N-Heterocyclic carbene-palladium(II)-1-methylimidazole complex-catalyzed Suzuki-Miyaura coupling of benzyl carbamates with arylboronic acids

Article abstract of DOI:10.1039/c5ob01782c

The Suzuki-Miyaura coupling of benzyl carbamates with arylboronic acids was achieved in an environmentally benign medium. Using water as the sole solvent, such transformation took place very well to give the desired diarylmethane derivatives in good to almost quantitative yields in the presence of a well-defined NHC-Pd(ii)-Im complex under mild conditions. It is worth noting here that this is the first example of benzyl carbamates used in coupling reaction, thus affording a new method for the formation of diarylmethanes by palladium-catalyzed C-O bond activation.

Full text of DOI:10.1039/c5ob01782c

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N-Heterocyclic
Carbene-Palladium(II)-1-Methylimidazole
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DOI: 10.1039/C5OB01782C
Complex-Catalyzed Suzuki-Miyaura Coupling of Benzyl
Carbamates with Arylboronic Acids
Xiao-Xia Wang, Mao-Jun Luo and Jian-Mei Lu*
5
Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X
First published on the web Xth XXXXXXXXX 200X
DOI: 10.1039/b000000x
The Suzuki-Miyaura coupling of benzyl carbamates with arylboronic acids was achieved in an
environmentally benign medium. Using water as the sole solvent, such transformation took place
10 very well to give the desired diarylmethane derivatives in good to almost quantitative yields in the
presence of a well-defined NHC-Pd(II)-Im complex under mild conditions. It is worthy of noting
here that this is the first example of benzyl carbamates used in coupling reaction, thus affording a
new method for the formation of diarylmethanes by palladium-catalyzed C-O bond activation.
complex-catalyzed Suzuki-Miyaura coupling of benzyl
carbamates with arylboronic acids in neat water in detail.
Introduction
15 Transition metal catalyzed cross-coupling reactions between
organonucelophiles and organoelectrophiles are versatile
methods for the formation of new C-C bonds.1 Among them,
since its first discovery in 1979,2 the organoboron involved
Suzuki-Miyaura coupling has become one of the most
20 powerful methods.3 Traditionally, organic halides were
applided as the electrophiles in such transformation. During
the past years, cross-coupling reactions involving more inert
O-based electrophiles have also been developed, mainly due
to the contribution from the development of nickel catalysts,4
25 and such transformation usually cannot take place easily in
the presence of palladium catalysts.5 From 2011, Shao and our
group developed two types of novel N-heterocyclcic carbene-
Pd(II) complexes and also found them to be efficient catalysts
in the Suzuki-Miyuara coupling of O-based electrophiles such
30 as aryl sulfonates and sulfamates, and benzyl sulfonates.6 For
instance, very recently, we found that a well-defined N-
heterocyclic carbene-palladium(II)-1-methylimidazole [NHC-
Pd(II)-Im] complex 17 can efficiently catalyze the Suzuki-
Miyaura coupling of benzyl sulfonates with arylboronic acids
35 to give the corresponding diarylmethanes in good to almost
quantitative yields.6c These results clearly showed that NHC-
Pd(II)-Im complex 1 can indeed promote the Suzuki-Miyaura
coupling involving O-based electrophiles. In addition, water
seems to be the most desirable solvent in organic synthesis
40 because it is the most abundant, non-toxic, non-flammable,
cheap and easily available solvent in the world. Therefore,
tremendous efforts were paid on the development of organic
reactions performed in water.8 As a consequence, NHC-Pd(II)
complexes were also found to be efficient catalysts in some
45 reactions performed in water.9 For instance, we also
developed some novel NHC-metal complexes and applied
them as catalyst in the C-C coupling reactions performed in
water.10 The above results thus prompted us to further
investigate NHC-Pd(II) complex-catalyzed Suzuki-Miyuara
50 coupling of other O-based electrophiles performed in water.
Herein, we report the first example of NHC-Pd(II)-Im
55 Results and discussion
At the outset of this investigation, the model reaction was
chosen using benzyl carbamate 2a (1.2 equiv) and
phenylboronic acid 3a (0.7 mmol) as the substrates, NHC-
Pd(II)-Im complex 1 (1.0 mol%) as the catalyst, H2O (2.0 mL)
o
60 as the solvent. The reactions were performed at 80 C for 12 h
to evaluate various bases (1.5 equiv) (Table 1, entries 1-8). It
seems that LiOtBu was the most suitable base for this reaction
to give the highest yield (Table 1, entry 8), and such yield
kept untouched even if the reaction time was prolonged to 24
65 h. In addition, in the presence of other bases such as NaOtBu,
KOtBu, K2CO3, KOH, NaOH, Na2CO3 and LiOH, inferior
results were observed (Table 1, entries 1-7). It is obvious that
LiOtBu will at least partially be hydrolysed to LiOH and
tBuOH. However, it seems that LiOH alone was not a good
t
70 base for this reaction (Table 1, entry 7), implying that BuOH
derived from the hydrolysis of LiOtBu may act as an
important role. Based on such assumption,
experiment was then carried out using LiOH as a base in the
presence of equivalent amount of BuOH, giving the desired
a control
t
75 coupling product 4a in comparable yield (Table 1, entry 8 vs
entry 9), which is consistent with our previous results.10e-h
Further studies showed that increasing the amount of benzyl
carbamate 2a will promote the reaction to some extent. For
instance, when the amount of 2a was elevated to 2.0 equiv,
80 the yield can increase to 86% (Table 1, entry 10) and the best
almost quantitative yield was achieved when 2.5 equiv 2a was
used (Table 1, entry 11). It should be noted here that 1.1 and
1.3 equiv starting materials 2a were recovered after flash
column chromatography when 2.0 and 2.5 equiv 2a were
85 applied, respectively (Table 1, entries 10 and 11), implying
that the hydrolysis of substrate 2a was not a serious problem
in such transformation.
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Organic & Biomolecular Chemistry
Page 2 of 6
Table 1.
reaction of benzyl carbamate
1
Optimization for the NHC-Pd(II)-Im complex catalyzed
entries 11 and 12,
7
and 8,
3
and 4). 3,5-
Dimethylphenylboronic acid 3k, havingDtwOIo: 130-.1s0u3Vb9ies/Cwti5tAOurteiBcnl0e1tOs7,n8l2inCe
30 was also a good substrate, giving high yield of product 4k
(Table 2, entry 13). Arylboronic acids 3n and 3o, having
strongly electron-withdrawing groups such as acetyl and
trifluoromethyl group, were also tolerated to give
satisfactory yields under suitable conditions (Table 2,
35 entries 16-18).
