Synthesis of functionalized 2-arylpyridines from 2-halopyridines and various aryl halides via a nickel catalysis

Article abstract of DOI:10.1016/j.tet.2009.05.044

An efficient nickel-catalyzed method devoted to the direct formation of functionalized 2-arylpyridines is described avoiding the prior preparation of organometallic species. Various functionalized 2-arylpyridines are obtained in moderate to excellent yields by a one-step chemical procedure from corresponding halides. The NiBr₂(2,2′-bipyridine) complex appears to be an extremely suitable catalyst for the activation in the presence of manganese dust of aromatic halides and pyridyl halides functionalized by reactive groups. The versatility of this original process represents a simple alternative to most known methods using organometallic reagents.

Full text of DOI:10.1016/j.tet.2009.05.044

Tetrahedron 65 (2009) 6141–6146
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis of functionalized 2-arylpyridines from 2-halopyridines and
various aryl halides via a nickel catalysis
,
b
c
Corinne Gosmini a , Carine Bassene-Ernst , Muriel Durandetti
*
a De´partement de Chimie, Laboratoire He´te´roe´le´ments et Coordination, UMR CNRS 7653, Ecole Polytechnique, 91128 Palaiseau Ce´dex, France
b Equipe Electrochimie et Synthe`se Organique, Institut de Chimie et des Materiaux Paris Est, ICMPE, C.N.R.S-Universite´ Paris 12 val de Marne, UMR 7182,
2 rue Henri Dunant 94320 Thiais, France
c
´
´
´
´
Laboratoire des Fonctions Azotees & Oxygenees Complexes de l’IRCOFdCNRS UMR 6014 & FR CNRS 3038, Universite de Rouen and INSA de Rouen,
76821 Mont St Aignan Cedex, France
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient nickel-catalyzed method devoted to the direct formation of functionalized 2-arylpyridines is
described avoiding the prior preparation of organometallic species. Various functionalized 2-arylpyr-
idines are obtained in moderate to excellent yields by a one-step chemical procedure from corresponding
halides. The NiBr2(2,20-bipyridine) complex appears to be an extremely suitable catalyst for the activa-
tion in the presence of manganese dust of aromatic halides and pyridyl halides functionalized by reactive
groups. The versatility of this original process represents a simple alternative to most known methods
using organometallic reagents.
Received 26 March 2009
Received in revised form 11 May 2009
Accepted 18 May 2009
Available online 23 May 2009
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
of pyridine N-oxides with aryl bromide.9 Alternatively, a method
based on the intermolecular radical addition of aryl or heteroaryl
The broad use of biaryl compounds and especially 2-arylpyr-
idines as key building blocks in materials1 and in medicinal
chemistry2 has aroused considerable effort to facilitate their
chemical accessibility. Among the diverse approaches developed
for the construction of 2-aryl/heteroarylpyridines the use of
a transition-metal catalyzed reaction has been the most successful.
These reactions involve the preparation of an organometallic re-
agent and the presence of a transition metal for the cross-coupling
reactions such as Pd, Ni, Fe or Co. A variety of aromatic organo-
metallic reagents3 could be implied in the coupling with 2-pyr-
idylhalides. However, only a few examples using 2-pyridylmetals
have been reported in the literature due to the instability of 2-
pyridylmetal reagents.4 More recently, a transition-metal free
regiospecific sequential addition of Grignard reagents to pyridine
N-oxides was reported.5 To avoid the preparation of a stoichio-
metric organometallic reagent, different one-pot selective cross-
coupling procedures have been reported. These include coupling of
a 2-halopyridine with an aryl halide under phase-transfer condi-
tions6 or using a stoichiometric amount of hexamethylditin,7 both
in the presence of Pd-catalysis. Functionalized 2-arylpyridines
could also be synthesized from 2-pyridylhalides and electron rich
arenes in the presence of AlCl38 or by Pd-catalyzed direct arylation
radicals gives arylpyridines in low yields.10 Few years ago, we have
developed two electrochemical methods leading to 2-arylpyr-
idines using NiBr2(2,20-bipyridine) as catalyst.11 However, although
theses methods lead to good yields in heterocoupling product,
electrochemical reactions are generally considered as being more
difficult to handle than conventional methods and electrochemical
synthesis is rarely applied by organic chemists in a larger scale.
Then, a conventional chemical is often preferred. Recently we have
discovered an efficient cobalt catalyzed method devoted to the
formation of unsymmetrical biaryls exhibiting high tolerance to-
wards sensitive functional groups on the aromatic nucleus.12
However, this protocol cannot be applied to 2-chloropyrimidine as
coupling partners except in the case of 3-substituted pyridines.
Therefore, we have decided to develop a cross-coupling chemical
method using a nickel catalyst instead of electrochemical process.
Moreover, we have reported recently a chemical method for acti-
vation of
a-chloroesters leading to aryl propanoic esters using
NiBr2(Bipy) as catalyst in the presence of manganese as reducing
metal.13 The main advantages of the method are the use of an
easily prepared Ni(II)bipy complex in catalytic amount, which is
not air sensitive and the easy control of the overall reactions.
Herein, we describe the details of a cross-coupling reaction using
a nickel complex in combination with manganese dust as a re-
ducing agent and establish its scope and synthetic utility for the
efficient formation of a variety of functionalized 2-arylpyridines
(Scheme 1).
* Corresponding author. Tel.: þ33 1 69334412; fax: þ33 1 69334440.
E-mail address: corinne.gosmini@polytechnique.edu (C. Gosmini).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.05.044

6142
C. Gosmini et al. / Tetrahedron 65 (2009) 6141–6146
position decreases the yield considerably (Table 1, entry 3). Gener-
"NiBr2Bpy" cata, Mn , H+
DMF
FG'
X
FG
ally, yields of coupling product are increased in some cases up to 30%
compared to results obtained by the electrochemical coupling. An
aryl bromide substituted by an halogen such as a fluorine (Table 1,
entry 8), less electron-withdrawing, was not enough reactive to
react with Ni(0) before the 2-bromopyridine. In this case the use of
2-chloropyridine was preferable as reported in the next section. To
extend the scope of this process, we intend to show that this method
can be suitable for coupling with less reactive 2-chloropyridine.
+
Y
FG'
N
FG
N
Scheme 1. Cross-coupling of 2-arylpyridines and functionalized aryl halides.
2. Results and discussion
2.1. Cross-coupling of various aryl halides with 2-
halopyridine
2.1.2. Cross-coupling of various aryl halides with 2-chloropyridine
The use of 2-chloropyridine is of great interest due to their wide
availability. As a consequence, the discovery of efficient procedures
for the coupling of this compound with various aryl halides is
highly desirable.
