylaniline 5h gave almost quantitative yield with 0.05
mol% 3a (entry 20).
To evaluate the catalytic properties of N-heterocyclic carbene-
palladacyclic complexes 3, the amination of chlorobenzene 4a
with morpholine 5a was selected as the model reaction (Table 1).
Using 3a (0.1 mol%) as the catalyst, KOtBu (1.3 equiv) as the
base, the reaction of chlorobenzene 4a (0.5 mmol) with
morpholine 5a (0.6 mmol) gave the corresponding aminated
o
product 6a in 94% yield in toluene at 90 C for 3 h (entry 1).
When NaOtBu was used as the base, very low yields of the
desired aminated product 6a was observed (entry 2). In the
presence of other bases such as LiOtBu and K2CO3, no reaction
occurred (entries 3 and 4). Using KOtBu as the base, a variety of
solvents was then tested. For instance, when THF and dioxane
were chosen as the solvents, 6a can be obtained in 85 and 56%
yields, respectively (entries 5 and 6). When polar solvent such as
DMF was used, only 5% yield was observed (entry 7). Catalytic
activity of 3b was also tested and only 9% yield of product 6a
was found (entry 8). The catalytic property of complex 3a at
lower catalyst loadings was then further investigated. When the
catalyst loading was lowered to 0.05 mol%, 6a can be achieved
in 79% yield within a prolonged reaction time (entry 9). The
reaction can proceed smoothly and afford satisfactory yield in the
o
presence of 0.04 mol% 3a at 110 C for 24 h (entry 10). When
the catalyst loading was further lowered to 0.03 mol%, 6a was
obtained in moderate yield even the reaction was carried out at
110 oC for 24 h (entry 11).
Entrya
1
4 (R)
[X]
Yield (%)b
5
4b (3-OMe)
0.015
6b, 90
5a
Entrya
1
Base
KOtBu
Solvent
toluene
Yield (%)b
94
2
3
4a (H)
0.02
6c, 86
6d, 97
3
5b
5b
3a
0.015
4b

3
4
5
6
7
4c (3-Me)
4d (3-F)
4e (4-F)
0.015
6e, 89
5b
5b
5b
5b
ACCEPTED MANUSCRIPT
0.025
6f, 93
6g, 90
6h, 93
0.025
0.05
4f (2-Me)
8
0.015
6i, 81
4b
Entrya
Base
Solvent
toluene
toluene
toluene
toluene
toluene
toluene
THF
Yield (%)b
5c
5c
5c
5c
1
2
3
4
5
6
7
8
9
KOtBu
NaOtBu
LiOtBu
KOH
<5
93
9
0.025
0.025
0.05
6j, 87
6k, 81
6l, 87
4d
4e
4f
10
11
<5
<5
NR
NR
<5
<5
<5
K3PO4
NaOH
NaOtBu
NaOtBu
NaOtBu
12
0.015
6m, 90
4b
5d
5d
5d
13
14
0.025
0.05
6n, 83
6o, 86
4d
4f
dioxane
DMF
a All reactions were carried out using 4i (0.6 mmol), 7a (0.5
15
0.05
6p, 94
4f
mmol), 3a (1.0 mol%), base (2.0 equiv) in solvent (1.0 mL) at 80
5e
5f
oC for 3 h. b Isolated yields.
Under the optimal reaction conditions, a series of aryl
chlorides and propiophenone derivatives were examined (Table
4). Most reactions performed well enough in the presence of 1.0
or 2.0 mol% 3a at 80 oC. It seems that the relative position of the
same substituents on the phenyl rings of aryl chlorides affected
the reactions to some extent. For example, para-substituted aryl
chlorides are better than ortho- and meta-substituted ones, giving
higher yields under the same reaction conditions (entries 4, 6, 7-9
and 12). When 2-chloroanisole and 3-chloroanisole were used,
the amount of complex 3a should be increased to 2.0 mol% to
achieve satisfactory results (entries 2 vs 3 and 10 vs 11).
Heteroaryl chloride such as 3-chloropyridine 4n was also a good
substrate, giving product 8k in 77% yield in the presence of 2.0
mol% 3a at 100 oC for 12 h (entry 14). Diverse electronic
substituents on the propiophenone derivatives are all tolerated in
such transformation. For instance, electron-rich groups such as
methoxy and methyl group and electron-poor group such as
fluorine atom are all tolerated to give the corresponding products
in good yields (entries 15-30). Ortho-subtituted propiophenone
derivative such as 2-fluoropropiophenone 7e gave somewhat
lower yield under the same reaction conditions (entry 28).
16 4g (2,6-Me2)
0.01
6q, 81
17
0.01
0.02
6r, 97
6s, 96
4g
4g
5g
18
5h
5g
5h
19 4h (2,6-iPr2)
20
0.04
0.05
6t, 79
6u, 98
4h
a All reactions were carried out using aryl chlorides 4 (0.7 mmol),
amines 5 (0.84 mmol), KOtBu (1.3 equiv), 3a (X mol%) in
toluene (1.0 mL) at 110 oC for 24 h. b Isolated yields.
2.3. α-Arylation of ketones with aryl chlorides
Then we investigated the use of N-heterocyclic carbene-
palladacyclic complex 3a as the catalyst in the α-arylation of
ketones with aryl chlorides (Table 3). Using 3a as the catalyst,
the reaction of 4-chloroanisole 4i with propiophenone 7a was
carried out in toluene at 80 oC for 3 h. A lot of bases were tested
and NaOtBu gave the best outcome, giving the corresponding α-
arylated product 8a in 93% yield (entry 2). Almost no reaction
was observed when other solvents such as THF, dioxane and
DMF were used (entries 7-9).
Entrya
4 (R)
4a (H)
4b (3-OMe)
4b
7 (R’)
7a (H)
7a
[X]
1.0
1.0
2.0
1.0
2.0
Yield (%)b
8b, 89
8c, 64
1
2
3
4
5
8c, 89
7a
4d (3-F)
4d
8d, 52
8d, 87
7a
7a

4
Tetrahedron
ACCEPTED MANUSCRIPT
6
7
4e (4-F)
4f (2-Me)
4j (3-Me)
4k (4-Me)
4l (2-OMe)
4l
1.0
8e, 81
8f, 89
8g, 89
8h, 95
8i, <5
8i, 99
8j, 58
8j, 77
7a
7a
7a
7a
7a
7a
7a
7a
Solvents were dried by standard methods. Amines were distilled
prior to use. Other commercially obtained reagents were used
without further purification. The mass analyzer type for the high
resolution mass spectra (HRMS) is quadrupole (for ESI). Flash
column chromatography was performed on silica gel (300-400
mesh).
1.0
1.0
1.0
1.0
2.0
2.0
2.0
8
9
10
11
12
13c
4.2. Experimental procedure
4.2.1. General procedure for the synthesis of N-heterocyclic
carbene-palladacyclic complexes 3. Under N2 atmosphere, a
mixture of imidazolium salts 1 (0.22 mmol), PdCl2 (0.2 mmol),
K2CO3 (0.44 mmol) and benzo[h]quinoline 2 (0.22 mmol) was
stirred in anhydrous THF (2.0 mL) at 50 or 90 oC for 18 h. Then
the solvent was removed under reduced pressure, and the residue
was purified by flash chromatography on silica gel (CH2Cl2) to
give complexes 3 as yellow solids.