2a
3a
.
with phenylboronic acid
O
NMe2
+
B(OH)2
1
NHC-Pd(II)-Im
(1.0 mol %)
O
base, H2O, 80 oC, 12 h
4a
3a
2a
Pri
Pri
Cl
N
N
Table 2.
carbamate
O
1
NHC-Pd(II)-Im complex catalyzed reactions of benzyl
1
NHC-Pd(II)-Im
:
Pd
Cl
N
2a
3
.
with arylboronic acids
N
Pri
NMe2
B(OH)2
Pri
O
1
NHC-Pd(II)-Im
+
LiOtBu, H2O
80 oC, 12 h
Yield (%)b
34
Entrya
1
Base
2a
(equiv)
R1
4
R1
3
NaOtBu
2a
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
2.0
2.5
1
Entrya
1
(R )
Yield (%)b
KOtBu
K2CO3
3
2
3
47
20
66
40
22
36
80
78
86d
98e
3b (2-OMe)
3b
4b, 62
2c
3
4b
, 82
4
KOH
3c (3-OMe)
3d (4-OMe)
4c, 87
4d, 77
5
NaOH
Na2CO3
4
6
5
3e
3e
4e
(2-Me)
, 61
, 80
7
LiOH
LiOtBu
6d
7
4e
8
9c
10
11
LiOH
3f (3-Me)
3g (4-Me)
3h (2-F)
3h
4f, 90
4g, 82
4h, 64
4h, 81
LiOtBu
LiOtBu
8
9
a
10c
11
12
13
14
15
16
17
2a 3
Otherwise specified, all reactions were carried out using
,
(0.7
o
1
mmol), base (1.5 equiv), (1.0 mol %) in H2O (2.0 mL) at 80 C for
12 h. b Isolated yields. c tBuOH (1.5 equiv) was added.
3i
4i
, 91
(3-F)
3j (4-F)
3k
4j, 87
4k, 89
4l, 79
d 2a
e 2a
(1.1 equiv) was recovered after flash column chromatography.
(3,5-Me2)
3l (4-Ph)
3m (1-naphthalenyl)
3n
(1.3 equiv) was recovered after flash column chromatography.
With the optimal conditions in hand, the limitation and
generality of this reaction was first tested using benzyl
carbamate 2a (2.5 equiv) and various arylboronic acids 3
(0.7 mmol) as the substrates. As can be seen from Table 2,
substituents on the arylboronic acids significantly affected
the reactions. First, it seems that the relative position of the
same substituent on the phenyl ring of arylboronic acids 3
10 had significant effect on the reactions. For example, 3-
substituted arylboronic acids 3c, 3f and 3i are the most
suitable substrates, giving the highest yields, and 4-
subtituted arylboronic acids 3d, 3g and 3j are better ones,
while the 2-substituted such compounds 3b, 3e and 3h are
15 the worst in these transformations (Table 2, entries 1, 3 and
4, 5, 7 and 8, 9, 11 and 12). To our pleasure, although 2-
subtituted arylboronic acids 3b, 3e and 3h gave the worst
yields under the optimal conditions, maybe partially due to
their steric hindrance, good yields can still be achieved by
20 simply elevating the amounts of NHC-Pd(II)-Im complex 1
or LiOtBu (Table 1, entries 1 and 2, 5 and 6, 9 and 10). The
electronegativity of the substituents on the arylboronic
acids 3 also affected the reactions to some extent. For
instance, slightly eletron-withdrawing 3- and 4-
25 flurophenylboronic acid 3i and 3j are the best ones than
4m, 79
4n
, 72
(4-Ac)
5
3o (4-CF3)
4o, 57
4o, 81
18d
3o
a
2
Otherwise specified, all reactions were carried out using (2.5
t
3
1
equiv), (0.7 mmol), LiO Bu (1.5 equiv), (1.0 mol%) in H2O (2.0
mL) at 80 oC for 12 h. b Isolated yields. c 1 (2.0 mol%) was added.
d LiOtBu (2.0 equiv) was added.
Encouraged by the above results,
a variety of benzyl
40 carbamates 2 and arylboronic acids 3 was then subjected to
the optimal conditions to further test the limitation and
generality of the reactions. The results are shown in Table 3.
All reactions performed well enough, giving the
corresponding coupling products
4 in good to almost
45 quantitative yields. Compared to the reactions of carbamate 2a
having electron-neutral group (H atom) shown in Table 2, it
seems that all carbamates 2 having electron-donating groups
(2b, 2c and 2d) or electron-withdrawing group (2e) gave
superior or comparable yields in the reactions with the same
50 arylboronic acids 3. For example, for the reactions involving
arylboronic acids 3 such as phenylboronic acid 3a, 3-
methoxyphenylboronic acid 3c, 3,5-dimethylphenylboronic
acid 3k and (1,1’-biphenyl)-4-ylboronic acid 3l, superior or
electron-donating
methoxyphenylboronic acids 3f and 3g, 3c and 3d (Table 2,
3-
and
4-methyl
or
-
2
|
Journal Name, [year], [vol], 00–00
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Page 3 of 6
Organic & Biomolecular Chemistry
comparable yields can be obtained. For the reactions
involving 4-methoxyphenylboronic acid 3d, 4-
Conclusions
View Article Online
In conclusion, the first Suzuki-MiyauraDcOoI:u1p0l.i1n0g39r/eCa5cOtiBo0n1s78o2fC
15 benzyl carbamates with arylboronic acids were reported in
this paper. In the presence of a well-defined NHC-Pd(II)-Im
complex, all reactions worked well enough to give the
corresponding diarylmethanes in moderate to almost
quantitative yields. Various substituents such as electron-
20 donating, -neutral, -withdrawing and sterically ones in both
substrates can be tolerated in such transformation. It should
also be noted here that the reactions were performed in the
environmentally benign medium using water as the sole
solvent.
methylphenylboronic acid 3g, 3-fluorophenylboronic acid 3i
and 4-fluorophenylboronic acid 3j, higher yields were
observed. In addition, it seems that sterically-hindered
substituent on the carbamates 2 did not affect the reactions.
For instance, 2-methylbenzyl carbamate 2c worked very well
to give products 4e and 4v-4aa in high to almost quantitative
yields (Table 3, entries 8-14).
5
10
25 Experimental
General Remarks. Melting points are uncorrected. NMR spectra
were recorded at 500 (for 1H NMR) or 125 MHz (for 13C NMR),
1
respectively. H NMR and 13C NMR spectra recorded in CDCl3
solutions were referenced to TMS (0.00 ppm) and the residual
30 solvent peak (77.0 ppm), respectively. J-values are in Hz. The
mass analyzer type for the high resolution mass spectra (HRMS,
EI) is FT-ICR. Other commercially obtained reagents were used
without further purification. Flash column chromatography was
performed on silica gel.