In this case, both an electro-withdrawing group and chlorine on
the aromatic nucleus or both an electron-donating group and
a bromide were necessary to react with 2-chloropyridine to avoid
the formation of Ar–Ar. Results are reported in Table 2.
Some years ago, we have adapted some electrochemical re-
actions in ‘pure chemical process’ employing an appropriate re-
ducing metal. After a brief survey of reducing metal, we have
found that manganese powder was the best one for the reduction
of cobalt,12,14,15 iron16 or nickel salt.13 On the basis of these im-
provements, we investigated the chemical coupling between
various 2-halopyridines and substituted aryl halides, using
NiBr2bipy as catalyst. Our work started with the synthesis of 2-
arylpyridines functionalized on the arene moiety. According to our
previous electrochemical studies, we assume that FG–C6H4NiX is
the first formed intermediate, being further reduced to FG–C6H4Ni
to react preferably with 2-halopyridine.11b Then, we would have
the best halogen on the aryl halide according to the nature of the
substituent for the coupling reaction to be efficient. Typical pro-
cedure: A 1:1.3 mixture of the aryl halide and the halopyridine is
stirred at room temperature in the presence of the catalytic
amount of NiBr2bpy (10 mol %), excess of manganese powder
(2.3 equiv) activated by trifluoroacetic acid in DMF. The manga-
nese has proven to be the adequate metal in order to achieve the
two successive oxidative additions followed by the reductive
elimination that constitute the mechanism involved in this re-
action. Reactions are conducted at room temperature except in the
case of ortho-substituted aryl halides (60 ꢀC).
Table 2
Cross-coupling between 2-chloropyridine and substituted aryl halides
X
FG
"NiBr2Bpy cata, Mn H+
Cl
DMF
FG
+
N
N
X=Br FG= electron-donating
X=Cl FG= electron-withdrawing goup
Entry
ArX
FG
Product
Reaction time
Yield (GC)%
X
1
2
3
4
5
6
7
8
p-CO2Me
m-CO2Me
o-CO2Mea
p-CN
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Br
Br
Br
Br
Br
Br
Br
Br
10
11
12
7
13
5
2 h
18 h
48 h
6 h
6 h
3 h
18 h
3 h
20 min
3 h 30 min
16 h
2 h 30 min
1 h
86 (94)
74 (78)
45 (46)
63 (76)
63 (77)
83 (89)
63 (70)
81 (92)
71 (90)
62 (76)
56 (72)
68 (80)
61 (71)
73 (86)
54 (60)
m-CNa
p-CF3
2.1.1. Cross-coupling of various aryl halide with 2-bromopyridine
This coupling-process has been successfully applied to 2-bro-
mopyridine and various aryl halides. However, the choice of both
the substituent and the halogen on the aromatic nucleus was im-
portant. The reactions were performed only with an aryl bromide
substituted by an electron-withdrawing group or with an aryl io-
dide substituted by an electron-donating group. Results are shown
in Table 1.
a
o-CF3
14
9
p-OMe
o-OMea
p-NH2
9
15
16
17
18
19
8
10
11
12
13
14
15
a
o-NH2
p-N(Me)2
o-Mea
p-F
1 h 30 min
1 h
p-Cl
20
Results show that the cross-coupling is efficient whatever the
meta or para position of the substituent. On the other hand, the ortho
a
Reaction conducted at 60 ꢀC.
Table 1
One more time, yields are slightly superior than those obtained
by our electrochemical method. An ortho substituent decrease the
yield in spite of a good yield (Table 2, entries 3, 7, 9, 11 and 13) if the
reaction is conducted at 60 ꢀC. Interestingly, the reaction conditions
allowed an efficient cross-coupling between 2-chloropyridine and
aryl halides bearing relatively acidic NH2 groups without protection
(Table 2, entries 10 and 11).
Cross-coupling between 2-bromopyridine and substituted aryl halides
X
FG
"NiBr2Bpy cata, Mn H+
FG
+
N
Br
DMF
N
X=I FG= electron-donating
X=Br FG= electron-withdrawing goup
Entry
ArX
FG
Product
Reaction time
Yielda (GC)%
2.2. Cross-coupling of various aryl halides with
functionalized 2-chloropyridines
X
1
2
3
4
5
6
7
8
9
p-CO2Et
m-CO2Et
o-CO2Et
p-COMe
p-CF3
m-CF3
p-CN
p-F
Br
Br
Br
Br
Br
Br
Br
Br
I
1
2
3
4
5
6
7
8
9
50 min
6 h
18 h
22 h
1 h
30 min
4 h
1 h
91 (93)
83 (84)
20 (48)
86 (97)
76 (84)
63 (85)
83 (92)
34 (43)
75 (85)
Encouraged by these previous works, we decided to go on with
the coupling of some functionalized 2-chloropyridines and various
functionalized aryl halides.
2.2.1. Cross-coupling of various aryl halides bearing an electro-
donating group with functionalized 2-chloropyridines
The presence of an electron-donating substituent on 2-chloro-
pyridines does not significantly change their reactivity. So, in this
p-OMe
5 min
a
Isolated yield.

C. Gosmini et al. / Tetrahedron 65 (2009) 6141–6146
6143
Table 3
manganese powder as reducing reagent in combination with
NiBr2Bpy catalyst enables the synthesis from commercially avail-
able chemicals of a broad spectrum of valuable compounds in
satisfactory to high yields under simple and mild conditions.
Cross-coupling between functionalized 2-chloropyridines and various aryl halides
substituted by an electron-donating group
X
FG
"NiBr2Bpy cata, Mn H+
DMF
FG
FG'
Cl
FG'
4. Experimental
4.1. General
N
N
Entry
PyrCl FG0
ArX FG
X
Product
Time (min)
Yielda (GC)%
1
2
3
4
5
6
5-CF3
5-CF3
6-Me
6-OMe
6-OMe
6-OMe
p-NH2
p-OMe
p-OMe
p-OMe
p-NMe2
p-NH2
I
I
Br
Br
Br
Br
21
22
23
24
25
26
30
50
240
10
20
20
44 (65)
35 (48)
82 (90)
50 (76)
54 (65)
47 (58)
The synthesis was monitored with a Gas Chromatograph (Var-
ian3300, apolar column CPSiL5CB, 25 m), dodecan C12H26 used as
an intern standard. Products were purified by flash silica gel
chromatography. 1H, 13C and 19F NMR spectra were measured on
spectrometers at 400.13, 100.62 and 376.46 MHz, respectively. 19F
NMR chemical shifts were referenced to external CFCl3 (0.0 ppm).