4m (2-F)
4m
14c,d
2.0
8k, 77
7a
4n
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
7b (4-Me)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
8l, 96
8m, 80
8n, 86
8o, 97
8p, 80
8q, 83
8r, 84
8s, 92
8t, 96
8u, 90
8v, 87
8w, 97
8x, 86
8y, 71
8z, 91
8aa, 93
4a
4.2.1.1. Compound 3a. yellow solid; m.p. 298 oC
(decomposed). 1H NMR (300 MHz, CDCl3, TMS) δ 9.44 (dd, J =
5.1, 1.2 Hz, 1H), 7.98 (dd, J = 8.1, 1.5 Hz, 1H), 7.56 (d, J = 8.7
Hz, 1H), 7.45-7.21 (m, 10H), 7.10 (dd, J = 7.2, 2.1 Hz, 2H), 6.96
(d, J = 7.2 Hz, 1H), 3.51-3.30 (m, 4H), 1.52 (d, J = 6.3 Hz, 6H),
1.18 (d, J = 6.9 Hz, 6H), 1.06 (d, J = 6.9 Hz, 6H), 0.66 (d, J = 6.3
Hz, 6H). 13C NMR (125 MHz, CDCl3) δ 177.9, 153.9, 153.5,
148.6, 147.8, 145.0, 142.0, 136.3, 135.9, 134.2, 132.8, 129.9,
128.23, 128.18, 125.7, 125.0, 124.2, 123.9, 123.0, 121.7, 120.6,
29.0, 28.4, 26.5, 26.2, 23.2, 23.0. IR (neat) ν 2977, 2927, 2860,
1624, 1593, 1565, 1462, 1394, 1380, 1364, 1330, 1266, 1196,
1182, 1115, 937, 830, 816, 801, 758 cm-1. MS (ESI): 672 [M-
Cl]+. HRMS (ESI) calcd. for C40H44N3Pd [M-Cl]+: 672.2579;
found: 672.2594. Anal. calcd. for C40H44ClN3Pd: C, 67.79%; H,
6.26%; N, 5.93%; found: C, 67.71%; H, 6.26%; N, 5.67%.
4.2.1.2. Compound 3b. yellow solid. m.p. 289 oC
(decomposed). 1H NMR (300 MHz, CDCl3, TMS) δ 9.45 (dd, J =
5.1, 1.5 Hz, 1H), 7.95 (dd, J = 8.1, 1.2 Hz, 1H), 7.54 (d, J = 9.0
Hz, 1H), 7.43 (d, J = 8.1 Hz, 1H), 7.34 (d, J = 8.7 Hz, 1H), 7.26-
7.21 (m, 4H), 6.97-6.95 (m, 3H), 6.75 (s, 2H), 2.50 (s, 6H), 2.28
(s, 6H), 2.17 (s, 6H). 13C NMR (125 MHz, CDCl3) δ 176.0,
153.9, 152.1, 148.9, 141.9, 138.5, 137.4, 136.4, 136.3, 136.0,
133.8, 132.9, 129.6, 128.9, 128.3, 127.0, 125.9, 123.8, 122.9,
122.1, 120.7, 20.9, 20.1, 19.8. IR (neat) ν 2918, 1739, 1565,
1486, 1393, 1368, 1320, 1264, 1219, 924, 850, 834, 820, 765,
746 cm-1. MS (ESI): 588 [M-Cl]+. HRMS (ESI) calcd. for
C34H32N3Pd [M-Cl]+: 588.1638; found: 588.1678. Anal. calcd. for
C34H32ClN3Pd: C, 65.39%; H, 5.16%; N, 6.73%; found: C,
65.17%; H, 5.36%; N, 6.66%.
4i (4-OMe)
7b
4j
4k
4a
4f
7b
7b
7c (4-F)
7c
4i
7c
4j
7c
7c
4k
4a
4i
7d (4-OMe)
7d
4k
4e
4k
4a
4k
7d
7d
7e (2-F)
7f (3-F)
7f
a
Otherwise specified, all reactions were carried out using 4 (0.6
mmol), 7 (0.5 mmol), 3a (X mol%), NaOtBu (2.0 equiv) in
toluene (1.0 mL) at 80 oC for 3 h. b Isolated yields.
c The reaction time was 12 h. d The temperature was 100 oC.
3. Conclusion
In conclusion, new N-heterocyclic carbene-palladacyclic
complexes 3 have been developed successfully by simple
operation between easily and commercially available starting
materials such as NHC.HCl, PdCl2 and benzo[h]quinoline. Initial
studies on their catalytic activity disclosed that they were
efficient catalysts toward Buchwald-Hartwig amination and α-
arylation of ketones using aryl chlorides even at very low catalyst
loadings.
4.2.2. General procedure for the complex 3a-catalyzed
amination of aryl chlorides. Under N2 atmosphere, KOtBu (1.3
equiv), toluene (1.0 mL), amines 5 (0.84 mmol), aryl chlorides 4
(0.7 mmol) and finally a solution of complex 3a (20-100 µL,
0.01-0.05 mol%, prepared from 0.014 mmol 3a in 4.0 mL
toluene) were successively added into a Schlenk reaction tube.
o
The mixture was stirred vigorously at 110 C for 24 h. Then the
solvent was removed under reduced pressure and the residue was
purified by flash column chromatography (SiO2) to give the
corresponding products.
4. Experimental section
4.1. General remarks
1
4.2.2.1. Compound 6a9c. white solid. H NMR (500 MHz,
Melting points are uncorrected. NMR spectra were recorded at
1
300 or 500 MHz (for H NMR) and 125 MHz (for 13C NMR),
CDCl3, TMS) δ 7.29-7.26 (m, 2H), 6.92-6.86 (m, 3H), 3.85 (t, J
= 5.0 Hz, 4H), 3.14 (t, J = 5.0 Hz, 4H). 13C NMR (125 MHz,
CDCl3) δ 151.2, 129.1, 119.9, 115.6, 66.8, 49.3.
respectively. 1H and 13C NMR spectra recorded in CDCl3
solutions were referenced to TMS (0.00 ppm) and the residual
solvent peak (77.0 ppm), respectively. J-values are in Hz.

5
1
4.2.2.2. Compound 6b9c. colorless liquid. 1H NMR (500 MHz,
CDCl3, TMS) δ 7.17 (t, J = 8.0 Hz, 1H), 6.53-6.51 (m, 1H), 6.45-
6.42 (m, 2H), 3.83 (t, J = 5.0 Hz, 4H), 3.77 (s, 3H), 3.13 (t, J =
5.0 Hz, 4H). 13C NMR (125 MHz, CDCl3) δ 160.6, 152.6, 129.7,
108.3, 104.6, 102.1, 66.7, 55.0, 49.2.
4.2.2.11. Compound 6k12. colorless liquid. H NMR (500
ACCEPTED MANUSCRIPT
MHz, CDCl3, TMS) δ 6.93 (t, J = 8.5 Hz, 2H), 6.87 (dd, J = 9.0,
4.5 Hz, 2H), 3.04 (t, J = 5.5 Hz, 4H), 1.73-1.68 (m, 4H), 1.57-
1.52 (m, 2H). 13C NMR (125 MHz, CDCl3) δ 156.9 (d, JC-F
=
236.9 Hz), 149.1 (d, JC-F = 2.3 Hz), 118.3 (d, JC-F = 7.5 Hz),
115.3 (d, JC-F = 22.0 Hz), 51.8, 26.0, 24.1.
1
4.2.2.3. Compound 6c9d. pale yellow liquid. H NMR (500
MHz, CDCl3, TMS) δ 7.30 (t, J = 7.5 Hz, 2H), 7.24-7.19 (m,
5H), 6.75 (d, J = 8.0 Hz, 2H), 6.70 (t, J = 7.5 Hz, 1H), 4.52 (s,
2H), 3.00 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 149.8, 139.0,
129.1, 128.5, 126.8, 126.7, 116.6, 112.4, 56.6, 38.4.
4.2.2.12. Compound 6l9b. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.16-7.12 (m, 2H), 6.99 (d, J = 8.0 Hz,
1H), 6.93 (t, J = 7.5 Hz, 1H), 2.83 (t, J = 5.0 Hz, 4H), 2.30 (s,
3H), 1.72-1.68 (m, 4H), 1.58-1.53 (m, 2H). 13C NMR (125 MHz,
CDCl3) δ 152.9, 132.6, 130.9, 126.4, 122.6, 118.9, 53.4, 26.6,
24.4, 17.8.
1
4.2.2.4. Compound 6d9c. pale yellow liquid. H NMR (500
MHz, CDCl3, TMS) δ 7.28 (t, J = 7.5 Hz, 2H), 7.21-7.19 (m,
3H), 7.10 (t, J = 8.0 Hz, 1H), 6.36 (dd, J = 8.0, 2.0 Hz, 1H), 6.29-
6.26 (m, 2H), 4.48 (s, 2H), 3.72 (s, 3H), 2.97 (s, 3H). 13C NMR
(125 MHz, CDCl3) δ 160.7, 151.0, 138.9, 129.8, 128.5, 126.8,
126.6, 105.4, 101.2, 98.8, 56.5, 54.9, 38.5.