35 General Procedure for the NHC-Pd(II)-Im Complex 1-
Catalyzed Reactions of Benzyl Carbamates
2
with
Arylboronic Acids 3. Under N2 atmosphere, benzyl carbamates
2 (1.75 mmol), arylboronic acids 3 (0.7 mmol), NHC-Pd(II)-Im
complex 1 (1.0 mol%), LiOtBu (1.5 equiv) and H2O (2.0 mL)
40 were successively added into a Schlenk reaction tube. The
o
mixture was stirred vigorously at 80 C for 12 h. The organic
phase in the aqueous layer was extracted with ethyl acetate (20
mL) and dried over anhydrous Na2SO4. Then the mixture was
filtered, concentrated under reduced pressure and purified by a
45 flash column chromatography (petroleum ether as the eluent) to
give the pure products 4.
Compound 4a6c: colorless liquid (115.2 mg, 98%). 1H NMR (500
MHz, CDCl3, TMS) δ 7.27 (t, J = 7.5 Hz, 4H), 7.19-7.17 (m, 6H),
3.97 (s, 2H). 13C NMR (125 MHz, CDCl3) δ 141.1, 128.9, 128.4,
50 126.0, 41.9.
1
Compound 4b6c: yellow liquid (113.7 mg, 82%). H NMR (500
MHz, CDCl3, TMS) δ 7.25 (t, J = 7.5 Hz, 2H), 7.21-7.16 (m, 4H),
7.05 (dd, J = 7.5, 1.0 Hz, 1H), 6.86 (t, J = 7.5 Hz, 2H), 3.97 (s,
2H), 3.80 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 157.4, 141.0,
55 130.3, 129.7, 128.9, 128.2, 127.4, 125.7, 120.5 110.5, 55.3, 35.8.
1
Compound 4c6c: yellow liquid (120.6 mg, 87%). H NMR (500
MHz, CDCl3, TMS) δ 7.27 (t, J = 7.5 Hz, 2H), 7.21-7.18 (m, 4H),
6.78 (d, J = 7.5 Hz, 1H), 6.74 (d, J = 6.5 Hz, 2H), 3.95 (s, 2H),
3.75 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 159.8, 142.7, 140.9,
60 129.4, 128.9, 128.4, 126.1, 121.4, 114.8, 111.3, 55.1, 42.0.
1
Compound 4d6c: yellow liquid (106.7 mg, 77%). H NMR (500
MHz, CDCl3, TMS) δ 7.27 (t, J = 8.0 Hz, 2H), 7.19-7.16 (m, 3H),
7.09 (d, J = 8.0 Hz, 2H), 6.82 (d, J = 8.0 Hz, 2H), 3.91 (s, 2H),
3.76 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 158.0, 141.6, 133.2,
65 129.8, 128.8, 128.4, 125.9, 113.9, 55.2, 41.0.
1
Compound 4e6c: yellow liquid (101.9 mg, 80%). H NMR (500
MHz, CDCl3, TMS) δ 7.25 (t, J = 7.5 Hz, 2H), 7.19-7.08 (m, 7H),
3.97 (s, 2H), 2.23 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 140.4,
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3

Organic & Biomolecular Chemistry
Page 4 of 6
138.9, 136.6, 130.3, 129.9, 128.7, 128.4, 126.4, 126.0, 125.9, 65 NMR (125 MHz, CDCl3) δ 159.7, 158.0, 143.2, 133.0, 129.8,
View Article Online
39.4, 19.6.
129.3, 121.2, 114.7, 113.9, 111.2, 55.2, 55.1,D4O1I.:01.0.1039/C5OB01782C
Compound 4f6c: colorless liquid (114.7 mg, 90%). 1H NMR (500
MHz, CDCl3, TMS) δ 7.27 (t, J = 7.5 Hz, 2H), 7.19-7.15 (m, 4H),
7.00-6.97 (m, 3H), 3.93 (s, 2H), 2.30 (s, 3H). 13C NMR (125
MHz, CDCl3) δ 141.2, 141.0, 138.0, 129.7, 128.9, 128.4, 128.3,
126.8, 125.99, 125.97, 41.9, 21.4.
Compound 4q13: yellow liquid (138.0 mg, 93%). H NMR (500
MHz, CDCl3, TMS) δ 7.09-7.04 (m, 6H), 6.80 (d, J = 8.5 Hz, 2H),
3.86 (s, 2H), 3.74 (s, 3H), 2.29 (s, 3H). 13C NMR (125 MHz,
70 CDCl3) δ 157.9, 138.5, 135.4, 133.5, 129.8, 129.1, 128.7, 113.9,
55.2, 40.6, 20.9.
1
5
Compound 4g6c: colorless liquid (104.5 mg, 82%). 1H NMR (500
MHz, CDCl3, TMS) δ 7.24 (d, J = 7.5 Hz, 2H), 7.16-7.15 (m, 3H),
1
Compound 4r: yellow liquid (149.7 mg, 99%). H NMR (500
MHz, CDCl3, TMS) δ 7.20 (dd, J = 14.0, 7.5 Hz, 1H), 7.08 (d, J
= 8.0 Hz, 2H), 6.94 (d, J = 8.0 Hz, 1H), 6.87-6.82 (m, 4H), 3.89
75 (s, 2H), 3.76 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 163.0 (d, JC-
F = 244.0 Hz), 158.2, 144.2 (d, JC-F = 7.0 Hz), 132.4, 129.8, 129.7
10 7.06 (s, 4H), 3.91 (s, 2H), 2.29 (s, 3H). 13C NMR (125 MHz,
CDCl3) δ 141.4, 138.1, 135.5, 129.1, 128.9, 128.8, 128.4, 125.9,
41.5, 20.9.
Compound 4h11: colorless liquid (105.5 mg, 81%). 1H NMR (500
MHz, CDCl3, TMS) δ 7.28 (t, J = 7.5 Hz, 2H), 7.22-7.11 (m, 5H),
15 7.03 (dd, J = 15.0, 8.0 Hz, 2H), 3.99 (s, 2H). 13C NMR (125 MHz,
CDCl3) δ 161.0 (d, JC-F = 243.875 Hz), 139.9, 131.0 (d, J = 4.625
Hz), 128.8, 128.5, 128.1 (d, JC-F = 15.75 Hz), 127.9 (d, JC-F = 8.0
Hz), 126.2, 124.0 (d, J = 3.5 Hz), 115.3 (d, JC-F = 21.875 Hz),
34.8 (d, J = 2.875 Hz).
