Site selective synthesis of pentaarylpyridines via multiple Suzuki-Miyaura cross-coupling reactions

Article abstract of DOI:10.1002/adsc.201400164

Pentaarylpyridines were conveniently prepared in one step by pentafold Suzuki-Miyaura reactions of pentachloropyridine. Moreover, site selective reactions were performed, leading to various substituted arylpyridines. Pentaarylpyridines were studied in det

Full text of DOI:10.1002/adsc.201400164

FULL PAPERS
DOI: 10.1002/adsc.201400164
Site Selective Synthesis of Pentaarylpyridines via Multiple
Suzuki–Miyaura Cross-Coupling Reactions
Sebastian Reimann,a,b Peter Ehlers,a,b Andranik Petrosyan,a,b,c Stefanie Kohse,a
Anke Spannenberg,b Annette E. Surkus,b Tariel V. Ghochikyan,c
Ashot S. Saghyan,c Stefan Lochbrunner,d Oliver Kꢀhn,d Ralf Ludwig,a,b
and Peter Langera,b,*
a
Universitꢁt Rostock, Institut fꢀr Chemie, A.-Einstein-Str. 3a, 18059 Rostock, Germany
E-mail: peter.langer@uni-rostock.de
Leibniz-Institut fꢀr Katalyse e.V. an der Universitꢁt Rostock, A.-Einstein-Str. 29a, 18059 Rostock, Germany
Faculty of Chemistry, Yerevan State University, Alex Manoogian 1, 0025 Yerevan, Armenia
Universitꢁt Rostock, Institut fꢀr Physik, Universitꢁtsplatz 3, 18055 Rostock, Germany
b
c
d
Received: February 13, 2014; Published online: && &&, 0000
Dedicated to Professor Armin de Meijere on the occasion of his 75th birthday.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400164.
Abstract: Pentaarylpyridines were conveniently pre- in detail by means of DFT calculations and by opti-
pared in one step by pentafold Suzuki–Miyaura reac- cal spectroscopy.
tions of pentachloropyridine. Moreover, site selective
reactions were performed, leading to various substi- Keywords: cross-coupling; palladium; pyridines; site
tuted arylpyridines. Pentaarylpyridines were studied selectivity; Suzuki–Miyaura reaction
Introduction
erocycles have gained increasing interest.[9] The differ-
ent distribution of the electron density of heterocycles
Pyridines are among the most widely studied six- allows the facile introduction of various substituents
membered heterocycles possessing an important role by palladium-catalyzed cross-coupling reactions with
as lead compounds in various natural products,[1,2] high selectivity.
pharmaceuticals[3] and functional materials, such as
building blocks used in supramolecular chemistry[4] or
ligands in transition metal catalysis.[5] As a result, the Results and Discussion
synthesis of functionalized pyridines, in particular
highly substituted derivatives, has attracted much at- Recently, we reported the pentafold Sonogashira re-
tention and a number of efficient and mild strategies action of commercially available pentachloropyridine
for their synthesis have been developed. Examples in- (1);[10] Reissig and co-workers recently reported that
clude simple condensation reactions of carbonyl com- the pentafold Suzuki–Miyaura reaction of pentachlor-
pounds,[6] thermal or metal-promoted cycloadditions[7] opyridine is a difficult task, due to increasing steric
and new efficient multicomponent reactions, such as hindrance in the course of the reaction and due to the
addition reactions with carbon-carbon multiple considerably higher electron density of position 3 as
bonds.[8] Unfortunately, several of these methodolo- compared to position 2.[11a] Very recently, Schmitt and
gies are often incompatible with various functional co-workers reported an approach to pentaarylated
groups or general substitution patterns, allowing only pyridines based on Pd-catalyzed coupling reactions of
for the construction of constricted substitutions 2-chloro-3-hydroyxpyridine.[11b] Despite the elegance
around the pyridine core. Palladium-catalyzed cross- and utility of this work, many synthetic steps were re-
coupling reactions may circumvent these drawbacks quired. In fact, a site selective pentafold arylation by
by successive introduction of the desired substituents cross-coupling reactions of pentachloropyridine (1) or
on the pyridine core. During the last years, site selec- of another pentahalogenated pyridine derivative has,
tive cross-coupling reactions of polyhalogenated het- to the best of our knowledge, not been reported so
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Table 1. Optimization of the synthesis of 3a.