4.2.2.13. Compound 6m9b. pale yellow liquid. H NMR (500
1
MHz, CDCl3, TMS) δ 7.13 (t, J = 8.0 Hz, 1H), 6.24 (dd, J = 8.0,
2.0 Hz, 1H), 6.20 (dd, J = 8.0, 1.5 Hz, 1H), 6.11 (s, 1H), 3.79 (s,
3H), 3.26 (t, J = 6.5 Hz, 4H), 1.99-1.97 (m, 4H). 13C NMR (125
MHz, CDCl3) δ 160.6, 149.2, 129.7, 104.8, 100.4, 97.8, 55.0,
47.5, 25.4.
1
4.2.2.5. Compound 6e9c. pale yellow liquid. H NMR (500
MHz, CDCl3, TMS) δ 7.28 (t, J = 7.5 Hz, 2H), 7.22-7.20 (m,
3H), 7.09 (t, J = 8.0 Hz, 1H), 6.57-6.53 (m, 3H), 4.48 (s, 2H),
2.95 (s, 3H), 2.28 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 149.8,
139.1, 138.8, 129.0, 128.5, 126.74, 126.70, 117.5, 113.0, 109.6,
56.5, 38.3, 21.9.
4.2.2.14. Compound 6n13. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.14-7.09 (m, 1H), 6.34-6.28 (m, 2H),
6.24-6.20 (m, 1H), 3.23 (t, J = 6.5 Hz, 4H), 2.01-1.95 (m, 4H).
13C NMR (125 MHz, CDCl3) δ 164.1 (d, JC-F = 240.1 Hz), 149.5
(d, JC-F = 11.1 Hz), 130.0 (d, JC-F = 10.5 Hz), 107.3 (d, JC-F = 2.0
Hz), 101.7 (d, JC-F = 21.8 Hz), 98.4 (d, JC-F = 25.5 Hz), 47.6,
25.4.
4.2.2.6. Compound 6f. pale yellow liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.30 (t, J = 7.5 Hz, 2H), 7.23 (t, J = 7.5
Hz, 1H), 7.18 (d, J = 7.0 Hz, 2H), 7.13-7.08 (m, 1H), 6.48-6.46
(m, 1H), 6.41-6.36 (m, 2H), 4.50 (s, 2H), 3.00 (s, 3H). 13C NMR
4.2.2.15. Compound 6o9b. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.10 (t, J = 7.0 Hz, 2H), 6.88 (d, J = 8.0
Hz, 1H), 6.82 (td, J = 7.0, 1.0 Hz, 1H), 3.19-3.16 (m, 4H), 2.32
(s, 3H), 1.94-1.89 (m, 4H). 13C NMR (125 MHz, CDCl3) δ 149.4,
131.6, 128.7, 126.2, 120.2, 115.8, 51.0, 24.9, 20.5.
(125 MHz, CDCl3) δ 164.1 (d, JC-F = 240.4 Hz), 151.3 (d, JC-F
10.6 Hz), 138.3, 130.1 (d, JC-F = 10.3 Hz), 128.6, 127.0, 126.5,
107.8 (d, JC-F = 2.1 Hz), 102.8 (d, JC-F = 21.5 Hz), 99.1 (d, JC-F
=
=
25.9 Hz), 56.3, 38.6. IR (neat) ν 1618, 1570, 1500, 1452, 1373,
1354, 1230, 1160, 1011, 959, 820, 754 cm-1. MS (ESI): 216
[M+H]+. HRMS (ESI) calcd. for C14H15NF [M+H]+: 216.1183;
found: 216.1179.
4.2.2.16. Compound 6p9b. yellow liquid. 1H NMR (500 MHz,
CDCl3, TMS) δ 7.17 (d, J = 7.5 Hz, 1H), 7.12-7.06 (m, 2H),
6.97-6.87 (m, 5H), 5.25 (s, 1H), 2.23 (s, 3H). 13C NMR (125
4.2.2.7. Compound 6g. pale yellow liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.30 (t, J = 7.5 Hz, 2H), 7.24 (d, J = 7.5
Hz, 1H), 7.21 (d, J = 7.5 Hz, 2H), 6.90 (t, J = 9.0 Hz, 2H), 6.66
(dd, J = 9.0, 4.0 Hz, 2H), 4.45 (s, 2H), 2.95 (s, 3H). 13C NMR
(125 MHz, CDCl3) δ 155.5 (d, JC-F = 233.8 Hz), 146.6, 138.8,
128.5, 126.9 (d, JC-F = 11.0 Hz), 115.5 (d, JC-F = 21.8 Hz), 113.7
(d, JC-F = 7.3 Hz), 57.5, 39.0. IR (neat) ν 1509, 1450, 1368, 1346,
1225, 1157, 1112, 944, 810, 733 cm-1. MS (ESI): 216 [M+H]+.
HRMS (ESI) calcd. for C14H15NF [M+H]+: 216.1183; found:
216.1186.
MHz, CDCl3) δ 157.8 (d, JC-F = 238.1 Hz), 142.0, 139.8 (d, JC-F
=
2.4 Hz), 130.9, 127.2, 126.8, 121.4, 120.1 (d, JC-F = 7.6 Hz),
117.4, 115.8 (d, JC-F = 22.3 Hz), 17.7.
1
4.2.2.17. Compound 6q9b. white solid. H NMR (500 MHz,
CDCl3, TMS) δ 7.12-7.05 (m, 4H), 6.95 (td, J = 7.5, 1.0 Hz, 1H),
6.70 (td, J = 7.5, 1.0 Hz, 1H), 6.14 (d, J = 8.0 Hz, 1H), 4.92 (s,
1H), 2.32 (s, 3H), 2.17 (s, 6H). 13C NMR (125 MHz, CDCl3) δ
144.1, 138.7, 135.5, 130.2, 128.5, 126.9, 125.5, 122.4, 118.1,
111.7, 18.2, 17.6.
1
4.2.2.18. Compound 6r9b. white solid. H NMR (500 MHz,
4.2.2.8. Compound 6h9b. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.38 (d, J = 7.5 Hz, 2H), 7.31 (t, J = 7.5
Hz, 2H), 7.24 (t, J = 7.0 Hz, 1H), 7.19-7.14 (m, 2H), 7.07 (d, J =
7.5 Hz, 1H), 6.97 (t, J = 7.5 Hz, 1H), 4.02 (s, 2H), 2.57 (s, 3H),
2.40 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 152.4, 139.1, 132.8,
131.1, 128.3, 128.2, 126.9, 126.4, 123.0, 120.0, 60.8, 40.9, 18.4.
CDCl3, TMS) δ 6.97 (d, J = 7.5 Hz, 4H), 6.83 (t, J = 7.5 Hz, 2H),
4.78 (s, 1H), 2.00 (s, 12H). 13C NMR (125 MHz, CDCl3) δ 141.8,
129.5, 128.7, 121.7, 19.0.
1
4.2.2.19. Compound 6s9b. white solid. H NMR (500 MHz,
CDCl3, TMS) δ 6.95 (d, J = 7.5 Hz, 2H), 6.80-6.77 (m, 3H), 4.69
(s, 3H), 4.70 (s, 1H), 2.24 (s, 3H), 1.99 (s, 6H), 1.98 (s, 6H). 13C
NMR (125 MHz, CDCl3) δ 142.2, 139.0, 131.5, 130.5, 129.2,
128.8, 128.4, 120.9, 20.6, 19.1, 19.0.