(d, JC-F = 8.25 Hz), 124.4 (d, JC-F = 2.75 Hz), 115.6 (d, JC-F
21.125 Hz), 114.0, 112.8 (d, JC-F = 21.0 Hz), 55.2, 40.7 (d, JC-F
=
=
1.625 Hz). MS (EI, %) m/z 216 (M+, 94), 210 (69), 195 (100).
80 HRMS (EI) calcd. for C14H13FO: 216.0950, found: 216.0946. IR
(neat) ν 3034, 2997, 2833, 2323, 1615, 1585, 1508, 1485, 1444,
1298, 1246, 1175, 1137, 1105, 1036, 949, 875, 829, 819, 785,
753, 703, 683 cm-1.
20 Compound 4i10b: colorless liquid (118.5 mg, 91%). 1H NMR (500
MHz, CDCl3, TMS) δ 7.27 (t, J = 7.5 Hz, 2H), 7.20 (t, J = 8.0 Hz,
2H), 7.16 (t, J = 7.5 Hz, 2H), 6.94 (d, J = 7.5 Hz, 1H), 6.87-6.84
(m, 2H), 3.94 (s, 2H). 13C NMR (125 MHz, CDCl3) δ 163.0 (d,
JC-F = 244.125 Hz), 143.7 (d, JC-F = 7.125 Hz), 140.3, 129.8 (d,
Compound 4s6c: yellow liquid (149.7 mg, 99%). H NMR (500
1
85 MHz, CDCl3, TMS) δ 7.11-7.05 (m, 4H), 6.94 (t, J = 8.5 Hz, 2H),
6.83 (d, J = 8.5 Hz, 2H), 3.87 (s, 2H), 3.76 (s, 3H). 13C NMR
(125 MHz, CDCl3) δ 161.4 (d, JC-F = 242.375 Hz), 158.1, 137.2
(d, JC-F = 3.0 Hz), 133.0, 130.1 (d, JC-F = 7.875 Hz), 129.7, 115.1
(d, JC-F = 21.125 Hz), 114.0, 55.2, 40.2.
25
JC-F = 8.25 Hz), 128.9, 128.6, 126.3, 124.5 (d, J = 2.75 Hz), 115.8
(d, JC-F = 21.0 Hz), 113.0 (d, JC-F = 21.0 Hz), 41.6 (d, J = 1.625
90 Compound 4t: yellow liquid (153.5 mg, 97%). 1H NMR (500
Hz).
MHz, CDCl3, TMS) δ 7.09 (d, J = 8.5 Hz, 2H), 6.82-6.78 (m, 5H),
3.82 (s, 2H), 3.75 (s, 3H), 2.25 (s, 6H). 13C NMR (125 MHz,
CDCl3) δ 157.9, 141.4, 137.8, 133.5, 129.8, 127.6, 126.6, 113.8,
55.2, 40.9, 21.2. MS (EI, %) m/z 226 (M+, 98), 211 (100). HRMS
95 (EI) calcd. for C16H18O: 226.1358, found: 226.1357. IR (neat) ν
3021, 2908, 2822, 1607, 1511, 1461, 1438, 1298, 1239, 1172,
1106, 1036, 852, 828, 816, 755, 693 cm-1.
Compound 4j6c: yellow liquid (113.3 mg, 87%). H NMR (500
1
MHz, CDCl3, TMS) δ 7.28 (t, J = 7.5 Hz, 2H), 7.22-7.11 (m, 5H),
30 6.95 (t, J = 8.5 Hz, 2H), 3.94 (s, 2H). 13C NMR (125 MHz,
CDCl3) δ 161.4 (d, JC-F = 242.5 Hz), 140.9, 136.8 (d, JC-F = 3.125
Hz), 130.3 (d, JC-F = 7.75 Hz), 128.8, 128.5, 126.2, 115.2 (d, JC-F
= 21.0 Hz), 41.1.
Compound 4k6c: colorless liquid (122.1 mg, 89%). H NMR (500
1
35 MHz, CDCl3, TMS) δ 7.26 (t, J = 7.5 Hz, 2H), 7.18-7.15 (m, 3H),
6.82 (s, 1H), 6.80 (s, 2H), 3.88 (s, 2H), 2.25 (s, 6H). 13C NMR
(125 MHz, CDCl3) δ 141.3, 141.0, 137.9, 128.9, 128.4, 127.7,
126.8, 125.9, 41.8, 21.2.
Compound 4u6c: white solid (170.7 mg, 89%). 1H NMR (500
MHz, CDCl3, TMS) δ 7.54 (d, J = 7.5 Hz, 2H), 7.48 (d, J = 8.0
100 Hz, 2H), 7.38 (t, J = 7.5 Hz, 2H), 7.28 (t, J = 7.5 Hz, 1H), 7.21 (d,
J = 8.0 Hz, 2H), 7.11 (d, J = 8.5 Hz, 2H), 6.82 (d, J = 8.5 Hz, 2H),
3.93 (s, 2H), 3.73 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 158.1,
141.0, 140.7, 138.9, 133.1, 129.8, 129.2, 128.7, 127.1, 127.0,
126.9, 113.9, 55.2, 40.7.
Compound 4l6c: white solid (134.9 mg, 79%). 1H NMR (500
40 MHz, CDCl3, TMS) δ 7.55 (d, J = 7.5 Hz, 2H), 7.50 (d, J = 8.0
Hz, 2H), 7.40 (t, J = 7.5 Hz, 2H), 7.31-7.18 (m, 8H), 4.00 (s, 2H).
13C NMR (125 MHz, CDCl3) δ 141.0, 140.2, 139.0, 129.3, 128.9,
128.7, 128.5, 127.2, 127.05, 126.98, 126.1, 41.6.
105 Compound 4v6c: yellow liquid (143.9 mg, 97%). H NMR (500
1
Compound 4m6c: colorless liquid (120.6 mg, 79%). 1H NMR
45 (500 MHz, CDCl3, TMS) δ 7.79-7.74 (m, 3H), 7.62 (s, 1H), 7.42
(pent, J = 7.0 Hz, 2H), 7.31-7.27 (m, 3H), 7.23-7.18 (m, 3H),
4.13 (s, 2H). 13C NMR (125 MHz, CDCl3) δ 141.0, 138.6, 133.6,
132.1, 129.0, 128.5, 128.1, 127.61, 127.60, 127.5, 127.1, 126.1,
126.0, 125.3, 42.1.
MHz, CDCl3, TMS) δ 7.18 (d, J = 8.0 Hz, 1H), 7.15-7.12 (m, 3H),
7.09-7.08 (m, 1H), 6.71 (t, J = 7.5 Hz, 2H), 6.67 (s, 1H), 3.94 (s,
2H), 3.73 (s, 3H), 2.23 (s, 3H). 13C NMR (125 MHz, CDCl3) δ
159.7, 142.1, 138.7, 136.6, 130.2, 129.9, 129.3, 126.4, 126.0,
110 121.2, 114.7, 111.1, 55.0, 39.4, 19.6.