Entry PhB(OH)2 (equiv.) Solvent
Temp. [8C] Catalyst (mol%)
Base (equiv.) GC Yield[a] [%]
1
2
3
4
5
6
7
8
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0
7.5
6.0
7.5
6.0
6.0
6.0
6.0
10.0
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
DMF
DMF
DMF
1,4-dioxane 100
1,4-dioxane 100
1,4 dioxane 100
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
100
100
100
100
100
100
100
100
100
100
100
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
G
KF (6)
52
9
2
30
7
5
72
11
2
4
25
1
KF (6)
KF (6)
KF (6)
KF (6)
K3PO4 (6)
Cs2CO3 (6)
KF (6)
K3PO4 (6)
Cs2CO3 (6)
KF (6)
K3PO4 (6)
Cs2CO3 (6)
K3PO4 (6)
K3PO4 (9)
K3PO4 (6)
K3PO4 (7.5)
K3PO4 (7.5)
K3PO4 (7.5)
K3PO4 (7.5)
K3PO4 (7.5)
K3PO4 (7.5)
K3PO4 (10)
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
4
100
100
100
100
100
110
110
110
110
100
PdCl
Pd
85
46
46
90
97b
36
33
23
17
99[b]
PdCl
PdCl
PdCl
PdCl
PdCl
PdCl
PdCl
PdCl
[a]
[b]
Hexadecane as internal GC standard was used.
Isolated yield.
observed that higher yields of several products were
obtained when 10.0 equiv. instead of 7.5 equiv. of bor-
onic acid were employed. Thus, all reactions were per-
formed in toluene at 1008C using 1.0 equiv. of penta-
chloropyridine, 10.0 equiv. of boronic acid 2,
10.0 equiv. of K3PO4, 5.0 mol% of PdCl
and 10.0 mol% of SPhos.
The reaction of 1 with various boronic acids 2,
using our optimized conditions, afforded the corre-
sponding pentaarylpyridines 3a–m in 42–99% yield
(Scheme 2, Table 2); Products containing electron-do-
2ACHTUNGTERN(NUNG CH3CN)2
Scheme 1. Optimization of the synthesis of 3a: i,
1 (1.0 equiv.), 2, “Pd” catalyst precursor, ligand, base, sol-
vent, 20 h.
far. Therefore, as a starting point of our studies, we nating as well as electron-withdrawing aryl groups
developed a general catalytic system for the pentafold could be prepared in high to quantitative yields. How-
Suzuki–Miyaura coupling of 1 with phenylboronic ever, the reaction with boronic acids bearing a para-
acid 2a (Scheme 1);
vinyl, para-fluorine or meta-substituent led to a signifi-
During the optimization (Table 1), the employment cant decrease of the yield. This might be explained by
of SPhos, a biarylphosphine ligand developed by side-reactions (in case of the vinyl group), electronic
Buchwald et al.,[12] proved to be the most efficient reasons in the case of fluorine and steric reasons in
ligand and allowed preparation of the desired product the case of meta-substituents.
3a in 52% yield. In contrast, other bulky phosphine li-
The structure of product 3b was independently con-
gands, such as XPhos,[13] cyclohexyl JohnPhos[14] or firmed by X-ray crystal structure analysis (Figure 1);
CataCXium A,[15] led to low yields. Nevertheless, The aryl groups attached to the pyridine moiety are
using SPhos, the yield could be enhanced from 52% twisted out of plane and oriented in a propeller-type
to up to 85% when KF and Pd
by K3PO4 and PdCl2A
(CH3CN)2, respectively. Finally, sition [C-4 C-3 C-20 C-25=À62.8(3)8] is more
in the presence of 7.5 equiv, of phenylboronic acid twisted out of plane than the aryl moieties located in
ACHTUNGRTEN(NUNG OAc)2 were replaced structure. The aryl substituent located in the para-po-
À
À
À
CTHUNGTRENNUNG
À
À
À
(2a) and K3PO4, an excellent yield of 97% could be ortho or meta positions [N-1 C-1 C-6 C-7=
achieved. During our studies related to the scope, we À48.3(3), N-1 C-5 C-34 C-39=À40.8(3), C-1 C-2
À
À
À
À
À
2
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Site Selective Synthesis of Pentaarylpyridines
Scheme 2. Synthesis of 3a–m: i,
1
(1.0 equiv.), 2a–m
(10.0 equiv.),
PdCl
(CH3CN)2
(5.0 mol%),
SPhos
(10.0 mol%), K3PO4 (10.0 equiv.), toluene, 1008C, 20 h.