The mass spectra were obtained by EI by GC–MS analysis. All the
solvents are used in the commercially form. The dimethylforma-
mide (HPLC quality) was kept under inert atmosphere. The starting
materials are commercially available (Aldrich, Acros) and are used
without further purification.
Br
7
6-Me
27
240
67 (70)
N
H
a
Isolated yield.
case, an aryl bromide should bear an electron-donating group
(Table 3, entries 3–7). On the other hand, a chloropyridine activated
by an electron-donating group should react with an aryl iodide
bearing an electro-withdrawing group (Table 3, entries 1 and 2).
Results are reported in Table 3.
Excellent to moderate yields are obtained depending on the na-
ture of the substituent on 2-chloropyridine. A protected amine leads
to similar yields than non-protected amine (Table 3, entries 5 and 6).
The nickel bromide 2,20-bipyridine complex was prepared from
nickel bromide and 2,20-bipyridine according to the reported pro-
cedures17 and stored in a hermetic flask.
4.2. Representative procedure for the direct cross-coupling
reactions catalyzed by nickel bromide 2,20-bipyridine
To a solution of nickel bromide 2,20-bipyridine (0.5 mmol, 10%)
and manganese powder (11.5 mmol) in dimethylformamide (8 mL)
were successively added at room temperature the halogen–aryl or
halogen–heteroaryl (5 mmol), the 2-halogenopyridine (6.5 mmol)
2.2.2. Cross-coupling of various aryl bromides bearing an electro-
withdrawing group with functionalized 2-chloropyridines
We have envisioned to couple various functionalized 2-chloro-
pyridines with different aryl bromides bearing an electron-with-
drawing group. In this case, 2-chloropyridine could bear either an
electron-donating or electron-withdrawing group due to the
highest reactivity of the aryl bromide in each case. This is in keeping
with our postulated mechanism, where the aryl halide should react
faster than the pyridine halide with the Ni(0). Results are reported
in Table 4.
and trifluoroacetic acid (100 mL), causing an immediate rise in
temperature and colour change to dark grey. The medium was then
stirred at room temperature until complete conversion of aryl ha-
lide. In all cases, the amounts of the coupling product were mea-
sured by GC using an internal reference (dodecane, 200 mL). The
reaction mixture was poured into a saturated aqueous solution of
NH4Cl and extracted with diethyl ether (3ꢁ70 mL). The organic
layer was washed with a saturated aqueous solution of NaCl and
dried over MgSO4. Evaporation of solvent and purification by col-
umn chromatography on silica gel (pentane/diethyl ether) afforded
the coupling product.
Table 4
Cross-coupling between functionalized 2-chloropyridines and various aryl bromides
substituted by an electron-withdrawing group
Br
FG
FG
"NiBr2Bpy cata, Mn H+
DMF
N
4.2.1. Ethyl 4-(pyridin-2-yl)benzoate (1)
FG'
Cl
+
FG'
CAS 4385-61-9.
N
13C NMR (CDCl3, 100 MHz)
d
ppm 14.3, 61.1, 121.6, 122.9, 126.8,
130.0, 130.8, 137.0, 143.2, 149.7, 156.1, 166.4. 1H NMR (CDCl3,
400 MHz)
Entry
PyrCl FG0
ArBr FG
p-CO2Me
Product
Time (h)
Yield (GC)%
d
ppm 1.43 (t, 3H, J¼7.1 Hz), 4.41 (q, 2H, J¼7.1 Hz), 7.25–
1
2
3
4
5
6
6-CN
6-CN
5-CF3
3-CO2Et
3-CO2Et
3-CO2Et
28
29
30
31
32
33
5
51 (58)
42 (58)
50 (68)
40 (72)
68 (78)
78 (86)
7.30 (m, 1H), 7.79 (t, 2H, J¼3.3 Hz), 8.13 (d, 2H, J¼8.2 Hz), 8.2 (d, 2H,
J¼8.2 Hz), 8.74 (d, 1H, J¼3.3 Hz), EIMS m/z 227 (M), 199, 182 (base),
154, 127.
p-COMe
p-CO2Et
p-CN
1.5
1.2
4
p-COMe
p-CO2Et
1
2.5
4.2.2. Ethyl 3-(Pyridin-2-yl)benzoate (2)
CAS 4550-32-7.
Br
13C NMR (CDCl3, 100 MHz)
d
ppm 14.2, 60.9, 120.3, 122.4, 127.7,
128.7, 129.8, 130.9, 131.0, 136.7, 139.4, 149.6, 155.9, 166.1. 1H NMR
(CDCl3, 400 MHz)
7.07 (m, 1H), 7.39 (t, 1H, J¼7 Hz), 7.58 (m, 2H), 7.97 (t, 1H, J¼8 Hz),
8.08 (t, 1H, J¼8 Hz), 8.56 (m, 2H). EIMS m/z 227 (M), 182, 155 (base),
154, 127.
7
3-CO2Et
34
18
50 (56)
S
d
ppm 1.27 (t, 3H, J¼7 Hz), 4.27(q, 2H, J¼7 Hz),
8
9
10
3-CN, 6-Me
5-Me
6-OMe
p-CO2Et
p-COMe
p-CO2Me
35
36
37
6.5
3.5
0.2
47a (55)
78 (87)
53 (61)
a
Reaction conducted at 80 ꢀC.
4.2.3. Ethyl 2-(pyridin-2-yl)benzoate (3)
3. Conclusion
CAS 28901-52-2.
13C NMR (CDCl3, 100 MHz)
d
ppm 13.8, 60.9, 120.3, 122.0, 123.0,
128.4, 129.8, 131.1, 131.7, 136.5, 140.6, 148.6, 158.7, 168.6. 1H NMR
(CDCl3, 400 MHz)
ppm 1.08 (t, 3H, J¼7.1 Hz), 4.12(q, 2H, J¼7.1 Hz),
In summary, we have devised an expedient route to function-
alized 2-arylpyridines on the basis of nickel catalysis. The use of
d

6144
C. Gosmini et al. / Tetrahedron 65 (2009) 6141–6146
7.28–7.30 (m, 1H), 7.52 (d, 2H, J¼7.6 Hz), 7.59–7.60 (m, 2H), 7.78 (t,
1H, J¼7.6 Hz), 7.85 (d, 1H, J¼7.5 Hz), 8.64 (d, 1H, J¼4.1 Hz). EIMS m/z
227 (M), 198, 182 (base), 154, 127.
J¼7.8 Hz), 8.62 (s, 1H), 8.68 (s, 1H). EIMS m/z 213 (M), 182, 155
(base), 127, 101, 77.
4.2.12. 2-Pyridin-2-yl-benzoic acid methyl ester (12)
4.2.4. 2-(4-Acetoxyphenyl)pyridine (4)
CAS 98061-19-9.