Compound 4w6c: yellow liquid (141.0 mg, 95%). H NMR (500
1
50 Compound 4n12: colorless liquid (105.8 mg, 72%). 1H NMR (500
MHz, CDCl3, TMS) δ 7.87 (d, J = 8.5 Hz, 2H), 7.30-7.25 (m, 4H),
7.20 (t, J = 7.5 Hz, 1H), 7.16 (d, J = 7.5 Hz, 2H), 4.01 (s, 2H),
2.55 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 197.6, 146.7, 134.0,
135.2, 129.0, 128.9, 128.5, 126.3, 41.8, 26.4.
MHz, CDCl3, TMS) δ 7.13-7.11 (m, 3H), 7.07-7.06 (m, 1H), 7.02
(d, J = 8.5 Hz, 2H), 6.79 (d, J = 8.5 Hz, 2H), 3.90 (s, 2H), 3.74 (s,
3H), 2.22 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 157.9, 139.3,
115 136.5, 132.4, 130.2, 129.7, 129.6, 126.3, 125.9, 113.8, 55.2, 38.5,
19.5.
1
55 Compound 4o6c: colorless liquid (133.8 mg, 81%). 1H NMR (500
MHz, CDCl3, TMS) δ 7.52 (d, J = 7.5 Hz, 2H), 7.31-7.29 (m, 4H),
7.23-7.20 (m, 1H), 7.17 (d, J = 7.5 Hz, 2H), 4.02 (s, 2H). 13C
NMR (125 MHz, CDCl3) δ 145.2, 140.0, 129.2, 128.9, 128.7,
128.5 (q, JC-F = 32.25 Hz), 126.5, 125.4 (q, J = 3.625 Hz), 124.3
60 (q, JC-F = 270.125 Hz), 41.7.
Compound 4x: colorless liquid (138.6 mg, 99%). H NMR (500
MHz, CDCl3, TMS) δ 7.21-7.12 (m, 4H), 7.09-7.07 (m, 1H), 6.89
(d, J = 8.0 Hz, 1H), 6.85 (td, J = 8.0, 2.5 Hz, 1H), 6.78 (d, J =
120 10.0 Hz, 1H), 3.95 (s, 2H), 2.20 (s, 3H). 13C NMR (125 MHz,
CDCl3) δ 163.0 (d, JC-F = 244.0 Hz), 143.1 (d, JC-F = 7.125 Hz),
138.1, 136.6, 130.4, 123.0, 129.7 (d, JC-F = 8.125 Hz), 126.7,
126.1, 124.3 (d, JC-F = 2.625 Hz), 115.5 (d, JC-F = 21.25 Hz),
112.8 (d, JC-F = 21.125 Hz), 39.2 (d, JC-F = 1.625 Hz), 19.5. MS
125 (EI, %) m/z 200 (M+, 91), 185 (100). HRMS (EI) calcd. for
C14H13F: 200.1001, found: 200.1002. IR (neat) ν 3070, 3011,
Compound 4p6c: yellow liquid (154.8 mg, 97%). H NMR (500
1
MHz, CDCl3, TMS) δ 7.18 (td, J = 7.5, 1.0 Hz, 1H), 7.09 (d, J =
8.5 Hz, 2H), 6.81 (d, J = 8.5 Hz, 2H), 6.76 (d, J = 7.5 Hz, 1H),
6.73-6.71 (m, 2H), 3.88 (s, 2H), 3.75 (s, 3H), 3.74 (s, 3H). 13C
4
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Organic & Biomolecular Chemistry
2934, 2364, 2337, 1613, 1585, 1483, 1444, 1264, 1248, 1134, 65 128.3, 127.7, 126.8, 126.7, 126.0, 41.8, 21.4, 21.2. MS (EI, %)
+
1105, 1073, 1048, 950, 936, 889, 875, 860, 768, 736, 683 cm-1.
Compound 4y6c: colorless liquid (138.7 mg, 99%). 1H NMR (500
MHz, CDCl3, TMS) δ 7.15-7.13 (m, 3H), 7.07-7.04 (m, 3H), 6.93
(t, J = 8.5 Hz, 2H), 3.93 (s, 2H), 2.21 (s, 3H). 13C NMR (125
MHz, CDCl3) δ 161.3 (d, JC–F = 242.375 Hz), 138.7, 136.5, 136.0
(d, JC–F = 3.125 Hz), 130.4, 130.0 (d, JC-F = 7.75 Hz), 129.8,
126.6, 126.1, 115.1 (d, JC–F = 21.125 Hz), 38.6, 19.6.
m/z 210 (M , 100). HRMS (EI) calcd. for C16H : 210.1409,
View Article Online
DOI: 10.1039/C5OB01782C
18
found: 210.1412. IR (neat) ν 3016, 2917, 1605, 1489, 1460, 1376,
1092, 1038, 877, 845, 787, 742, 709, 691 cm-1.
o
5
Compound 4ag: white solid (151.7 mg, 84%); mp: 63.2-64.3 C.
70 1H NMR (500 MHz, CDCl3, TMS) δ 7.55 (d, J = 8.0 Hz, 2H),
7.49 (d, J = 8.5 Hz, 2H), 7.39 (t, J = 7.5 Hz, 2H), 7.29 (t, J = 7.5
Hz, 1H), 7.24 (d, J = 8.0 Hz, 2H), 7.18 (t, J = 7.5 Hz, 1H), 7.03-
7.00 (m, 3H), 3.96 (s, 2H), 2.30 (s, 3H). 13C NMR (125 MHz,
CDCl3) δ 141.0, 140.9, 140.4, 139.0, 138.1, 129.7, 129.3, 128.7,
75 128.4, 127.2, 127.03, 126.98, 126.9, 126.0, 41.5, 21.4. MS (EI, %)
m/z 258 (M+, 100), 243 (47). HRMS (EI) calcd. for C20H18:
258.1409, found: 258.1403. IR (neat) ν 3052, 3025, 2920, 2852,
2369, 1601, 1487, 1453, 1408, 1378, 1194, 1180, 1118, 1036,
1005, 918, 885, 847, 819, 785, 763, 740, 727, 703, 687 cm-1.