1
4.2.2.9. Compound 6i9c. pale yellow liquid. H NMR (500
MHz, CDCl3, TMS) δ 7.14 (t, J = 8.0 Hz, 1H), 6.54 (dd, J = 8.0,
2.5 Hz, 1H), 6.47 (t, J = 2.0 Hz, 1H), 6.37 (dd, J = 8.0, 2.0 Hz,
1H), 3.77 (s, 3H), 3.14 (t, J = 5.0 Hz, 4H), 1.71-1.66 (m, 4H),
1.58-1.54 (m, 2H). 13C NMR (125 MHz, CDCl3) δ 160.5, 153.5,
129.5, 109.2, 103.9, 102.7, 55.1, 50.5, 25.7, 24.3.
1
4.2.2.20. Compound 6t9b. pale yellow liquid. H NMR (500
MHz, CDCl3, TMS) δ 7.15-7.09 (m, 3H), 6.93 (d, J = 7.5 Hz,
2H), 6.71 (t, J = 7.5 Hz, 1H), 4.78 (s, 1H), 3.14 (hept, J = 7.0 Hz,
2H), 1.97 (s, 6H), 1.11 (d, J = 7.0 Hz, 12H). 13C NMR (125
MHz, CDCl3) δ 144.1, 143.1, 138.8, 129.5, 125.6, 124.8, 123.2,
119.6, 28.0, 23.4, 19.3.
1
4.2.2.10. Compound 6j. pale yellow liquid. H NMR (500
MHz, CDCl3, TMS) δ 7.15 (dd, J = 15.5, 8.0 Hz, 1H), 6.67 (dd, J
= 8.5, 2.5 Hz, 1H), 6.58 (dt, J = 13.0, 2.5 Hz, 1H), 6.47 (td, J =
8.5, 2.0 Hz, 1H), 3.15 (t, J = 5.5 Hz, 4H), 1.70-1.65 (m, 4H),
1.59-1.55 (m, 2H). 13C NMR (125 MHz, CDCl3) δ 163.9 (d, JC-F
= 241.0 Hz), 153.7 (d, JC-F = 9.6 Hz), 129.9 (d, JC-F = 10.1 Hz),
4.2.2.21. Compound 6u9b. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.09 (s, 3H), 6.75 (s, 2H), 4.69 (s, 1H),
3.12 (hept, J = 7.0 Hz, 2H), 2.22 (s, 3H), 1.95 (s, 6H), 1.11 (d, J
= 7.0 Hz, 12H). 13C NMR (125 MHz, CDCl3) δ 143.3, 140.4,
139.2, 130.0, 129.1, 126.3, 124.1, 123.2, 28.0, 23.4, 20.4, 19.2.
111.4 (d, JC-F = 2.4 Hz), 105.0 (d, JC-F = 21.3 Hz), 102.7 (d, JC-F
=
24.6 Hz), 50.0, 25.6, 24.2. IR (neat) ν 2936, 1613, 1579, 1495,
1447, 1382, 1250, 1219, 1180, 1160, 1124, 997, 965, 831, 758
cm-1. MS (ESI): 180 [M+H]+. HRMS (ESI) calcd. for C11H15NF
[M+H]+: 180.1180; found: 180.1181.
4.2.3. General procedure for the complex 3a-catalyzed α-
arylation of ketones. Under N2 atmosphere, 3a (1.0 or 2.0 mol%),
NaOtBu (2.0 equiv), toluene (1.0 mL), propiophenones 7 (0.5
mmol) and aryl chlorides 4 (0.6 mmol) were successively added

6
Tetrahedron
ACCEPTED MANUSCRIPT
3H), 1.46 (d, J = 6.5 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ
201.3, 155.7, 136.5, 132.5, 130.1, 128.4, 128.2, 128.0, 127.9,
121.0, 110.7, 55.4, 40.3, 17.5.
into a Schlenk reaction tube. The mixture was stirred vigorously
at 80 C for 3 h. Then the solvent was removed under reduced
pressure and the residue was purified by flash column
chromatography (SiO2) to give the corresponding products.
o
1
4.2.3.10. Compound 8j17. pale yellow liquid. H NMR (500
MHz, CDCl3, TMS) δ 7.96 (d, J = 7.5 Hz, 2H), 7.48 (t, J = 7.5
Hz, 1H), 7.38 (t, J = 7.5 Hz, 2H), 7.21-7.11 (m, 2H), 7.06-7.02
(m, 2H), 5.03 (q, J = 6.5 Hz, 1H), 1.52 (d, J = 6.5 Hz, 3H). 13C
NMR (125 MHz, CDCl3) δ 199.8, 159.6 (d, JC-F = 243.3 Hz),
136.0, 132.9, 128.7 (d, JC-F = 3.9 Hz), 128.6, 128.52, 128.50,
4.2.3.1. Compound 8a14. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.94 (d, J = 8.0 Hz, 2H), 7.45 (t, J = 8.0
Hz, 1H), 7.36 (t, J = 8.0 Hz, 2H), 7.19 (d, J = 8.5 Hz, 2H), 6.82
(d, J = 8.5 Hz, 2H), 4.64 (q, J = 7.0 Hz, 1H), 3.72 (s, 3H), 1.50
(d, J = 7.0 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 200.5, 158.4,
136.4, 133.4, 132.6, 128.70, 128.67, 128.4, 114.3, 55.1, 46.9,
19.4.
128.3 (d, JC-F = 15.3 Hz), 124.6 (d, JC-F = 3.5 Hz), 115.6 (d, JC-F
=
22.5 Hz), 39.5, 18.0.
4.2.3.11. Compound 8k4m. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 8.61 (d, J = 2.0 Hz, 1H), 8.46 (dd, J = 4.5,
1.5 Hz, 1H), 7.95 (dd, J = 8.5, 1.0 Hz, 2H), 7.61 (dt, J = 8.0, 2.0
Hz, 1H), 7.51 (tt, J = 7.5, 1.5 Hz, 1H), 7.41 (t, J = 7.5 Hz, 2H),
7.21 (dd, J = 8.0, 4.5 Hz, 1H), 4.76 (q, J = 7.0 Hz, 1H), 1.56 (d, J
= 7.0 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 199.5, 149.4,
148.3, 136.8, 135.8, 134.9, 133.1, 128.6, 128.5, 123.7, 44.8, 19.3.
4.2.3.12. Compound 8l18. colorless liquid. 1H NMR (500
MHz, CDCl3) δ 7.86 (d, J = 8.0 Hz, 2H), 7.28-7.24 (m, 4H),
7.20-7.16 (m, 3H), 4.66 (q, J = 7.0 Hz, 1H), 2.33 (s, 3H), 1.52 (d,
J = 7.0 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 199.9, 143.5,
141.7, 133.9, 129.1, 128.9, 128.8, 127.7, 126.7, 47.7, 21.5, 19.4.
4.2.3.13. Compound 8m14. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.85 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 8.5
Hz, 2H), 7.16 (d, J = 8.0 Hz, 2H), 6.81 (d, J = 8.5 Hz, 2H), 4.61
(q, J = 7.0 Hz, 1H), 3.73 (s, 3H), 2.33 (s, 3H), 1.49 (d, J = 7.0
Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 200.1, 158.4, 143.4,
134.0, 133.7, 129.1, 128.8, 128.7, 114.3, 55.1, 46.8, 21.5, 19.4.
1
4.2.3.2. Compound 8b14. yellow liquid. H NMR (500 MHz,
CDCl3, TMS) δ 7.95 (d, J = 7.5 Hz, 2H), 7.46 (t, J = 7.5 Hz, 1H),
7.37 (t, J = 7.5 Hz, 2H), 7.31-7.28 (m, 4H), 7.22-7.18 (m, 1H),
4.68 (q, J = 7.0 Hz, 1H), 1.53 (d, J = 7.0 Hz, 3H). 13C NMR (125
MHz, CDCl3) δ 200.3, 141.5, 136.5, 132.7, 128.9, 128.7, 128.4,
127.7, 126.9, 47.9, 19.5.