CAS 173681-56-6.
13C NMR (CDCl3, 100 MHz)
d
ppm 51.9, 121.8, 122.9, 128.1, 129.6,
131.2, 132.7, 136.5, 140.5, 148.6, 158.4, 169.2. 1H NMR (CDCl3,
400 MHz) ppm 3.65 (s, 3H), 7.21 (m, 1H), 7.44–7.55 (m, 4H), 7.70
13C NMR (CDCl3, 100 MHz)
d
ppm 26.6, 120.9, 122.3, 126.9, 128.7,
136.8, 137.0, 143.5, 149.8, 157.0, 197.0. 1H NMR (CDCl3, 400 MHz)
d
d
ppm 2.6 (s, 3H), 7.2 (dd,1H, J¼4.4 and 8.1 Hz), 7.7 (d, 2H, J¼8.1 Hz),
(t, 1H, J¼7.2 Hz), 7.78 (d, 1H, J¼8.0 Hz), 8.62 (d, 1H, J¼4.5 Hz). EIMS
8.0–8.1 (m, 4H), 8.6 (dd, 1H, J¼4.4 and 1.2 Hz). EIMS m/z 197 (M),
m/z 213 (M), 182 (base), 169, 154, 127, 101, 77.
182 (base), 154, 127.
4.2.13. 3-Pyridin-2-yl-benzonitrile (13)
4.2.5. 2-(4-Trifluoromethyl-phenyl)pyridine (5)
CAS 4350-51-0.
CAS 203065-88-7.
13C NMR (CDCl3,100 MHz)
d
ppm 112.9,118.7,120.4,123.2, 129.5,
130.5, 130.9, 132.1, 137.1, 140.4, 149.9, 154.7. 1H NMR (CDCl3,
400 MHz)
13C NMR (CDCl3, 100 MHz)
d
ppm 121.7, 124.4 (q, J¼272 Hz),
127.1, 128.6, 128.9, 131.5 (q, J¼32 Hz), 136.1, 144.1, 151.4, 157.2. 1H
d
ppm 7.28 (m, 1H), 7.52 (m, 1H), 7.61 (d, 1H, J¼7.7 Hz),
NMR (CDCl3, 400 MHz)
d
ppm 7.1 (ddd, 1H, J¼8.6, 4.7, 2.1 Hz), 7.55
7.69 (d, 1H, J¼7.9 Hz), 7.75 (dd, 1H, J¼7.7 and 1.5 Hz), 8.17 (d, 1H,
J¼7.9 Hz), 8.27 (s, 1H), 8.65 (d, 1H, J¼4.8 Hz). EIMS m/z 180 (M,
base), 179, 170, 153, 140, 125, 100, 76.
(d, 4H, J¼7.5 Hz), 7.93 (d, 2H, J¼8 Hz), 8.56 (d, 1H, J¼4.4 Hz). 19F
NMR (CDCl3, 377 MHz)
184, 175, 154, 127.
d
ppm ꢂ62.6. EIMS m/z 223 (M, base), 203,
4.2.14. 2-(2-Trifluoromethyl-phenyl)-pyridine (14)
4.2.6. 2-(3-Trifluoromethyl-phenyl)pyridine (6)
CAS 441072-21-5.
CAS 5957-84-6.
13C NMR (CDCl3, 100 MHz)
d
ppm 122.5, 123.9, 124.1 (q,
J¼272 Hz), 125.5, 126.3, 128.1, 128.2 (q, J¼30 Hz), 131.5, 135.9, 140.0,
149.1, 157.8. 1H NMR (CDCl3, 400 MHz)
ppm 7.2–7.6 (m, 4H), 7.49
(d, 1H, J¼7.2 Hz), 7.55 (d, 1H, J¼7.3 Hz), 7.65–7.8 (m, 1H), 8.60 (m,
1H). 19F NMR (CDCl3, 377 MHz)
ppm ꢂ56.7. EIMS m/z 222 (Mꢂ1),
205 (base), 189, 177, 161, 145, 121.
13C NMR (CDCl3, 100 MHz)
d
ppm 122.3, 122.4, 128.7, 128.8,
129.7, 131.0, 136.4, 136.6, 139.7, 149.2, 149.5, 155.1. 1H NMR (CDCl3,
400 MHz)
d
d
ppm 7.1 (m, 1H), 7.44 (t, 1H, J¼7.8 Hz), 7.59–7.71 (m,
3H), 8.06 (d, 1H, J¼7.8 Hz), 8.3 (s, 1H), 8.62 (dd, 1H, J¼4.7 and
d
0.9 Hz). EIMS m/z 223 (M, base), 203, 184, 175, 154, 127.
4.2.7. 4-Pyridin-2-yl-benzonitrile (7)
4.2.15. 2-(2-Methoxy-phenyl)-pyridine (15)
CAS 32111-34-5.
CAS 5957-89-1.
13C NMR (CDCl3, 100 MHz)
d
ppm 112.3, 118.6, 121.1, 123.3, 127.7,
13C NMR (CDCl3, 100 MHz)
d
ppm 55.4, 111.4, 120.9, 121.5, 125.2,
129.0, 129.9, 131.2, 135.6, 149.4, 156.0, 156.9. 1H NMR (CDCl3,
400 MHz) ppm 3.7 (s, 3H), 6.9–7.2 (m, 3H), 7.3–7.4 (m, 1H), 7.6 (dt,
132.2,136.9,143.4,149.7,155.0. 1H NMR (400 MHz, CDCl3)
(m, 1H), 7.68–7.81 (m, 4H), 8.0 (d, 2H, J¼8.4 Hz), 8.62 (d, 1H,
J¼4.8 Hz). EIMS m/z 180 (M, base), 179, 153, 140, 125, 75.
d
ppm 7.2
d
1H, J¼7.7 and 2.0 Hz), 7.8 (d, 2H, J¼7.8 Hz), 8.7 (d, 1H, J¼5.1 Hz).
EIMS m/z: 184 (Mꢂ1, base), 167, 154, 141, 127, 115.
4.2.8. 2-(4-Fluoro-phenyl)-pyridine (8)
CAS 58861-53-3.
4.2.16. 4-Pyridin-2-yl-phenylamine (16)
13C NMR (CDCl3, 100 MHz)
d
ppm 115.5, 115.7, 120.1, 122.0, 128.6,
CAS 18471-73-3.