Table 2. Synthesis of 3a–m.
Entry
R
3 [%][a]
a
b
c
d
e
f
g
h
i
C6H5
4-MeC6H4
4-EtC6H4
4-t-BuC6H4
4-(MeO)C6H4
4-PhC6H4
4-(vinyl)C6H4
4-FC6H4
4-(CF3)C6H4
4-(CF3O)C6H4
3-(MeO)C6H4
3-(NO2)C6H4
2-thienyl
99
93
71
89
99
81
42
46
99
89
60
57
79
Figure 1. ORTEP plot of 3b. Displacement ellipsoids are
drawn at the 30% probability level.
j
k
l
rylpyridines in moderate to good yield (Scheme 3,
Table 4); The moderate yields of some products can
be explained by difficulties in their separation from
monoarylated side-product. All reactions took place
selectively at positions 2 and 6 of the pyridine moiety.
m
[a]
Yields of isolated products.
À
À
À
À
C1-3 C-14=À56.9(3) and C-5 C-4 C-27 C-32= In contrast, an arylation of positions 3 or 4 was not
À58.2(3)8]. As a consequence, a conjugation of the p observed.
orbitals between the pyridine core and the phenyl
The synthesized 3,4,5-trichloro-2,6-diarylpyridines
moieties might be unlikely affecting the photophysical were easily converted to the corresponding pentaaryl-
properties notably (vide infra); pyridines 5a–g, containing two different aryl moieties
With our new procedure in hand, we envisioned in good to excellent yields (Scheme 4, Table 5);
that 1 might also be an ideal substrate for site selec- In the following studies, we attempted the selective
tive arylation of pyridine by palladium-catalyzed synthesis of tetraarylated pyridines using 4.5 equiv. of
Suzuki–Miyaura reactions. We already reported the the appropriate boronic acid. However, in all cases
synthesis of 3,4,5-trichloro-2,6-diarylpyridines 4.[16] we isolated inseparable mixtures of the expected 3-
After a more thorough optimization (Table 3) we chloro-2,4,5,6-tetraarylpyridine 6 and of regioisomeric
were able to synthesize various 3,4,5-trichloro-2,6-dia- 4-chloro-2,3,5,6-tetraarylpyridine 7 in ratios of 4:1 up
Table 3. Optimization of the synthesis of 4a.
Entry Catalyst (mol%)
Base (equiv.) Equiv. PhB(OH)2 Temp. [8C] Solvent
4a [%][a]
1
2
3
4
5
6
7
8
9
10
Pd
Pd
PdCl
PdCl
Pd
Pd
Pd
Pd
Pd
Pd
N
K3PO4 (3.0)
K3PO4 (3.0)
K3PO4 (3.0)
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
3.0
100
60
60
60
100
80
100
80
80
toluene
toluene
toluene
toluene
1,4-dioxane 47
CH3CN
DMF
CH3CN
CH3CN
CH3CN
55
<1
30
(CH3CN)2 (5), P(Cy)3 (10)
E
(CH3CN)2 (5), CatCXium A (10) K3PO4 (3.0)
13
K3PO4 (3.0)
K3PO4 (3.0)
K3PO4 (3.0)
KF (3.0)
Cs2CO3 (3.0)
K3PO4 (3.5)
59
54
24
<1
46
80
[a]
Yields of isolated product.
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to 5:1 (see also the Supporting Information)
(Scheme 5);
We considered that the gradual introduction of aryl
substituents might influence the electronic properties
of the pyridine, thus explaining the reaction pattern.
NBO analysis of non-, mono- and diarylated penta-
chloropyridines support this hypothesis (cf. the Sup-
porting Information);
In fact, substitution of one or two chlorine atoms
by aryl substituents at positions 2 and 6 leads to an in-
tense reduction of NBO charge differences on the ad-
jacent positions 3 and 5 of the pyridine, respectively.
