Palladium-catalyzed Kumada reaction employing aminophosphine as ligand

Article abstract of DOI:10.1080/00397910701572217

In this article a palladium-catalyzed Kumada reaction was reported. The procedure was mild and tolerated a series of aryl bromides, affording the biaryls in good to excellent yield. Copyright Taylor & Francis Group, LLC.

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Palladium‐Catalyzed Kumada Reaction
Employing Aminophosphine as Ligand
a
a
a
a
a
Lin Zhang , Jiang Cheng , Weiwei Zhang , Baoda Lin , Changduo Pan
a
&
a
Jing Chen
College of Chemistry and Material Engineering, Wenzhou University ,
Wenzhou, China
Published online: 19 Oct 2007.
To cite this article: Lin Zhang , Jiang Cheng , Weiwei Zhang , Baoda Lin , Changduo Pan & Jing Chen (2007)
Palladium‐Catalyzed Kumada Reaction Employing Aminophosphine as Ligand, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 37:21, 3809-3814, DOI:
10.1080/00397910701572217
To link to this article: http://dx.doi.org/10.1080/00397910701572217
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Synthetic Communications , 37: 3809–3814, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701572217
Palladium-Catalyzed Kumada Reaction
Employing Aminophosphine as Ligand
Lin Zhang, Jiang Cheng, Weiwei Zhang, Baoda Lin,
Changduo Pan, and Jing Chen
College of Chemistry and Material Engineering, Wenzhou University,
Wenzhou, China
Abstract: In this article a palladium-catalyzed Kumada reaction was reported. The
procedure was mild and tolerated a series of aryl bromides, affording the biaryls in
good to excellent yield.
Keywords: aryl bromide, biaryl, Kumada reaction, palladium
The search for efficient methods for the construction of carbon–carbon bonds
[1]
is a central theme of research in organic synthesis. Transition metal–
catalyzed cross-coupling of organometallic reagents with halide or triflates
constitutes one of the most powerful methods to generate the carbon–
[2]
[3]
carbon bond. The development of palladium-catalyzed Stille, Suzuki,
[
4]
and Kumada reactions has profoundly moved the synthesis of bi- and
polyaryl compounds forward.
Grignard reagents cannot tolerate the sensitive functional group.
However, in the absence of a sensitive functional group, employing
Grignard reagents is almost the best choice for the synthesis of bi- and
polyaryl compounds because most organoborons and organozincs were
derived form Grignard reagents.
Received August 3, 2006
Address correspondence to Jiang Cheng, College of Chemistry and Material Eng-
ineering, Wenzhou University, Mid. Xueyuan Rd., Wenzhou 325027, China. E-mail:
shchengjiang@yahoo.com.cn
3
809

3
810
L. Zhang et al.
In general, the Kumada reaction is performed in the presence of nickel as
[6]
[5]
a catalyst, and few of the Pd-catalyzed reaction have been reported.
Herein, we report a palladium-catalyzed Kumada reaction using aminopho-
sphine as a ligand. In Zhang’s previous work, phosphinamide L1 iPr NPPh
was reported as a highly efficient ligand in the Suzuki reaction as well as
2
2
[7]
copper- and amine-free Sonogashira reaction. Accordingly, we attempted
to extend the use of the ligand to other reactions. L1 is easy to prepare
from commercially available material, and it is air stable. In fact, no change
3
1
of P NMR was found when L1 was exposed in the air for 30 days.
Treatment of a mixture of 1a, 4-bromoanisole (374 mg, 2 mmol), and 2a,
p-tolylmagnesium bromide (5 mmol in 5 mL of THF), with Pd(OAc)2
(
11.2 mg, 0.05 mmol) and L1 (43.1 mg, 0.15 mmol) at 658C under an inert
atmosphere for 8 h produced the desired product 3aa in 86% yield. This is
a promising result. Then a series of aryl bromides and arylmagnesium
bromides were tested in the reaction conditions. Results are summarized in
Table 1 (Scheme 1).
Table 1. Palladium-catalyzed Kumada reaction
0
a
Entry
1
Aryl bromide 1
Ar MgBr 2
3 Yield (%)
4-Bromotoluene
4-MeO-Ph
86
3aa
87
1
3-Bromotoluene
a
2a
2a
2
3
4
5
6
7
8
1
2-Bromotoluene
b
3ba
80
2a
2a
1
c
3-Bromopyridine
3ca
44
1
d
3da
89
1b
1c
1c
1b
1-Nap
2b
2b
3bb
66
3
cb
97
2-Me-Ph
2
c
3cc
80
2-,6-Dimethyl
Phenyl
3bd
2
d
2d
9
4-Bromoanisole
88
3dd
80
1d
1a
1
0
2,4,6-Trimethyl
Phenyl
3ae
2
e
a
0
Isolated yield, all reactions were run with aryl bromide (2 mmol), Ar MgBr
(11.2 mg, 0.05 mmol), and L1 (43.1 mg, 0.15 mmol) at 658C
(
5 mmol), Pd(OAc)
for 8 h.
2