135.5, 136.8, 149.6, 156.4, 163.5 (d, JCF¼247 Hz). 1H NMR (CDCl3,
13C NMR (CDCl3, 100 MHz)
d
ppm 115.1, 119.4, 121.0, 128.0, 129.5,
400 MHz)
d
ppm 7.03 (m, 3H), 7.55 (m, 2H), 7.84 (t, 2H, J¼7.1 Hz),
136.7, 147.6, 149.4, 157.4. 1H NMR (CDCl3, 400 MHz)
d
ppm 3.80 (s,
8.57 (d, 1H, J¼4.7 Hz).19F NMR (CDCl3, 377 MHz)
d
ppm ꢂ112.95.
2H), 6.75 (d, 2H, J¼8.3 Hz), 7.10–7.30 (m, 1H), 7.64 (m, 2H), 7.84 (d,
2H, J¼8.3 Hz), 8.63 (d, 1H, J¼4.7 Hz). EIMS m/z 170 (M, base), 154,
143, 117.
EIMS m/z 173 (M, base), 172, 163, 153, 146, 133, 125.
4.2.9. 2-(4-Methoxy-phenyl)-pyridine (9)
CAS 5957-90-4.
4.2.17. 2-Pyridin-2-yl-phenylamine (17)
13C NMR (CDCl3, 100 MHz)
d
ppm 55.3, 114.1, 119.8, 121.4, 128.2,
CAS 19528-30-1.
132.0, 136.7, 149.6, 157.1, 160.5. 1H NMR (CDCl3, 400 MHz)
(s, 3H), 6.9 (dd, 2H, J¼9 and 1.2 Hz), 7.0 (m, 1H), 7.5–7.7 (m, 2H), 7.8
(d, 2H, J¼9 Hz), 8.5 (dd, 1H, J¼4.7 and 2.0 Hz). EIMS m/z 185 (M,
base), 170, 154, 142, 115.
d
ppm 3.7
13C NMR (CDCl3, 100 MHz)
d
ppm 117.3, 117.7, 121.0, 122.3, 129.4,
129.5, 130.0, 137.0, 144.3, 147.9, 159.5. 1H NMR (CDCl3, 400 MHz)
d
ppm 5.63 (s, 2H), 6.85 (m, 2H), 7.23 (m, 2H), 7.58 (d, 1H, J¼7.8 Hz),
7.65–7.85 (m, 2H), 8.65 (d, 1H, J¼3.7 Hz). EIMS m/z 169 (Mꢂ1, base),
142, 115.
4.2.10. 4-Pyridin-2-yl-benzoic acid methyl ester (10)
CAS 98061-21-3.
4.2.18. Dimethyl-(4-pyridin-2-yl-phenyl)-amine (18)
13C NMR (CDCl3, 100 MHz)
d
ppm 52.0, 120.5, 122.8, 127.0, 130.1,
130.6, 136.8, 143.4, 149.8, 155.9, 166.6. 1H NMR (CDCl3, 400 MHz)
ppm 3.87 (s, 3H), 7.18 (m, 1H), 7.68 (m, 2H), 8.05 (2d, 4H,
CAS 100381-45-1.
13C NMR (CDCl3, 100 MHz)
d
ppm 40.4, 112.3, 119.3, 120.6, 128.0,
d
136.9, 148.9, 151.0, 167.0. 1H NMR (CDCl3, 400 MHz)
d
ppm 3.03 (s,
J¼8.4 Hz), 8.66 (d, 1H, J¼4.7 Hz). EIMS m/z 213 (M), 182 (base), 154,
6H), 6.82 (d, 2H, J¼8.0 Hz), 7.13 (m, 1H), 7.67 (m, 2H), 7.98 (d, 2H,
J¼8.0 Hz), 8.66 (m, 1H). EIMS m/z 198 (M, base), 182, 168, 154, 127.
127.
4.2.11. 3-Pyridin-2-yl-benzoic acid methyl ester (11)
4.2.19. 2-o-Tolyl-pyridine (19)
CAS 98061-20-2.
CAS 10273-89-9.
13C NMR (CDCl3, 100 MHz)
d
ppm 52.1, 120.2, 122.2, 127,5,
129.1, 130.1, 131.5, 136.5, 137.1, 139.6, 149.7, 156.0, 166.8. 1H NMR
(CDCl3, 400 MHz) ppm 3.92 (s, 3H), 7.20 (m, 1H), 7.48 (t, 1H,
J¼7.8 Hz), 7.70 (m, 2H), 8.05 (d, 1H, J¼7.7 Hz), 8.18 (d, 1H,
13C NMR (CDCl3, 100 MHz)
d
ppm 20.3, 123.0, 123.6, 128.1, 129.8,
130.5, 135.5, 136.5, 137.5, 138.0, 149.8, 160.1. 1H NMR (CDCl3,
400 MHz) ppm 2.28 (s, 3H), 7.20–7.40 (m, 6H), 7.66 (m, 1H), 8.56–
8.62 (m, 1H). EIMS m/z 169 (M, base), 141, 115, 84.
d
d

C. Gosmini et al. / Tetrahedron 65 (2009) 6141–6146
6145
4.2.20. 2-(4-Chloro-phenyl)-pyridine (20)
4.2.28. 4-(6-Cyano-pyridin-2-yl)-benzoic acid methyl ester (28)
CAS 5969-83-5.
CAS 296776-88-0.
13C NMR (CDCl3, 100 MHz)
d
ppm 120.2, 122.3, 124.4, 128.4,
13C NMR (CDCl3, 100 MHz)
d
ppm 52.3, 116.4, 121.5, 122.4, 123.9,
128.9, 134.7, 138, 149.4, 156.0. 1H NMR (CDCl3, 400 MHz)
d
ppm 7.03
126.9, 130.3, 131.6, 141.2, 150.6, 157.6, 166.5. 1H NMR (CDCl3,
(m,1H), 7.28 (d, 2H, J¼8.3 Hz), 7.5 (m, 2H), 7.8 (d, 2H, J¼8.3 Hz), 8.53
(d, 1H, J¼3.8 Hz). EIMS m/z 189–191(M), 154 (base), 127.
400 MHz)
d
ppm 3.99 (s, 3H), 7.50 (d, 1H, J¼4.4 Hz), 8.00 (t, 1H,
J¼4.4 Hz), 8.10 (d, 2H, J¼4.4 Hz), 8.20 (d, 2H, J¼8.1 Hz), 8.92 (d, 1H,
J¼8.1 Hz). EIMS m/z 238 (M), 207 (base), 194, 179, 170, 152.
4.2.21. 4-(5-Trifluoromethyl-pyridine-2-yl)-phenylamine (21)
CAS 910036-88-3.