Notably, electron-donating or electron-withdrawing
groups have virtually no impact on the NBO charges
(cf. the Supporting Information);
Therefore, we synthesized 2,3,5,6-tetrachloro-4-(4-
methoxyphenyl)pyridine (8a) and 2,3,5,6-tetrachloro-
4-[4-(trifluoromethyl)phenyl]pyridine (8b) by aromat-
ic substitution[17] to circumvent the problems regard-
ing the site selective synthesis of tetraarylated pyri-
dines. Starting from these substrates, we were able to
achieve a site selective synthesis of various pentaary-
lated pyridines containing two or three different aryl
substituents in a two-step procedure. In general, tri-
arylated products 9, substituted by R1 =CF3, gave
lower yields than the corresponding methoxy-substi-
tuted derivatives, due to purification problems during
the column chromatography. The conditions were
again thoroughly optimized (Table 6); The second
step proceeded without any influence of the substitu-
ents located at position 4 and the desired pentaarylat-
ed products were isolated in up to quantitative yields
in the last step (Scheme 6, Table 7);
Scheme 3. Synthesis of 4a–h: i, 1 (1.0 equiv.), 2 (3.0 equiv.)
Pd(PPh3)4 (5.0 mol%), K3PO4 (3.5 equiv.) CH3CN, 808C,
20 h.
ACHTUNGTRENNUNG
Table 4. Synthesis of 4a–h.
4
R
4 [%][a]
a
b
c
d
e
f
C6H5
4-MeC6H4
4-EtC6H4
4-t-BuC6H4
4-(MeO)C6H4
3-(MeO)C6H4
3-MeC6H4
2-(MeO)C6H4
56
74
42
42
59
71
38
42
g
h
[a]
Yields of isolated products
Scheme 4. Synthesis of 5a–g: i, 4 (1.0 equiv.), 2 (6.0 equiv.),
PdCl2A(CH3CN)2 (5.0 mol%), SPhos (10.0 mol%), K3PO4
CHTUNGTRENNUNG
Furthermore, starting from 8a or 8b, tetraarylated
pyridines 11a–c, containing two different aryl moiet-
ies, were successfully synthesized. However, these
products were isolated only in moderate yields, due to
the formation of lesser and higher arylated side prod-
5 [%][a] ucts. Suzuki–Miyaura reactions of 11a–c afforded pen-
(6.0 equiv.), toluene, 1008C, 20 h.
Table 5. Synthesis of 5a–g.
Entry
R1
R2
taarylpyridines 12a–e, containing three different aryl
a
b
c
d
e
f
C6H5
C6H5
C6H5
4-MeC6H4
4-EtC6H4
4-EtC6H4
4-EtC6H4
4-(MeO)C6H4
4-(CF3)C6H4
4-EtC6H4
4-(MeO)C6H4
C6H5
83
groups, in good to excellent yields (Scheme 7,
79
Table 8);
67
Finally, we studied the complete arylation of 8a and
8b. Application of the reaction conditions optimized
for the synthesis of 3 gave the desired pentaarylpyri-
dines 13a–l in good yields (Scheme 8, Table 9);
85
92
96
92
4-(CF3)C6H4
3-(MeO)C6H4
g
[a]
Yields of isolated products.
Scheme 5. Synthesis of 6 and 7 (regioisomeric mixtures); i: 1 (1.0 equiv.), 2 (4.5 equiv.), PdCl
(10.0 mol%), K3PO4 (6.5 equiv.), toluene, 1008C, 20 h.
2ACHTUGNTRENN(GNU CH3CN)2 (5.0 mol%), SPhos
4
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Site Selective Synthesis of Pentaarylpyridines
Table 6. Optimization of the synthesis of 9d.
Entry
Catalyst (mol%)
Pd(PPh3)4
Base (equiv.)
Equiv. PhB(OH)2
Temp. [8C]
9d[a] [%]
1
2
3
4
N
K3PO4 (3.0)
K3PO4 (3.0)
K3PO4 (3,0)
K3PO4 (3.0)
3.0
2.5
2.4
2.5
100
20
100
100
71
<1
31
53
PdCl
PdCl
PdCl
2A
2A(CH3CN)2 (5), SPhos (10)
2A(CH3CN)2 (5), P(Cy)3 (10)
G
CHTUNGTRENNUNG
[a]
Yield of isolated product.