4.2.3.3. Compound 8c14. colorless liquid. 1H NMR (500 MHz,
CDCl3, TMS) δ 7.95 (d, J = 7.5 Hz, 2H), 7.46 (t, J = 7.5 Hz, 1H),
7.36 (t, J = 7.5 Hz, 2H), 7.20 (t, J = 7.5 Hz, 1H), 6.87 (d, J = 7.5
Hz, 1H), 6.82 (s, 1H), 6.73 (dd, J = 7.5, 2.5 Hz, 1H), 4.65 (q, J =
7.0 Hz, 1H), 3.74 (s, 3H), 1.52 (d, J = 7.0 Hz, 3H). 13C NMR
(125 MHz, CDCl3) δ 200.1, 159.9, 143.0, 136.4, 132.7, 129.9,
128.7, 128.4, 120.1, 113.4, 112.1, 55.1, 47.9, 19.4.
1
4.2.3.4. Compound 8d15. pure yellow liquid. H NMR (500
MHz, CDCl3) δ 7.94 (d, J = 7.5 Hz, 2H), 7.49 (t, J = 7.5 Hz, 1H),
7.39 (t, J = 7.5 Hz, 2H), 7.25-7.23 (m, 1H), 7.06 (d, J = 7.5 Hz,
1H), 7.01 (d, J = 10.0 Hz, 1H), 6.89 (td, J = 8.5, 2.0 Hz, 1H),
4.69 (q, J = 7.0 Hz, 1H), 1.53 (d, J = 7.0 Hz, 3H). 13C NMR (125
1
4.2.3.14. Compound 8n. pale yellow liquid. H NMR (500
MHz, CDCl3) δ 199.7, 163.0 (d, JC-F = 245.0 Hz), 143.8 (d, JC-F
=
MHz, CDCl3, TMS) δ 7.86 (d, J = 8.0 Hz, 2H), 7.17-7.14 (m,
3H), 7.08 (s, 2H), 6.98 (d, J = 7.0 Hz, 1H), 4.62 (q, J = 7.0 Hz,
1H), 2.31 (s, 3H), 2.27 (s, 3H), 1.50 (d, J = 7.0 Hz, 3H). 13C
NMR (125 MHz, CDCl3) δ 199.9, 143.4, 141.5, 138.5, 133.9,
129.1, 128.8, 128.7, 128.2, 127.5, 124.8, 47.6, 21.5, 21.3, 19.5.
IR (neat) ν 1674, 1604, 1486, 1447, 1405, 1368, 1332, 1242,
1202, 1180, 954, 843, 786, 762 cm-1. MS (ESI): 261 [M+Na]+.
HRMS (ESI) calcd. for C17H18NaO [M+Na]+: 261.1250; found:
261.1254.
7.0 Hz), 136.2, 133.0, 130.4 (d, JC-F = 8.1 Hz), 128.7, 128.5,
123.4 (d, JC-F = 2.9 Hz), 114.7 (d, JC-F = 21.4 Hz), 113.9 (d, JC-F
=
21.1 Hz), 47.4 (d, JC-F = 1.6 Hz), 19.3.
1
4.2.3.5. Compound 8e16. yellow liquid. H NMR (500 MHz,
CDCl3, TMS) δ 7.94 (d, J = 7.5 Hz, 2H), 7.48 (t, J = 7.5 Hz, 1H),
7.38 (t, J = 7.5 Hz, 2H), 7.26-7.23 (m, 2H), 6.97 (t, J = 8.5 Hz,
2H), 4.69 (q, J = 7.0 Hz, 1H), 1.51 (d, J = 7.0 Hz, 3H). 13C NMR
(125 MHz, CDCl3) δ 200.2, 161.7 (d, JC-F = 244.0 Hz), 137.1 (d,
JC-F = 3.3 Hz), 136.2, 132.9, 129.2 (d, JC-F = 8.0 Hz), 128.7,
128.5, 115.8 (d, JC-F = 21.3 Hz), 46.9, 19.5.
1
4.2.3.15. Compound 8o19. pale yellow liquid. H NMR (500
MHz, CDCl3) δ 7.85 (d, J = 7.5 Hz, 2H), 7.16 (d, J = 7.5 Hz,
2H), 7.15 (d, J = 7.5 Hz, 2H), 7.08 (d, J = 7.5 Hz, 2H), 4.62 (q, J
= 7.0 Hz, 1H), 2.32 (s, 3H), 2.26 (s, 3H), 1.50 (d, J = 7.0 Hz,
3H). 13C NMR (125 MHz, CDCl3) δ 200.0, 143.4, 138.6, 136.3,
133.9, 129.6, 129.1, 128.8, 127.5, 47.2, 21.5, 21.0, 19.4.
4.2.3.6. Compound 8f14. colorless liquid. 1H NMR (500 MHz,
CDCl3, TMS) δ 7.82 (d, J = 7.5 Hz, 2H), 7.43 (t, J = 7.5 Hz, 1H),
7.33 (t, J = 7.5 Hz, 2H), 7.19 (d, J = 7.0 Hz, 1H), 7.11-7.01 (m,
3H), 4.75 (q, J = 6.5 Hz, 1H), 2.49 (s, 3H), 1.47 (d, J = 6.5 Hz,
3H). 13C NMR (125 MHz, CDCl3) δ 200.9, 140.1, 136.5, 134.5,
132.6, 130.9, 128.4, 126.9, 126.8, 126.7, 44.5, 19.6, 18.0.
4.2.3.7. Compound 8g14. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.96 (d, J = 7.5 Hz, 2H), 7.46 (t, J = 7.5
Hz, 1H), 7.37 (t, J = 7.5 Hz, 2H), 7.18 (t, J = 7.5 Hz, 1H), 7.09
(s, 2H), 7.00 (d, J = 7.5 Hz, 1H), 4.65 (q, J = 7.0 Hz, 1H), 2.29
(s, 3H), 1.51 (d, J = 7.0 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ
200.4, 141.4, 138.6, 136.6, 132.7, 128.8, 128.7, 128.4, 128.3,
127.6, 124.8, 47.8, 21.4, 19.5.
4.2.3.16. Compound 8p15. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.97 (dd, J = 9.0, 5.5 Hz, 2H), 7.31-7.25
(m, 4H), 7.20 (t, J = 7.0 Hz, 1H), 7.03 (t, J = 8.5 Hz, 2H), 4.62
(q, J = 7.0 Hz, 1H), 1.52 (d, J = 7.0 Hz, 3H). 13C NMR (125
MHz, CDCl3) δ 198.6, 165.4 (d, JC-F = 253.0 Hz), 141.3, 132.8
(d, JC-F =3.0 Hz), 131.4 (d, JC-F = 9.3 Hz), 129.0, 127.6, 127.0,
115.5 (d, JC-F = 21.6 Hz), 48.0, 19.4.
1
4.2.3.17. Compound 8q. pale yellow liquid. H NMR (500
MHz, CDCl3, TMS) δ 7.83 (dd, J = 8.0, 5.5 Hz, 2H), 7.21 (d, J =
7.5 Hz, 1H), 7.12 (t, J = 7.0 Hz, 1H), 7.08 (t, J = 7.5 Hz, 1H),
7.03-6.98 (m, 3H), 4.69 (q, J = 6.5 Hz, 1H), 2.49 (s, 3H), 1.46 (d,
J = 6.5 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 199.3, 165.3 (d,
JC-F = 253.0 Hz), 140.0, 134.4, 132.9 (d, JC-F = 3.1 Hz), 131.1 (d,
JC-F = 9.4 Hz), 127.0, 126.9, 126.8, 115.5 (d, JC-F = 21.6 Hz),
44.7, 19.6, 17.9. IR (neat) ν 1677, 1596, 1500, 1447, 1404, 1320,
1224, 1157, 1146, 1003, 948, 848, 788, 761 cm-1. MS (ESI): 265
[M+Na]+. HRMS (ESI) calcd. for C16H15FNaO: 265.0999; found:
265.1012.
1
4.2.3.8. Compound 8h14. colorless liquid. H NMR (500 MHz,
CDCl3, TMS) δ 7.95 (d, J = 7.5 Hz, 2H), 7.45 (t, J = 7.5 Hz, 1H),
7.36 (t, J = 7.5 Hz, 2H), 7.17 (d, J = 8.0 Hz, 2H), 7.09 (d, J = 8.0
Hz, 2H), 4.65 (q, J = 7.0 Hz, 1H), 2.27 (s, 3H), 1.51 (d, J = 7.0
Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 200.4, 138.4, 136.5,
136.4, 132.6, 129.6, 128.7, 128.4, 127.6, 47.4, 20.9, 19.4.