4.2.29. 6-(4-Acetyl-phenyl)-pyridine-2-carbonitrile (29)
13C NMR (CDCl3, 100 MHz)
d
ppm 115.0, 118.4, 123.4 (q,
13C NMR (CDCl3, 100 MHz)
d
ppm 26.8, 116.3, 121.8, 123.1,
125.8, 127.1, 129.0, 138.1, 144.3, 150.3, 155.5, 197.5. 1H NMR
(CDCl3, 400 MHz)
J¼32.0 Hz), 124.0 (q, J¼270 Hz), 127.9, 128.6, 133.6, 146.3, 148.5,
160.6. 1H NMR (CDCl3, 400 MHz)
d
ppm 3.92 (s, 2H), 6.77 (d, 2H,
d
ppm 2.80 (s, 3H), 7.60 (d, 1H, J¼4.6 Hz), 7.70
J¼8.1 Hz), 7.72 (d, 1H, J¼7.3 Hz), 7.89 (m, 3H), 8.88 (s, 1H). 19F NMR
(d, 2H, J¼8.2 Hz), 8.10 (m, 3H), 8.87 (d, 1H, J¼4.7 Hz). EIMS m/z
222 (M), 207 (base), 179, 170, 152, 125. Anal. Calcd for C14H10N2O:
C, 75.66; H, 4.54; N, 12.6; O, 7.20. Found: C, 75.40; H, 4.33; N,
12.81.
(CDCl3, 377 MHz)
185, 169.
d
ppm ꢂ62.08. EIMS m/z 238 (M, base), 217, 197,
4.2.22. 2-(4-Methoxy-phenyl)-5-trifluoromethyl-pyridine (22)
CAS 296776-84-6.
4.2.30. 4-(5-Trifluoromethyl-pyridin-2-yl)-benzoic acid
ethyl ester (30)
13C NMR (CDCl3, 100 MHz)
d
ppm 55.4, 114.4, 119.1, 123.8 (q,
J¼272 Hz), 124.1 (q, J¼33.1 Hz), 128.9, 130.3, 133.9, 146.3, 160.2,
161.4. 1H NMR (CDCl3, 400 MHz)
ppm 3.90 (s, 3H), 7.04 (d, 2H,
CAS 1089330-74-4.
d
13C NMR (CDCl3, 100 MHz)
d
ppm 14.3, 61.2, 120.4, 123.6 (q,
J¼271 Hz), 125.5 (q, J¼33 Hz), 127.2, 130.0, 131.8, 134.2, 141.6,
146.6, 159.4, 166.1. 1H NMR (CDCl3, 400 MHz)
ppm 1.33 (t, 3H,
J¼8.8 Hz), 7.78 (d, 1H, J¼8.3 Hz), 7.93 (d, 1, H, J¼8.3 Hz), 8.03 (d, 2H,
J¼8.8 Hz), 8.92 (s, 1H). 19F NMR (CDCl3, 377 MHz)
EIMS m/z 253 (M, base), 238, 210, 190, 141.
d
ppm ꢂ62.39.
d
J¼7.5 Hz), 4.33 (q, 2H, J¼7.5 Hz), 7.53 (d, 1H, J¼8.3 Hz), 7.74 (d,
1H, J¼8.3 Hz), 7.95–8.05 (m, 4H), 8.85 (s, 1H). 19F NMR (CDCl3,
4.2.23. 2-(4-Methoxy-phenyl)-6-methyl-pyridine (23)
377 MHz)
d
ppm ꢂ62.48. EIMS m/z 295 (M), 267, 250 (base), 222,
CAS 4385-63-1.
202, 182, 153. HRMS for C14H12N2: calcd 208.2586; found:
208.2582.
13C NMR (CDCl3, 100 MHz)
d
ppm 22.5, 53.1, 112.2, 114.9, 118.9,
126.4, 130.1, 134.8, 154.3, 155.9, 159.2. 1H NMR (CDCl3, 400 MHz)
d
ppm 2.62 (s, 3H), 3.82 (s, 3H), 6.99 (d, 3H, J¼8.8 Hz), 7.43 (d, 1H,
4.2.31. 2-(4-Cyano-phenyl)-nicotinic acid ethyl ester (31)
J¼7.8 Hz), 7.55 (d, 1H, J¼7.8 Hz), 7.97 (d, 2H, J¼7.8 Hz). EIMS m/z 199
CAS 296776-85-7.
(M, base), 184, 156, 141, 128.
13C NMR (CDCl3, 100 MHz)
d
ppm 13.7, 61.8, 112.3, 118.7, 122.6,
127.1, 129.4, 131.8, 138.4, 144.7, 151.5, 157.2, 166.8. 1H NMR (CDCl3,
400 MHz)
4.2.24. 2-Methoxy-6-(4-methoxy-phenyl)-pyridine (24)
d
ppm 1.05 (t, 3H, J¼7.3 Hz), 4.11 (q, 2H, J¼7.3 Hz), 7.36
CAS 296776-83-5.
(dd, 1H, J¼4.8 and 7.7 Hz), 7.56 (d, 2H, J¼8.1 Hz), 7.65 (d, 2H,
J¼8.1 Hz), 8.14 (d,1H, J¼7.7 Hz), 8.72 (d,1H, J¼4.8 Hz). EIMS m/z 252
(M), 223 (base), 207, 179, 152, 140, 125.
13C NMR (CDCl3, 100 MHz)
d
ppm 53.2, 108.3, 110.9, 111.9, 113.6,
114.0, 128.3, 131.7, 139.2, 153.4, 154.4, 160.4, 163.4. 1H NMR (CDCl3,
400 MHz)
d
ppm 3.95 (s, 6H), 6.70 (d, 1H, J¼8.2 Hz), 6.89 (d, 2H,
J¼8.4 Hz), 7.20 (d, 1H, J¼7.6 Hz), 7.60 (t, 1H, J¼7.5 Hz), 7.93 (m, 2H).
4.2.32. 2-(4-Acetyl-phenyl)-nicotinic acid ethyl ester (32)
EIMS m/z 215 (M), 214 (base), 199, 186, 170, 157, 142.
CAS 296776-86-8.
13C NMR (CDCl3, 100 MHz)
d
ppm 13.7, 26.8, 61.7, 122.3, 127.3,
128.1, 128.9, 136.8, 138.2, 144.7, 151.4, 157.9, 167.4, 197.8. 1H NMR
(CDCl3, 400 MHz)
4.2.25. [4-(6-methoxy-pyridin-2-yl)-phenyl]-dimethyl-amine (25)
CAS 31640-81-0.
d
ppm 1.10 (t, 3H, J¼7 Hz), 2.67 (s, 3H), 4.20 (q,
13C NMR (CDCl3, 100 MHz)
d
ppm 40.6, 53.0, 107.4, 111.3, 112.5,
2H, J¼7 Hz), 7.40 (dd, 1H, J¼5 and 8 Hz), 7.66 (d, 2H, J¼8 Hz), 8.05
(d, 2H, J¼8 Hz), 8.11 (dd, 1H, J¼8.and 2 Hz), 8.81 (dd, 1H, J¼5 and
1.5 Hz). EIMS m/z 269 (M), 254 (base), 240, 226, 198, 182, 170,
154.