1
Compound 4z: colorless liquid (145.5 mg, 99%). H NMR (500
10 MHz, CDCl3, TMS) δ 7.15-7.08 (m, 4H), 6.81 (s, 1H), 6.73 (s,
2H), 3.89 (s, 2H), 2.245 (s, 6H), 2.242 (s, 3H). 13C NMR (125
MHz, CDCl3) δ 140.3, 139.1, 137.8, 136.6, 130.2, 129.9, 127.6,
126.6, 126.3, 125.9, 39.3, 21.2, 19.7. MS (EI, %) m/z 210 (M+,
92), 195 (100), 104 (50). HRMS (EI) calcd. for C16H18: 210.1409,
15 found: 210.1416. IR (neat) ν 3016, 2920, 1604, 1495, 1464, 1379,
1056, 1034, 848, 830, 769, 743, 726, 692 cm-1.
80 Compound 4ah6c: yellow liquid (140.6 mg, 93%). H NMR (500
1
1
Compound 4aa: colorless liquid (147.8 mg, 91%). H NMR (500
MHz, CDCl3, TMS) δ 7.19 (t, J = 7.5 Hz, 1H), 7.12 (dd, J = 8.5,
5.5 Hz, 2H), 6.95 (t, J = 8.5 Hz, 2H), 6.75-6.73 (m, 2H), 6.70 (s,
1H), 3.90 (s, 2H), 3.75 (s, 3H). 13C NMR (125 MHz, CDCl3) δ
161.4 (d, JC–F = 242.5 Hz), 159.8, 142.5, 136.6 (d, JC–F = 3.125
85 Hz), 130.3 (d, JC–F = 7.75 Hz), 129.5, 121.2, 115.2 (d, JC–F
21.125 Hz), 114.7, 111.4, 55.1, 41.1.
MHz, CDCl3, TMS) δ 7.74 (d, J = 7.0 Hz, 1H), 6.92 (t, J = 9.0 Hz,
2H), 7.48 (s, 1H), 7.39-7.35 (m, 2H), 7.25 (d, J = 8.5 Hz, 1H),
20 7.14-7.09 (m, 4H), 4.09 (s, 2H), 2.23 (s, 3H). 13C NMR (125
MHz, CDCl3) δ 138.7, 137.9, 136.7, 133.6, 132.1, 130.3, 130.0,
127.9, 127.6, 127.51, 127.47, 126.9, 126.5, 126.0, 125.9, 125.2,
39.6, 19.6. MS (EI, %) m/z 232 (M+, 100), 217 (66), 104 (80).
HRMS (EI) calcd. for C18H16: 232.1252, found: 232.1259. IR
25 (neat) ν 3047, 3007, 2908, 2835, 1630, 1597, 1508, 1492, 1460,
=
1
Compound 4ai: colorless liquid (139.9 mg, 98%). H NMR (500
MHz, CDCl3, TMS) δ 7.23 (td, J = 7.5, 6.0 Hz, 1H), 7.11 (dd, J =
8.5, 5.5 Hz, 2H), 6.99-6.93 (m, 3H), 6.88 (td, J = 8.5, 2.5 Hz, 1H),
1358, 1272, 1149, 1123, 1103, 1050, 957, 947, 927, 892, 853, 90 6.84 (d, J = 10.0 Hz, 1H), 3.92 (s, 2H). 13C NMR (125 MHz,
813, 778, 763, 740, 732, 697 cm-1.
CDCl3) δ 163.0 (d, JC-F = 244.375 Hz), 161.6 (d, JC-F = 243.0 Hz),
143.5 (d, JC-F = 6.875 Hz), 135.9, 130.3 (d, JC-F = 7.875 Hz),
129.9 (d, JC-F = 8.375 Hz), 124.4, 115.6 (d, JC-F = 21.125 Hz),
115.3 (d, JC-F = 21.25 Hz), 113.1 (d, JC-F = 21.0 Hz), 40.7. MS
1
Compound 4ab6c: yellow liquid (123.2 mg, 83%). H NMR (500
MHz, CDCl3, TMS) δ 7.21-7.15 (m, 2H), 7.01-6.98 (m, 3H), 6.78
30 (d, J = 7.5 Hz, 1H), 6.75-6.73 (m, 2H), 3.91 (s, 2H), 3.77 (s, 3H),
2.31 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 159.8, 142.8, 140.8, 95 (EI, %) m/z 204 (M+, 100), 203 (81). HRMS (EI) calcd. for
138.0, 129.7, 129.3, 128.3, 126.8, 125.9, 121.4, 114.8, 111.3,
55.1, 41.9, 21.3.
C13H10F2: 204.0751, found: 204.0750. IR (neat) ν 3038, 2906,
1615, 1587, 1508, 1485, 1449, 1410, 1248, 1219, 1157, 1137,
1091, 1075, 1014, 949, 935, 877, 844, 834, 821, 785, 746, 685
cm-1.
1
Compound 4ac6c: yellow liquid (132.1 mg, 89%). H NMR (500
35 MHz, CDCl3, TMS) δ 7.15 (t, J = 7.5 Hz, 1H), 7.08 (d, J = 8.5 Hz,
2H), 6.99-6.95 (m, 3H), 6.81 (d, J = 9.0 Hz, 2H), 3.86 (s, 2H),
3.74 (s, 3H), 2.29 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 158.0,
141.5, 137.9, 133.4, 129.8, 129.6, 128.3, 126.7, 125.8, 113.9,
55.2, 41.0, 21.3.
1
100 Compound 4aj6c: yellow liquid (134.2 mg, 94%). H NMR (500
MHz, CDCl3, TMS) δ 7.10 (dd, J = 8.5, 5.5 Hz, 4H), 6.96 (t, J =
8.5 Hz, 4H), 3.90 (s, 2H). 13C NMR (125 MHz, CDCl3) δ 161.5
(d, JC–F = 242.875 Hz), 136.6 (d, JC–F = 3.125 Hz), 130.2 (d, JC–F
= 7.75 Hz), 115.3 (d, JC–F = 21.125 Hz), 40.2.
40 Compound 4ad: colorless liquid (138.5 mg, 99%). 1H NMR (500
MHz, CDCl3, TMS) δ 7.22-7.15 (m, 2H), 7.01 (d, J = 7.5 Hz, 1H),
6.98-6.94 (m, 3H), 6.87-6.84 (m, 2H), 3.90 (s, 2H), 2.30 (s, 3H).
13C NMR (125 MHz, CDCl3) δ 163.0 (d, JC-F = 244.125 Hz),
143.8 (d, JC-F = 7.125 Hz), 140.2, 138.2, 129.8 (d, JC-F = 8.375
45 Hz), 129.7, 128.4, 127.1, 126.0, 124.5 (d, JC-F = 2.75 Hz), 115.7
(d, JC-F = 21.0 Hz), 112.9 (d, JC-F = 20.875 Hz), 41.6 (d, JC-F = 1.5
Hz), 21.3. MS (EI, %) m/z 200 (M+, 81), 185 (100). HRMS (EI)
calcd. for C14H13F: 200.1001, found: 200.1004. IR (neat) ν 3020,
2911, 2852, 1938, 1613, 1585, 1485, 1449, 1246, 1137, 1089,
50 1068, 951, 885, 861, 794, 776, 736, 697 cm-1.