Palladium-Catalyzed Kumada Reaction
3811
Scheme 1.
All of the aryl bromide substrates worked well in the reaction. For
example, the aryl bromides containing electron-donating substituents were
reluctant to react in oxidative addition to Pd(0). However, 4-bromoanisole
1
d was a good coupling partner in the procedure, 88% product (3dd) was
isolated (Table 1, entry 9) when the substrate 2d with heavy hindrance was
employed. In some cases, the ortho group in the aryl bromide had some
effect in the reaction; the yield slightly decreased to 66% (Table 1, entry 6).
Because of the coordination of the herero-atom with palladium, 3-bromo
pyridine afforded only 44% isolated product 3db (Table 1, entry 4).
In conclusion, we have developed a palladium-catalyzed Kumada
reaction. It is a facile and mild way for the synthesis of bi- and polyaryl
compounds. Aminophosphine was used as the ligand. The ligand is easy to
prepare from commercially available material and is air stable.
EXPERIMENTAL
General
All reactions and manipulations were conducted under a nitrogen atmosphere
using standard Schlenk techniques. Column chromatography was performed
1
using EM silica gel 60 (300–400 mesh) or Al O . H NMR and C NMR
13
2
3
were recorded on 300- and 75- MHz spectrometers, respectively. Chemical
shifts were reported in parts per million (ppm) downfield from tetramethyl-
silane with the solvent resonance as the internal standard.
Materials
THF was distilled from sodium-benzophenone prior to use. Aryl bromides
were used directly as obtained commercially unless otherwise noted.
General Procedure for the Kumada Reaction
Under a nitrogen atmosphere, a Schlenk reaction tube was charged with aryl
0
bromide (2 mmol), Ar MgBr (5 mmol in 5 mL of THF), Pd(OAc) (11.2 mg,
2
0
.05 mmol), and L1 (43.1 mg, 0.15 mmol). The reaction tube was purged with
N under a dry-ice bath. After the mixture was heated at 658C for 8 h, the
2