124.1, 127.6, 139.0, 150.7, 154,9, 163.6. 1H NMR (CDCl3, 400 MHz)
d
ppm 2.83 (s, 6H), 3.95 (s, 3H), 6.47 (d, 1H, J¼8.1 Hz), 6.71 (d, 2H,
J¼8.4 Hz), 7.15 (d, 1H, J¼7.4 Hz), 7.46 (m, 1H), 7.88 (d, 2H, J¼8.4 Hz).
EIMS m/z 228 (M, base), 211, 199, 183, 169, 154.
4.2.33. 2-(4-ethoxycarbonyl-phenyl)-nicotinic acid ethyl ester (33)
4.2.26. 4-(6-Methoxy-pyridin-2-yl)-phenylamine (26)
13C NMR (CDCl3, 100 MHz)
d
ppm 13.6, 14.2, 60.9, 61.5; 122.1,
127.3, 128.3, 129.4, 130.6, 137.7, 144.4, 151.2, 157.8, 166.1, 167.3. 1H
NMR (CDCl3, 400 MHz)
13C NMR (CDCl3, 100 MHz)
d
ppm 53.1, 107.7, 111.4, 114.9, 127.9,
129.5, 139.1, 147.3, 154.9, 163.6. 1H NMR (CDCl3, 400 MHz)
d
ppm
d
ppm 0.97 (t, 3H, J¼7.1 Hz), 1.3 (t, 3H,
3.79 (s, 2H), 4.07 (s, 3H), 6.60 (d, 1H, J¼6.9 Hz), 6.70 (d, 2H, J¼6 Hz),
7.23 (d, 1H, J¼6 Hz), 7.6 (m, 1H), 7.95 (d, 2H, J¼6 Hz). EIMS m/z 200
(M, base); 171, 169, 155, 144, 130, 115, 103. Anal. Calcd for
C12H12N2O: C, 71.98; H, 6.04; N, 13.99; O, 7.99. Found: C, 71.82; H,
5.95; N, 13.93.
J¼7.1 Hz), 4.07 (q, 2H, J¼7.1 Hz), 4.31 (q, 2H, J¼7.1 Hz), 7.26 (dd, 1H,
4.8 and 7.8 Hz), 7.53 (d, 2H, J¼8.1 Hz), 8.04 (m, 3H), 8.67 (d, 1H,
J¼4.8 Hz). EIMS m/z 299 (M), 270 (base), 254, 242, 226, 198, 170,
154. Anal. Calcd for C17H17NO4: C, 68.21; H, 5.72; N, 4.68; O, 21.38.
Found: C, 68.11; H, 5.65; N, 4.70.
4.2.27. 5-(6-Methyl-pyridin-2-yl)-1H-indole (27)
4.2.34. 2-Thiophen-3-yl-nicotinic acid ethyl ester (34)
13C NMR (CDCl3, 100 MHz)
d
ppm 24.5, 103.3, 111.3, 117.9, 119.8,
120.8, 121.6, 125.0, 128.3, 131.2, 136.5, 137.3, 157.8, 158.1. 1H NMR
(CDCl3, 400 MHz) ppm 2.69 (s, 3H), 6.62 (s, 1H), 7.06 (d, 1H,
CAS 296776-91-5.
13C NMR (CDCl3, 100 MHz)
d
ppm 14.1, 61.6, 121.4, 125.2, 125.3,
127.2, 128.0, 137.4, 140.9, 151.1, 153.1, 168.1. 1H NMR (CDCl3,
400 MHz)
d
J¼7.4 Hz), 7.21 (s, 1H), 7.42 (d, 1H, J¼8.4 Hz), 7.58 (d, 1H, J¼7.7 Hz),
7.65 (m, 1H), 7.86 (d, 1H, J¼8.4 Hz), 8.27 (s, 1H), 8.59 (s, 1H). EIMS m/
z 208 (M, base), 192, 180, 166, 152, 142. HRMS for C14H12N2: calcd
208.2586; found: 208.2582.
d
ppm 1.15 (t, 3H, J¼7.1 Hz), 4.23 (q, 2H, J¼7.1 Hz), 7.23
(dd, 1H, J¼4.8 and 7.8 Hz), 7.32 (m, 2H), 7.61 (d, 1H, J¼4.1 Hz), 7.8
(dd, 1H, J¼1.6 and 7.8 Hz), 8.69 (dd, 1H, J¼4.8 and 1.6 Hz). EIMS m/z
233(M), 204 (base), 188, 176, 161, 148, 133, 116, 89.

6146
C. Gosmini et al. / Tetrahedron 65 (2009) 6141–6146
ford, N. D. P. Bioorg. Med. Chem. Lett. 2004, 14, 3993; (c) Dupriest, M. T.; Schmidt,
C. L.; Kuzmich, D.; Williams, S. B. J. Org. Chem. 1986, 51, 2021; (d) Bach, T.;
Heuser, S. Synlett 2002, 2089.
4.2.35. 4-(3-Cyano-6-methyl-pyridin-2-yl)-benzoic acid
ethyl ester (35)
CAS 296776-90-4.
3. (a) Rieke, R. D.; Suh, Y.; Kim, S.-H. Tetrahedron Lett. 2005, 46, 5961; (b) Cahiez,
G.; Knochel, P. Synlett 2003, 1892; (c) Korn, T. J.; Schade, M. A.; Cheemala, M. N.;
Wirth, S.; Guevara, S. A.; Cahiez, G.; Knochel, P. Synthesis 2006, 3547; (d)
Rueping, M.; Leowsuwan, W. Synlett 2007, 247; (e) Nokami, T.; Tomida, Y.;
Kamei, T.; Itami, K.; Yoshida, J.-I. Org. Lett. 2006, 8, 729; (f) Bonnet, V.; Mongin,
F.; Trecourt, F.; Queguiner, G.; Knochel, P. Tetrahedron 2002, 58, 4429; (g) Ne-
gishi, E.-I.; Luo, F.-T.; Brisbee, R.; Matsushita, H. Heterocycles 1982, 18, 117; (h)
Gauthier, D. R.; Szumigala, R. H.; Dormer, P. G.; Armstrong, J. D.; Volante, R. P.;
Reider, P. J. Org. Lett. 2002, 4, 375; (i) Riguet, E.; Alami, M.; Cahiez, G. Tetrahe-
dron Lett. 1997, 38, 4397; (j) Lee, H. M.; Nolan, S. P. Org. Lett. 2000, 2, 2053; (k)
Takami, K.; Yorimitsu, H.; Shinokubo, H.; Matsubara, S.; Oshima, K. Org. Lett.