1
105 Compound 4ak: yellow liquid (134.8 mg, 90%). H NMR (500
MHz, CDCl3, TMS) δ 7.11 (dd, J = 8.5, 5.5 Hz, 2H), 6.94 (t, J =
8.5 Hz, 2H), 6.83 (s, 1H), 6.77 (s, 2H), 3.84 (s, 2H), 2.26 (s, 6H).
13C NMR (125 MHz, CDCl3) δ 161.4 (d, JC-F = 242.375 Hz),
140.8, 138.0, 137.0 (d, JC-F = 3.25 Hz), 130.2 (d, JC-F = 7.75 Hz),
110 127.8, 126.7, 115.1 (d, JC-F =21.0 Hz), 41.0, 21.2. MS (EI, %) m/z
214 (M+, 68), 199 (100). HRMS (EI) calcd. for C15H15F:
214.1158, found: 214.1160. IR (neat) ν 3004, 2926, 1604, 1509,
1219, 1157, 1090, 1014, 855, 823, 762, 712, 691 cm-1.
Compound 4al10b: colorless liquid (128.8 mg, 92%). 1H NMR
115 (500 MHz, CDCl3, TMS) δ 7.11-7.07 (m, 4H), 7.03 (d, J = 8.5 Hz,
2H), 6.93 (t, J = 8.5 Hz, 2H), 3.88 (s, 2H), 2.30 (s, 3H). 13C NMR
(125 MHz, CDCl3) δ 161.4 (d, JC-F = 242.375 Hz), 137.9, 137.1
(d, JC-F = 3.125 Hz), 135.7, 130.2 (d, JC-F = 7.75 Hz), 129.2,
128.7, 115.1 (d, JC-F = 21.0 Hz), 40.7, 20.9.
1
Compound 4ae: colorless liquid (138.4 mg, 99%). H NMR (500
MHz, CDCl3, TMS) δ 7.16 (t, J = 7.5 Hz, 1H), 7.11 (dd, J = 8.5,
5.5 Hz, 2H), 7.01 (d, J = 7.5 Hz, 1H), 6.97-6.93 (m, 4H), 3.89 (s,
2H), 2.30 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 161.4 (d, JC-F
=
55 242.375 Hz), 140.9, 138.1, 136.9 (d, J = 3.125 Hz), 130.2 (d, J =
7.75 Hz), 129.6, 128.4, 126.9, 125.9, 115.2 (d, J = 21.125 Hz),
41.0, 21.3. MS (EI, %) m/z 200 (M+, 81), 185 (100). HRMS (EI)
calcd. for C14H13F: 200.1001, found: 200.1005. IR (neat) ν 3032,
2909, 1607, 1503, 1438, 1219, 1157, 1093, 1014, 848, 833, 819,
120 Compound 4am: white solid (154.1 mg, 84%); mp: 84.3-85.0 oC.
1H NMR (500 MHz, CDCl3, TMS) δ 7.55 (d, J = 7.5 Hz, 2H),
7.50 (d, J = 8.0 Hz, 2H), 7.39 (t, J = 7.5 Hz, 2H), 7.30 (t, J = 7.5
Hz, 1H), 7.20 (d, J = 8.0 Hz, 2H), 7.16-7.13 (m, 2H), 6.96 (t, J =
8.5 Hz, 2H), 3.95 (s, 2H). 13C NMR (125 MHz, CDCl3) δ 161.5
60 789, 743, 694 cm-1.
1
Compound 4af: colorless liquid (145.5 mg, 99%). H NMR (500 125 (d, JC-F = 242.625 Hz), 140.9, 140.0, 139.2, 136.6 (d, JC-F = 3.25
MHz, CDCl3, TMS) δ 7.15 (t, J = 7.5 Hz, 1H), 6.99-6.97 (m, 3H),
6.72 (s, 1H), 6.80 (s, 2H), 3.84 (s, 2H), 2.29 (s, 3H), 2.26 (s, 6H).
13C NMR (125 MHz, CDCl3) δ 141.3, 141.1, 137.9, 137.8, 129.7,
Hz), 130.3 (d, JC-F = 7.75 Hz), 129.2, 128.7, 127.2, 127.1, 127.0,
115.2 (d, JC-F = 21.125 Hz), 40.7. MS (EI, %) m/z 262 (M+, 100).
HRMS (EI) calcd. for C19H15F: 262.1158, found: 262.1160. IR
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Organic & Biomolecular Chemistry
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65 8 For some selected reviews, please see: (a) R. N. Butler, A. G. Coyne,
(neat) ν 3025, 2920, 2852, 1599, 1503, 1487, 1442, 1403, 1214,
1155, 1123, 1071, 1041, 1005, 905, 868, 824, 808, 776, 746, 730,
685 cm-1.
View Article Online
Chem. Rev., 2010, 110, 6302; (b) J. Mlynarski, J. Paradowska,
DOI: 10.1039/C5OB01782C
Chem. Soc. Rev., 2008, 37, 1502; (c) C. I. Herrerias, X.-Q. Yao, Z.-
P. Li, C.-J. Li, Chem. Rev., 2007, 107, 2546; (d) D. Dallinger, C.
Oliver Kappe, Chem. Rev., 2007, 107, 2563; (e) C.-J. Li, L. Chen,
Chem. Soc. Rev., 2006, 35, 68; (f) S. Kobayashi, C. Ogawa, Chem.
Eur. J., 2006, 12, 5954; (g) C.-J. Li, Chem. Rev., 2005, 105, 3095;
(h) Organic Reactions in Water; Ed.: U. M. Lindström, Blackwell
Publishing: Oxford, 2007.
For reviews, please see: (a) E. Levin, E. Ivry, C. E. Diesendruck, N.
Gabriel Lemcoff, Chem. Rev., 2015, 115, 4607; (b) H. D. Velazquez,
F. Verpoort, Chem. Soc. Rev., 2012, 41, 7032.
Acknowledgement
70
75
80
85
90
5
Financial support from the National Natural Science
Foundation of China (No. 21471115) is greatly appreciated.
Mao-Jun Luo thanks Science and Technology Department of
Zhejiang Province (Xinmiao Progamme) for financial support
(No. 2014R424025).
9
10 (a) Y. Zhang, S.-C. Yin, J.-M. Lu, Tetrahedron, 2015, 71, 544; (b) Y.