4.2.3.9. Compound 8i4m. colorless liquid. 1H NMR (500 MHz,
CDCl3, TMS) δ 7.95 (d, J = 7.5 Hz, 2H), 7.43 (t, J = 7.5 Hz, 1H),
7.34 (t, J = 7.5 Hz, 2H), 7.16 (t, J = 8.0 Hz, 1H), 7.11 (d, J = 7.5
Hz, 1H), 6.86-6.83 (m, 2H), 5.08 (q, J = 6.5 Hz, 1H), 3.85 (s,

7
4.2.3.18. Compound 8r14. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.97 (dd, J = 8.5, 5.5 Hz, 2H), 7.18 (d, J =
8.5 Hz, 2H), 7.02 (t, J = 8.5 Hz, 2H), 6.82 (d, J = 8.5 Hz, 2H),
4.58 (q, J = 7.0 Hz, 1H), 3.73 (s, 3H), 1.49 (d, J = 7.0 Hz, 3H).
13C NMR (125 MHz, CDCl3) δ 198.8, 165.3 (d, JC-F = 252.9 Hz),
158.5, 133.3, 132.8, 131.3 (d, JC-F = 9.1 Hz), 128.6, 115.5 (d, JC-F
= 21.6 Hz), 114.4, 55.1, 47.0, 19.4.
(125 MHz, CDCl3) δ 199.0 (d, JC-F = 2.0 Hz), 162.7 (d, JC-F =
ACCEPTED MANUSCRIPT
246.3 Hz), 141.0, 138.5 (d, JC-F = 6.1 Hz), 130.0 (d, JC-F = 7.6
Hz), 129.1, 127.7, 127.0, 124.4 (d, JC-F = 3.0 Hz), 119.7 (d, JC-F
=
21.5 Hz), 115.4 (d, JC-F = 22.3 Hz), 48.2, 19.4. IR (neat) ν 1669,
1599, 1582, 1492, 1447, 1377, 1340, 1259, 1230, 1188, 1166,
1149, 1065, 973, 888, 878, 855, 782, 771 cm-1. MS (ESI): 229.
HRMS (ESI) calcd. for C15H14FO: 229.1023; found: 229.1056.
4.2.3.27. Compound 8aa. colorless liquid. 1H NMR (500 MHz,
CDCl3, TMS) δ 7.71 (d, J = 7.5 Hz, 1H), 7.62 (d, J = 10.0 Hz,
1H), 7.33 (dd, J = 13.5, 8.0 Hz, 1H), 7.16-7.14 (m, 3H), 7.10 (d,
J = 8.0 Hz, 2H), 4.58 (q, J = 6.5 Hz, 1H), 2.28 (s, 3H), 1.51 (d, J
= 6.5 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 199.1 (d, JC-F = 2.1
Hz), 162.7 (d, JC-F = 246.0 Hz), 138.6 (d, JC-F = 6.1 Hz), 138.0,
136.7, 130.0 (d, JC-F = 7.6 Hz), 129.8, 127.5, 124.4 (d, JC-F = 2.9
Hz), 119.7 (d, JC-F = 21.3 Hz), 115.5 (d, JC-F = 22.1 Hz), 47.8,
21.0, 19.4. IR (neat) ν 1683, 1587, 1511, 1481, 1438, 1374,
1326, 1253, 1183, 1166, 1149, 973, 879, 861, 798, 768, 750 cm-1.
MS (ESI): 265 [M+Na]+. HRMS (ESI) calcd. for C16H15FNaO:
265.0999; found: 265.1010.
4.2.3.19. Compound 8s14. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.97 (dd, J = 8.5, 5.5 Hz, 2H), 7.18 (t, J =
8.0 Hz, 1H), 7.07-7.00 (m, 5H), 4.58 (q, J = 7.0 Hz, 1H), 2.29 (s,
3H), 1.51 (d, J = 7.0 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ
198.7, 165.4 (d, JC-F = 252.9 Hz), 141.2, 138.7, 132.8 (d, JC-F
=
3.1 Hz), 131.3 (d, JC-F = 9.1 Hz), 128.9, 128.2, 127.7, 124.7,
115.5 (d, JC-F = 21.8 Hz), 47.9, 21.4, 19.5.
4.2.3.20. Compound 8t14. colorless liquid. 1H NMR (300 MHz,
CDCl3, TMS) δ 7.96 (dd, J = 9.0, 5.5 Hz, 2H), 7.15 (d, J = 8.0
Hz, 2H), 7.09 (d, J = 8.0 Hz, 2H), 7.01 (t, J = 9.0 Hz, 2H), 4.58
(q, J = 7.0 Hz, 1H), 2.27 (s, 3H), 1.50 (d, J = 7.0 Hz, 3H). 13C
NMR (125 MHz, CDCl3) δ 198.8, 165.3 (d, JC-F = 252.9 Hz),
138.3, 136.6, 132.9 (d, JC-F = 3.0 Hz), 131.3 (d, JC-F = 9.1 Hz),
129.7, 127.5, 115.5 (d, JC-F = 21.6 Hz), 47.6, 20.9, 19.4.
Acknowledgments
4.2.3.21. Compound 8u14. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.94 (d, J = 9.0 Hz, 2H), 7.28-7.24 (m,
4H), 7.20-7.16 (m, 1H), 6.84 (d, J = 9.0 Hz, 2H), 4.64 (q, J = 6.5
Hz, 1H), 3.78 (s, 3H), 1.51 (d, J = 6.5 Hz, 3H). 13C NMR (125
MHz, CDCl3) δ 198.8, 163.1, 141.9, 131.0, 129.4, 128.8, 127.6,
126.7, 113.6, 55.3, 47.4, 19.5.
Financial support from the National Natural Science
Foundation of China (No. 21471115) is greatly appreciated.
References and notes
4.2.3.22. Compound 8v14. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.94 (d, J = 9.0 Hz, 2H), 7.19 (d, J = 9.0
Hz, 2H), 6.84 (d, J = 9.0 Hz, 2H), 6.81 (d, J = 9.0 Hz, 2H), 4.59
(q, J = 7.0 Hz, 1H), 3.78 (s, 3H), 3.72 (s, 3H), 1.48 (d, J = 7.0
Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 199.0, 163.1, 158.3,
133.9, 130.9, 129.4, 128.6, 114.2, 113.5, 55.3, 55.1, 46.5, 19.5.
4.2.3.23. Compound 8w14. colorless liquid. 1H NMR (500
MHz, CDCl3, TMS) δ 7.94 (d, J = 8.5 Hz, 2H), 7.17 (d, J = 7.5
Hz, 2H), 7.09 (d, J = 7.5 Hz, 2H), 6.84 (d, J = 8.5 Hz, 2H), 4.60
(q, J = 7.0 Hz, 1H), 3.79 (s, 3H), 2.27 (s, 3H), 1.49 (d, J = 7.0
Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 198.9, 163.1, 138.9,
136.3, 131.0, 129.6, 129.4, 127.5, 113.6, 55.3, 47.1, 21.0, 19.5.
4.2.3.24. Compound 8x. colorless liquid. 1H NMR (500 MHz,
CDCl3, TMS) δ 7.93 (d, J = 9.0 Hz, 2H), 7.25 (dd, J = 9.0, 5.0
Hz, 2H), 6.97 (t, J = 9.0 Hz, 2H), 6.87 (d, J = 9.0 Hz, 2H), 4.64
(q, J = 7.0 Hz, 1H), 3.81 (s, 3H), 1.50 (d, J = 7.0 Hz, 3H). 13C
NMR (125 MHz, CDCl3) δ 198.7, 163.3, 161.6 (d, JC-F = 243.8
Hz), 137.5 (d, JC-F = 3.3 Hz), 131.0, 129.2 (d, JC-F = 4.4 Hz),
129.1, 115.7 (d, JC-F = 21.3 Hz), 113.7, 55.4, 46.5, 19.6. IR (neat)
ν 1680, 1599, 1509, 1461, 1413, 1332, 1309, 1264, 1245, 1216,
1166, 1157, 1017, 956, 837, 807, 781 cm-1. MS (ESI): 259
[M+H]+. HRMS (ESI) calcd. for C16H16FO2 [M+H]+: 259.1129;
found: 259.1130.