2001, 3, 1997; (l) Rau, M. L.; Yamazaki, O.; Shimada, S.; Tanaka, T.; Suzuki, Y.;
Tanaka, M. Org. Lett. 2001, 3, 4103; (m) Molander, G.; Biolatto, B. J. Org. Chem.
2003, 68, 4302; (n) Liu, S. Y.; Choi, M. J.; Fu, G. C. Chem. Commun. 2001, 2408.
4. (a) Sakamoto, T.; Kondo, Y.; Murata, N.; Yamanaka, H. Tetrahedron 1993, 49,
9713; (b) Sakamoto, T.; Kondo, Y.; Murata, N.; Yamanaka, H. Tetrahedron Lett.
1992, 33, 5373; (c) Kondo, Y.; Murata, N.; Sakamoto, T. Heterocycles 1994, 37,
1467; (d) Simkovsky, N. M.; Ermann, M.; Roberts, S. M.; Parry, D. M.; Baxter, A.
D. J. Chem. Soc., Perkin Trans. 1 2002, 1847; (e) Chinchilla, R.; Najera, C.; Yus, M.
Arkivoc 2007, 10, 152; (f) Deng, J. Z.; Paone, D. V.; Ginnetti, A. T.; Kurihara, H.;
Dreher, S. D.; Weissman, S. A.; Stauffer, S. R.; Burgey, C. S. Org. Lett. 2009, 11, 345.
5. Anderson, H.; Almquist, F.; Olsson, R. Org. Lett. 2007, 9, 1335.
13C NMR (CDCl3, 100 MHz)
d
ppm 14.3, 25.2, 61.2, 104.8, 117.7,
121.9, 129.8, 130.3, 131.7, 141.3, 141.7, 159.5, 162.9, 166.1. 1H NMR
(CDCl3, 400 MHz)
d
ppm 1.43 (t, 3H, J¼7.1 Hz), 2.7 (s, 3H), 4.42 (q,
2H, J¼7.1 Hz), 7.27 (d, 1H, J¼7.8 Hz), 7.98 (dd, 3H, J¼8.2 and 7.8 Hz),
8.19 (d, 2H, J¼8.2 Hz). EIMS m/z 266 (M, base), 237, 221, 193, 166,
140.
4.2.36. 1-[4-(5-Methyl-pyridin-2-yl)-phenyl]-ethanone (36)
CAS 953420-67-2.
13C NMR (CDCl3, 100 MHz)
d
ppm 18.2, 26.7, 120.6, 126.8, 128.8,
132.8, 137.0, 137.7, 143.3, 150.1, 153.2, 197.7. 1H NMR (CDCl3,
400 MHz)
d
ppm 2.40 (s, 3H), 2.65 (s, 3H), 7.62 (dd, 1H, J¼8 and
1.4 Hz), 7.71 (d, 1H, J¼8 Hz), 8.07 (2d, 4H, J¼8.4 Hz), 8.57 (s, 1H).
EIMS m/z 211 (M), 196 (base), 168, 115.
4.2.37. 4-(6-Methoxy-pyridin-2-yl)-benzoic acid methyl ester (37)
6. Hassan, J.; Hathroubi, C.; Gozzi, C.; Lemaire, M. Tetrahedron 2001, 57, 7845.
7. Zhang, N.; Thomas, L.; Wu, B. J. Org. Chem. 2001, 66, 1500.
8. Pal, M.; Batchu, V. R.; Dager, I.; Swamy, N. K.; Padakanti, S. J. Org. Chem. 2005, 70,
2376.
9. Campeau, L. C.; Rousseaux, S.; Fagnou, K. J. Am. Chem. Soc. 2005, 127, 18020.
10. Nunez, A.; Sanchez, A.; Burgos, C.; Alvarez-Builla, J. Tetrahedron 2004, 60, 6217.
11. (a) Gosmini, C.; Nedelec, J. Y.; Perichon, J. Tetrahedron Lett. 2000, 41, 5039; (b)
Gosmini, C.; Lasry, S.; Nedelec, J. Y.; Perichon, J. Tetrahedron 1998, 54, 1289.
12. Amatore, M.; Gosmini, C. Angew. Chem., Int. Ed. 2008, 47, 2089.
CAS 223127-56-8.
13C NMR (CDCl3, 100 MHz)
d
ppm 52.1, 53.3, 110.3, 113.4, 128.6,
129.9, 130.2, 139.3, 143.1, 153.3, 163.8, 166.9. 1H NMR (CDCl3,
400 MHz)
d
ppm 3.96 (s, 3H), 4.06 (s, 3H), 6.77 (d, 1H, J¼8.2 Hz),
7.42 (d, 1H, J¼7.4 Hz), 7.74 (t, 1H, J¼7.8 Hz), 8.13 (s, 4H). EIMS m/z
243 (M), 242 (base), 212, 198, 184, 169, 154, 141, 127, 114. HRMS for
C14H13NO3: calcd 243.0894; found: 243.0891.
13. Durandetti, M.; Gosmini, C.; Perichon, J. Tetrahedron 2007, 63, 1146.
14. Gosmini, C.; Begouin, J. M.; Moncomble, A. Chem. Commun. 2008, 3221.
15. (a) Amatore, A.; Gosmini, C.; Pe´richon, J. Eur. J. Chem. 2005, 989; (b) Amatore,
References and notes
´
A.; Gosmini, C.; Perichon, J. J. Org. Chem. 2006, 71, 2117.
16. (a) Durandetti, M.; Perichon, J. Tetrahedron Lett. 2006, 47, 6255; (b) Durandetti,
M.; Perichon, J. Synthesis 2006, 1542.
17. (a) Uchino, M.; Asagi, K.; Yamamoto, A.; Ikeda, S. J. Organomet. Chem. 1975, 84,
93; (b) Dunach, E.; Pe´richon, J. J. Organomet. Chem. 1988, 352, 239.
1. Fang, A. G.; Mello, J. V.; Finney, N. S. Org. Lett. 2003, 5, 967.
2. (a) Davies, I. W.; Marcoux, J. F.; Reider, P. Org. Lett. 2001, 3, 209; (b) Roppe, J. R.;
Wang, B.; Huang, D.; Tehrani, L.; Kamenecka, T.; Schweiger, E. J.; Anderson, J. J.;
Brodkin, J.; Jiang, X.; Cramer, M.; Chung, J.; Reyes-Manalo, G.; Munoz, B.; Cos-