Zhang, M.-T. Feng, J.-M. Lu, Org. Biomol. Chem., 2013, 11, 2266;
(c) W.-X. Chen, C.-Y. Zhang, J.-M. Lu, J. Chem. Res., 2013, 611;
(d) X.-F. Lin, Y. Li, S.-Y. Li, Z.-K. Xiao, J.-M. Lu, Tetrahedron,
2012, 68, 5806; (e) M.-T. Ma, J.-M. Lu, Appl. Organometal. Chem.,
2012, 26, 175; (f) Y.-Q. Tang, C.-Y. Chu, L. Zhu, B. Qian, L.-X.
Shao, Tetrahedron, 2011, 67, 9479; (g) X.-X. Zhou, L.-X. Shao,
Synthesis, 2011, 3138; (h) Y.-Q. Tang, H. Lv, J.-M. Lu, L.-X. Shao,
J. Organomet. Chem., 2011, 696, 2576; (i) Y.-Q. Tang, H. Lv, X.-N.
He, J.-M. Lu, L.-X. Shao, Catal. Lett., 2011, 141, 705; (j) X.-B.
Shen, T.-T. Gao, J.-M. Lu, L.-X. Shao, Appl. Organometal. Chem.,
2011, 25, 497.
10 Notes and references
College of Chemistry and Materials Engineering, Wenzhou University,
Chashan University Town, Wenzhou, Zhejiang Province 325035,
People’s Republic of China. Fax: 86 57786689300; Tel: 86 57786689300;
E-mail: ljm@wzu.edu.cn
15 † Electronic Supplementary Information (ESI) available: [Copy of 1H and
13C NMR spectra of compounds 4]. See DOI: 10.1039/b000000x/
‡ Footnotes should appear here. These might include comments relevant
to but not central to the matter under discussion, limited experimental and
spectral data, and crystallographic data.
11 S. K. Yen, L. L. Koh, H. V. Huynh, T. S. Andy Hor, Eur. J. Inorg.
Chem., 2009, 4288.
20 1 (a) Metal-Catalyzed Cross-Coupling Reactions and More; Eds.: A.
de Meijere, S. Bräse, M. Oestreich; Wiley-VCH: Weinheim, 2014;
(b) L.-X. Yin, J. Liebscher, Chem. Rev., 2007, 107, 133; (c) J.-P.
Corbet, G. Mignani, Chem. Rev., 2006, 106, 2651; (d) A. Roglans,
A. Pla-Quintana, M. Moreno-Mañas, Chem. Rev., 2006, 106, 4622;
12 D. Srimani, A. Bej, A. Sarkar, J. Org. Chem., 2010, 75, 4296.
13 R. Ghosh, A. Sarkar, J. Org. Chem., 2010, 75, 8283.
25
30
35
(e) Metal-Catalyzed Cross-Coupling Reactions; 2nd Ed.; Eds.: A. de
Meijere, F. Diederich; Wiley-VCH: Weinheim, Germany, 2004;
Vols. 1-2; (f) M. Beller, C. Bolm, Transition Metals for Organic
Synthesis. Building Blocks and Fine Chemicals; 2nd Ed.; Wiley-
VCH: Weinheim, Germany, 2004; (g) Handbook of
Organopalladium Chemistry for Organic Synthesis; Eds.: E.
Negishi, A. de Meijere; John Wiley & Sons: New York, 2002; (h) J.
Hassan, M. Sévignon, C. Gozzi, E. Schulz, M. Lemaire, Chem. Rev.,
2002, 102, 1359.
2
3
N. Miyaura, K. Yamada, A. Suzuki, Tetrahedron Lett., 1979, 20,
3437.
(a) G. A. Molander, B. Canturk, Angew. Chem. Int. Ed., 2009, 48,
9240; (b) F. Alonso, I. P. Beletskaya, M. Yus, Tetrahedron, 2008,
64, 3047; (c) A. Suzuki, Chem. Commun., 2005, 4759; (d) N.
Miyaura, Topics in Current Chemistry; Springer Verlag: Berlin,
2002, Vol. 219, pp11-59; (e) N. Miyaura, J. Organomet. Chem.,
2002, 653, 54; (f) A. Suzuki, J. Organomet. Chem., 1999, 576, 147;
(g) N. Miyaura, A. Suzuki, Chem. Rev., 1995, 95, 2457.
(a) E. J. Tollefson, L. E. Hanna, E. R. Jarvo, Acc. Chem. Res., 2015,
48, 2344; (b) M. Tobisu, N. Chatani, Acc. Chem. Res., 2015, 48, 1717;
(c) J. Cornella, C. Zarate, R. Martin, Chem. Soc. Rev., 2014, 43, 8081;
(d) T. Mesganaw, N. K. Garg, Org. Process Res. Dev., 2013, 17, 29;
(e) F.-S. Han, Chem. Soc. Rev., 2013, 42, 5270; (f) J. Yamaguchi, K.
Muto, K. Itami, Eur. J. Org. Chem., 2013, 19; (g) C. M. So, F. Y.
Kwong, Chem. Soc. Rev., 2011, 40, 4963; (h) B. M. Rosen, K. W.
Quasdorf, D. A. Wilson, N. Zhang, A.-M. Resmerita, N. K. Garg, V.
Percec, Chem. Rev., 2011, 111, 1346; (i) B.-J. Li, D.-G. Yu, C.-L. Sun,
Z.-J. Shi, Chem. Eur. J., 2011, 17, 1728; (j) D.-G. Yu, B.-J. Li, Z.-J.
Shi, Acc. Chem. Res., 2010, 43, 1486.
40
45
50
55
4
5
6
For a pioneering paper on the comparison of nickel catalysts with
palladium catalysts, please see: S. Z. Tasker, E. A. Standley, T. F.
Jamison, Nature, 2014, 509, 299.
(a) Z.-Y. Wang, G.-Q. Chen, L.-X. Shao, J. Org. Chem., 2012, 77,
6608; (b) Z.-Y. Wang, Q.-N. Ma, R.-H. Li, L.-X. Shao, Org. Biomol.
Chem., 2013, 11, 7899; (c) X.-X. Wang, B.-B. Xu, W.-T. Song, K.-
X. Sun, J.-M. Lu, Org. Biomol. Chem., 2015, 13, 4925.
60
7
For the synthesis of NHC-Pd(II)-Im complex 1, please see: (a) L.
Zhu, T.-T. Gao, L.-X. Shao, Tetrahedron, 2011, 67, 5150; (b) H. Lv,
L. Zhu, Y.-Q. Tang, J.-M. Lu, Appl. Organometal. Chem., 2014, 28,
27.
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