3
812
L. Zhang et al.
solvent was evaporated under reduced pressure, and the residue was purified
by flash-column chromatography on silica gel to give the product 3.
Data
[8]
3aa 4-Methyl-4-methoxyl-biphenyl
1
H NMR (CDCl ): 7.52 (d, J ¼ 8.6 Hz, 2H), 7.46 (d, J ¼ 8.0 Hz, 2H), 7.26
3
(
d, J ¼ 7.9 Hz, 2H), 6.97 (d, J ¼ 8.6 Hz, 2H), 3.86 (s, 3H), 2.39 (s, 3H).
1
3
C NMR (CDCl ): 158.9, 138.0, 136.3, 133.7, 129.4, 127.9, 126.6, 114.4,
3
5
5.3, 21.0.
[9]
3
ba 3-Methyl-4-methoxyl-biphenyl
1
H NMR (CDCl ): 7.55–7.52 (m, 2H), 7.39–7.32 (m, 3H), 7.15–7.13
3
1
3
(m, 1H), 6.99 (d, J ¼ 8.7 Hz, 2H), 3.86 (s, 3H), 2.43 (s, 3H). C NMR
(
CDCl ): 159.1, 140.8, 138.2, 133.9, 128.6, 128.1, 127.5, 127.4, 123.8,
3
114.1, 55.3, 21.5.
[10]
3ca 2-Methyl-4-methoxyl-biphenyl
1
H NMR (CDCl ): 7.28–7.23 (m, 6H), 7.98–7.95 (m, 2H), 3.86 (s, 3H), 2.29
3
1
3
s, 3H). C NMR (CDCl ): 158.5, 141.5, 135.4, 134.4, 130.2, 130.2, 129.9,
(
3
1
26.9, 125.7, 113.5, 55.2, 20.5.
[11]
3
da 3-(4-Methoxyphenyl)pyridine
1
H NMR (CDCl ): 8.82–8.81 (m, 1H), 8.55–8.53 (m, 1H), 7.85–7.81
3
(
m, 1H), 7.52 (d, J ¼ 6.9 Hz, 2H), 7.36-7.31 (m, 1H), 7.02 (d, J ¼ 6.9 Hz,
1
H), 3.87 (s, 6H). C NMR (CDCl ): 159.8, 148.0, 147.8, 136.2, 133.8,
3
2
1
3
30.0, 128.2, 123.4, 114.5, 55.3.
[
12]
3bb 1-m-Tolylnaphthalene
1
13
H NMR (CDCl ): 7.94–7.84 (m, 3H), 7.52–7.25 (m, 8H), 2.45 (s, 3H).
C
NMR (CDCl ): 140.7, 140.4, 137.9, 133.8, 131.7, 130.8, 128.3, 128.2, 128.0,
3
3
127.6, 127.2, 126.9, 126.2, 126.0, 125.8, 125.4, 21.6.
[
13]
3cb 1-o-Tolylnaphthalene
1
H NMR (CDCl ): 7.92–7.84 (m, 2H), 7.75–7.46 (m, 3H), 7.39–7.25 (m, 6H),
3
1
.05 (s, 3H). C NMR (CDCl ): 140.2, 139.8, 136.8, 133.5, 132.0, 130.3, 129.8,
3
2
1
3
28.2, 127.5, 127.4, 126.6, 126.1, 126.0, 125.7, 125.5, 125.3, 20.0.

Palladium-Catalyzed Kumada Reaction
3813
0
cc 2,2 -Dimethylbiphenyl
[14]
3
1
13
H NMR (CDCl ): 7.30–7.24 (m, 6H), 7.15–7.12 (m, 2H), 2.09 (s, 6H).
3
C
NMR (CDCl ): 141.6, 135.8, 129.8, 129.3, 127.1, 125.5, 19.8.
3
0
3
bd 2,6,3 -Trimethylbiphenyl
1
H NMR (CDCl ): 7.35–7.33 (m, 1H), 7.19–7.13 (m, 4H), 7.00–6.97
3
1
m, 2H), 2.42 (s, 3H), 2.08 (s, 6H). C NMR (CDCl ): 142.0, 141.0, 137.9,
3
(
3
1
1
1
9
36.0, 129.7, 128.3, 127.3, 127.2, 126.9, 126.0, 21.5, 20.9. MS (EI): m/z
þ
21
96 (M ), IR (cm ): 3067 (w), 2732 (m), 1590 (s), 1656 (s), 1604 (s),
465 (s), 1099 (s). Anal. calcd. for C H : C, 91.78; H, 8.22. Found: C,
1.47; H, 8.44.
1
5 16
0
[15]
3
dd 2,6-Dimethyl-4 -methoxylbiphenyl
1
H NMR (CDCl ): 7.14–7.06 (m, 5H), 7.00–6.97 (m, 2H), 3.87 (s, 3H), 2.05
3
1
s, 6H). C NMR (CDCl ): 158.2, 141.5, 136.5, 133.3, 130.0, 127.2, 126.9,
3
(
3
1
13.8, 55.2, 20.9.
0
[16]
3
ae 2,4,6,4 -Tetramethybiphenyl
1
H NMR (CDCl ): 7.27 (d, J ¼ 7.5 Hz, 2H), 7.09 (d, J ¼ 7.5 Hz, 2H), 6.99
3
1
s, 2H), 2.45 (s, 3H), 2.38 (s, 3H), 2.07 (s, 6H). C NMR (CDCl ): 139.0,
3
(
3
1
38.0, 136.4, 136.1, 136.0, 129.2, 129.1, 128.0, 21.2, 21.0, 20.8.
ACKNOWLEDGMENT
We thank the National Natural Science Foundation of China (No. 20504023)
and the Natural Science Foundation of Zhejiang Province (No. Y404039) for
financial support.
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