1. (a) Tsuji, J. Palladium Reagents and Catalysis: Innovations in
Organic Synthesis, Wiley, New York, 1995. (b) Handbook of
Organopalladium Chemistry for Organic Synthesis (Eds.: Negishi,
E.; de Meijere, A.), John Wiley & Sons, New York, 2002. (c)
Metal-Catalyzed Cross-Coupling Reactions, vols. 1 and 2 (Eds.:
de Meijere, A.; Diederich, F.), Wiley-VCH, Weinheim, Germany,
2004.
2. (a) Bedford, R. B.; Cazin, C. S. J.; Holder, D. Coord. Chem. Rev.
2004, 248, 2283-2321. (b) Littke, A. F.; Fu, G. C. Angew. Chem.
Int. Ed. 2002, 41, 4176-4211.
3. For some representative examples, please see: (a) Wong, S. M.;
Yuen, O. Y.; Choy, P. Y.; Kwong, F. Y. Coord. Chem. Rev. 2015,
293-294, 158-186. (b) Wong, S. M.; So, C. M.; Kwong, F. Y.
Synlett 2012, 23, 1132-1153. (c) Chung, K. H.; So, C. M.; Wong,
S. M.; Luk, C. H.; Zhou, Z.-Y.; Lau, C. P.; Kwong, F. Y. Synlett
2012, 23, 1181-1186. (d) Rodriguez, S.; Qu, B.; Haddad, N.;
Reeves, D. C.; Tang, W.-J.; Lee, H.; Krishnamurthy, D.;
Senanayake, C. H. Adv. Synth. Catal. 2011, 353, 533-537. (e)
Lundgren, R. J.; Sappong-Kumankumah, A.; Stradiotto, M. Chem.
Eur. J. 2010, 16, 1983-1991. (f) Chen, G.-S.; Lam, W. H.; Fok,
W. S.; Lee, H. W.; Kwong, F. Y. Chem. Asian J. 2007, 2, 306-309.
(g) Ackermann, L.; Spatz, J. H.; Gschrei, C. J.; Born, R.;
Althammer, A. Angew. Chem. Int. Ed. 2006, 45, 7627-7630. (h)
Liu, D.; Gao, W.-Z.; Dai, Q.; Zhang, X.-M. Org. Lett. 2005, 7,
4907-4910. (i) Rataboul, F.; Zapf, A.; Jackstell, R.; Harkal, S.;
Riermeier, T.; Monsees, A.; Dingerdissen, U.; Beller, M. Chem.
Eur. J. 2004, 10, 2983-2990. (j) Urgaonkar, S.; Nagarajan, M.;
Verkade, J. G. Org. Lett. 2003, 5, 815-818. (k) Singer, R. A.;
Caron, S.; McDermott, R. E.; Arpin, P.; Do, N. M. Synthesis 2003,
1727-1731. (l) Li, G. Y.; Zheng, G.; Andrew, A. F. J. Org. Chem.
2001, 66, 8677-8681. (m) Biscoe, M. R.; Buchwald, S. L. Org.
Lett. 2009, 11, 1773-1775. (n) Hama, T.; Hartwig, J. F. Org. Lett.
2008, 10, 1549-1552.
4. For Nolan’s contribution, please see: (a) Bastug, G.; Nolan, S. P.
Organometallics 2014, 33, 1253-1258. (b) Meiries, S.; Le Duc,
G.; Chartoire, A.; Collado, A.; Speck, K.; Athukorala Arachchige,
K. S.; Slawin, A. M. Z.; Nolan, S. P. Chem. Eur. J. 2013, 19,
17358-17368. (c) Le Duc, G.; Meiries, S.; Nolan, S. P.
Organometallics 2013, 32, 7547-7551. (d) Martin, A. R.; Makida,
Y.; Meiries, S.; Slawin, A. M. Z.; Nolan, S. P. Organometallics
2013, 32, 6265-6270. (e) Meiries, S.; Speck, K.; Cordes, D. B.;
Slawin, A. M.; Nolan, S. P. Organometallics 2013, 32, 330-339.
(f) Chaetoire, A.; Boreux, A.; Martin, A. R.; Nolan, S. P. RSC
Adv. 2013, 3, 3840-3843. (g) Meireis, S.; Chaartoire, A.; Slawin,
A. M. Z.; Nolan, S. P. Organometallics 2012, 31, 3402-3409. (h)
Chartoire, A.; Frogneux, X.; Boreux, A.; Slawin, A. M. Z.; Nolan,
4.2.3.25. Compound 8y. colorless liquid. 1H NMR (500 MHz,
CDCl3, TMS) δ 7.71 (t, J = 7.5 Hz, 1H), 7.40 (dd, J = 12.5, 6.5
Hz, 1H), 7.14-7.12 (m, 3H), 7.07 (d, J = 7.5 Hz, 2H), 7.02 (dd, J
= 10.5, 8.5 Hz, 1H), 4.57 (q, J = 7.0 Hz, 1H), 2.27 (s, 3H), 1.51
(d, J = 7.0 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 199.8 (d, JC-F
= 4.4 Hz), 160.8 (d, JC-F = 252.1 Hz), 137.4, 136.5, 133.9 (d, JC-F
= 9.0 Hz), 131.0 (d, JC-F = 2.9 Hz), 129.4, 128.0, 126.1 (d, JC-F
=
13.1 Hz), 124.3 (d, JC-F = 3.4 Hz), 116.5 (d, JC-F = 23.8 Hz), 51.5,
21.0, 18.9. IR (neat) ν 1680, 1610, 1517, 1481, 1452, 1267,
1205, 1152, 1104, 1003, 955, 895, 865, 819, 757 cm-1. MS (ESI):
265 [M+Na]+. HRMS (ESI) calcd. for C16H15FNaO [M+Na]+:
265.0999; found: 265.1011.
4.2.3.26. Compound 8z. colorless liquid. 1H NMR (500 MHz,
CDCl3, TMS) δ 7.71 (d, J = 7.5 Hz, 1H), 7.62 (dt, J = 9.5, 2.0
Hz, 1H), 7.35-7.25 (m, 5H), 7.22-7.19 (m, 1H), 7.17-7.13 (m,
1H), 4.62 (q, J = 7.0 Hz, 1H), 1.53 (d, J = 7.0 Hz, 3H). 13C NMR

8
Tetrahedron
ACCEPTED MANUSCRIPT
S. P. Organometallics 2012, 31, 6947-6951. (i) Chartoire, A.;
1-5. (e) Baier, H. B.; Metzner, P.; Körzdörfer, T.; Kelling, A.;
Holdt, H.-J. Eur. J. Inorg. Chem. 2014, 2952-2960. (f) Dang, L.;
Guo, J.; Song, H.; Liu, B.; Wang, B. Dalton Trans. 2014, 43,
17177-17183. (g) Naya, L.; Vázquez-García, D.; Fernández, A.;
López-Torres, M.; Marcos, I.; Lenis, O. A.; Pereira, M. T.; Vila, J.
M. J. Organometal. Chem. 2014, 772-773, 192-201.
11. CCDC 1848173 contains the supplementary crystallographic data
for this paper.
Frogneux, X.; Nolan, S. P. Adv. Synth. Catal. 2012, 354, 1897-
1901. (j) Marion, N.; Navarro, O.; Ecarnot, E. C.; Bell, A.;
Amoroso, D.; Nolan, S. P. Chem. Asian J. 2010, 5, 841-846. (k)
Winkelmann, O. H.; Riekstins, A.; Nolan, S. P.; Navarro, O.
Organometallics 2009, 28, 5809-5813. (l) Marion, N.; Navarro, O.;
Mei, J.-G.; Stevens, E. D.; Scott, N. M.; Nolan, S. P. J. Am. Chem.
Soc. 2006, 128, 4101-4111. (m) Navarro, O.; Marion, N.; Oonishi,
Y.; Kelly, R. A. III; Nolan, S. P. J. Org. Chem. 2006, 71, 685-692.
(n) Viciu, M. S.; Kelly, R. A. III; Stevens, E. D.; Naud, F.; Studer,
M.; Nolan, S. P. Org. Lett. 2003, 5, 1479-1482.
12. Qian, X.; Yu, Z.-L.; Auffrant, A.; Gosmini, C. Chem. Eur. J.
2013, 19, 6225-6229.
13. Lipshutz, B. H.; Frieman, B. A.; Lee, C. T.; Lower, S.; Nihan, D.
M.; Taft, B. R. Chem. Asian. J. 2006, 1, 417-429.
14. Xiao, Z.-K.; Shao, L.-X. Synthesis 2012, 44, 711-716.
15. Xu, Z. F.; Cai, C. X.; Liu, J. T. Org. Lett. 2013, 15, 2096-2099.
16. Gonell, S.; Poyatos, M.; Peris, E. Angew. Chem. Int. Ed. 2013, 52,
7009-7013.
17. Yang, J.-F.; Seto, Y. W.; Yoshikai, N. Catalysis 2015, 5, 3054-
3057.
18. Bugarin, A.; Connell, B. T. A. Chem. Commum. 2011, 47, 7218-
7220.
5. For Organ’s contribution, please see: (a) Froese, R. D. J.;
Lombardi, C.; Pompeo, M.; Rucker, R. P.; Organ, M. G. Acc.
Chem. Res. 2017, 50, 2244-2253. (b) Khadra, A.; Mayer, S.;
Organ, M. G. Chem. Eur. J. 2017, 23, 3206-3212. (c) Lombardi,
C.; Day, J.; Chandrasoma, N.; Mitchell, D.; Rodriguez, M. J.;
Farmer, J. L.; Organ, M. G. Organometallics 2017, 36, 251-254.
(d) Sharif, S.; Rucker, R. P.; Chandrasoma, N.; Mitchell, D.;
Rodriguez, M. J.; Froese, R. D. J.; Organ, M. G. Angew. Chem.
Int. Ed. 2015, 54, 9507-9511. (e) Pompeo, M.; Farmer, J. L.;
Froese, R. D. J.; Organ, M. G. Angew. Chem. Int. Ed. 2014, 53,
3223-3226. (f) Hoi, K. H.; Coggan, J. A.; Organ, M. G. Chem.
Eur. J. 2013, 19, 843-845. (g) Hoi, K. H.; Çalimsiz, S.; Froese, R.
D. J.; Hopkinson, A. C.; Organ, M. G. Chem. Eur. J. 2012, 18,
145-151. (h) Hoi, K. H.; Organ, M. G. Chem. Eur. J. 2012, 18,
804-807. (i) Hoi, K. H.; Çalimsiz, S.; Froese, R. D. J.; Hopkinson,
A. C.; Organ, M. G. Chem. Eur. J. 2011, 17, 3086-3090. (j)
Organ, M. G.; Abdel-Hadi, M.; Avola, S.; Dubovyk, I.; Hadei, N.;
Kantchev, E. A. B.; O’Brien, C. J.; Sayah, M.; Valente, C. Chem.
Eur. J. 2008, 14, 2443-2452.
19. Deng, Z.; Chen, C.; Cui, S. RSC Adv. 2016, 6, 93753-93755.
6. For Lavigne’s contribution, please see: (a) Zhang, Y.; Lavigne, G.;
Lugan, N.; Cesar, V. Chem. Eur. J. 2017, 23, 13792-13801. (b)
Zhang, Y.; César, V.; Lavigne, G. Eur. J. Org. Chem. 2015, 2042-
2050. (c) Zhang, Y.; César, V.; Storch, G.; Lugan, N.; Lavigne, G.
Angew. Chem. Int. Ed. 2014, 53, 6482-6486.
7. a) Deng, Q.; Zhang, Y.; Zhu, H.; Tu, T. Chem. Asian J. 2017, 12,
2364-2368. b) Deng, Q.; Shen, Y.; Zhu, H.; Tu, T. Chem. Comm.
2017, 53, 13063-13066. c) Fang, W.-W.; Jiang, J.; Xu, Y.; Zhou,
J.-F.; Tu, T. Tetrahedron 2013, 69, 673-679. d) Tu, T.; Fang, W.-
W.; Jiang, J. Chem. Commun. 2011, 47, 12358-12360.
8. (a) Fizia, A.; Gaffga, M.; Lang, J.; Sun, Y.; Niedner-Schatteburg,
G.; Thiel, W. R. Chem. Eur. J. 2017, 23, 14563-14575. (b)
Kilincarslan, R.; Gunay, M. E.; Firinci, R.; Denizalti, S.;
Cetinkaya, B. Appl. Organometal. Chem. 2016, 30, 268-272. (c)
Yang, J.; Li, P.-H.; Zhang, Y.-C.; Wang, L. Dalton Trans. 2014,
43, 14114-14122; (d) Yang, J.; Li, P.-H.; Zhang, Y.-C.; Wang, L.
J. Organomet. Chem. 2014, 766, 73-78. (e) Krinsky, J. L.;
Martínez, A.; Godard, C.; Castillón, S.; Claver, C. Adv. Synth.
Catal. 2014, 356, 460-474. (f) Chen, M.-T.; Vicic, D. A.; Chain,
W. J.; Turner, M. L.; Navarro, O. Organometallics 2011, 30,
6770-6773. (g) Chen, M.-T.; Vicic, D. A.; Turner, M. L.; Navarro,
O. Organometallics 2011, 30, 5052-5056. (h) Peh, G.-R.;
Kantchev, E. A. B.; Er, J.-C.; Ying, J. Y. Chem. Eur. J. 2010, 16,
4010-4017. (i) Tang, Y.-Q.; Lu, J.-M.; Shao, L.-X. J.
Organometal. Chem. 2011, 696, 3741-3744. (j) Jin, Z.; Guo, S.-X.;
Gu, X.-P.; Qiu, L.-L.; Song, H.-B.; Fang, J.-X. Adv. Synth. Catal.
2009, 351, 1575-1585.
9. (a) Zhang, Z.-M.; Gao, Y.-J.; Lu, J.-M. Tetrahedron 2017, 73,
7308-7314. (b) Liu, F.; Zhu, Y.-R.; Song, L.-G.; Lu, J.-M. Org.
Biomol. Chem. 2016, 14, 2563-2571. (c) Zhao, X.-Y.; Zhou, Q.;
Lu, J.-M. RSC Adv. 2016, 6, 24484-24490. (d) Huang, P.; Wang,
Y.-X.; Yu, H.-F.; Lu, J.-M. Organometallics 2014, 33, 1587-1593.
(e) Xiao, Z.-K.; Yin, H.-Y.; Lu, J.-M. Inorg. Chim. Acta 2014, 423
(Part A), 106-108. (f) Lv, H.; Zhu, L.; Tang, Y.-Q.; Lu, J.-M.
Appl. Organometal. Chem. 2014, 28, 27-31. (g) Gu, Z.-S.; Shao,
L.-X.; Lu, J.-M. J. Organometal. Chem. 2012, 700, 132-134.
10. For some recent representative examples of N-heterocyclic
carbene-palladacyclic complexes, please see: (a) Kilincarslan, R.;
Günay, M. E.; Firinci, R.; Denizalti, S.; Cetinkaya, B. Appl.
Organometal. Chem. 2016, 30, 268-272. (b) Naya, L.; Vázquez-
García, D.; Fernández, A.; López-Torres, M.; Ojea, V.; Marcos, I.;
Vila, J. M.; Fernández, J. Eur. J. Inorg. Chem. 2016, 422-431. (c)
Serrano, J. L.; Pérez, J.; García, L.; Sánchez, G.; Lozano, P.;
Zende, V.; Kapdi, A. Organometallics 2015, 34, 522-533. (d) Xu,
C.; Wang, Z.-Q.; Yuan, X.-E.; Han, X.; Xiao, Z.-Q.; Fu, W.-J.; Ji,
B.-M.; Hao, X.-Q.; Song, M.-P. J. Organomet. Chem. 2015, 777,