Scheme 6. Synthesis of 10a–h: i, 8 (1.0 equiv.), 2 (2.5 equiv.), PdACHTUGNTRENNNUG
ii, 9 (1.0 equiv.), 2 (4.0 equiv.), PdCl
2ACHTUNGTRENNUNG
The UV/Vis and fluorescence spectroscopic data of
pentaarylpyridines 3a, 3e and 3i measured in DCM
are summarized in Table 10. The absorption wave-
Table 7. Synthesis of 10a–h.
lengths of 3 are in the UV region of l1–4abs =227–
10 R1
R2
R3
9 [%][a] 10 [%][a] 316 nm and exhibit four conspicuous transitions
a
b
c
d
e
f
OMe C6H5
OMe C6H5
OMe 4-(MeO)C6H4 4-(CF3)C6H4 69
4-tBuC6H4
4-MeC6H4
71
71
85
84
79
91
99
82
73
74
Table 8. Synthesis of 12a–e.
11 12 R1
R2
R3
11 [%][a] 12 [%][a]
OMe 4-(MeO)C6H4 C6H5
69
63
OMe 4-FC6H4
CF3 C6H5
CF3 C6H5
CF3 C6H5
4-MeC6H4
4-(MeO)C6H4 47
4-PhC6H4
4-(CF3)C6H4 47
a
b
c
c
c
a
b
c
d
e
OMe C6H5
OMe 4-MeC6H4 4-(CF3)C6H4 34
CF3 C6H5
CF3 C6H5
CF3 C6H5
4-iPrC6H4
54
98
93
77
78
89
g
h
47
4-(MeO)C6H4 43
4-PhC6H4 43
4-(CF3)C6H4 43
[a]
Yields of isolated products.
[a]
Yields of isolated products.
Scheme 7. Synthesis of 10a–h: i, 8 (1.0 equiv.), 2 (3.0 equiv.), PdCl2ACHTUNGTRENNUNG
(3.0 equiv.), toluene, 1008C, 20 h; ii, 11 (1.0 equiv.), 2 (2.5 equiv.), PdCl
(2.5 equiv.), toluene, 1008C, 20 h.
(CH3CN)2 (5 mol%), SPhos (10 mol%), K3PO4
CHTUNGTRENNUNG
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Scheme 8. Synthesis of 13a–l: i, 8 (1.0 equiv.), 2 (8.0 equiv.),
PdCl2A(CH3CN)2 (5 mol%), SPhos (10 mol%), K3PO4
CHTUNGTRENNUNG
(8.0 equiv.), toluene, 1008C, 20 h.
Table 9. Synthesis of 13a–l.
Figure 2. Normalized absorption and emission spectra of 3a,
3e and 3i measured in CH2Cl2.
13
R1
R2
13 [%][a]
a
b
c
d
e
f
g
h
i
OMe
OMe
OMe
OMe
OMe
OMe
OMe
CF3
CF3
CF3
CF3
CF3
C6H5
66
62
93
78
61
81
79
68
56
68
59
69
4-t-BuC6H4
4-(i-PrO)C6H4
4-FC6H4
4-MeC6H4
4-(CF3)C6H4
4-(EtO)C6H4
C6H5
4-MeC6H4
4-(MeO)C6H4
4-(PhO)C6H4
3-(MeO)C6H4
stituted derivative 3a (labs2–4); In contrast, compound
3i, bearing electron-withdrawing trifluoromethyl
groups, caused no significant shift of the transitions.
Furthermore, the position of the high-energy band lo-
cated at 227–228 nm is to some extent independent of
the substitution pattern and can be assigned to local
p-p* transitions involving the arylpyridine core.[18]
However, the lower energy transitions strongly
depend on the presence of the substituent attached to
the arylpyridine moiety. The emission spectra of 3 are
displayed in Figure 2, also showing the same trend as
observed for the absorption spectra. The fluorescence
quantum yields, determined using naphthalene as ref-
erence,[19] show an emission efficiency for compound
3e slightly higher than that of derivatives 3a and 3i.
Anyhow, the obtained quantum yields in the range of
ffluo =0.01–0.04 are rather low indicating a weak fluo-
rescence response (Table 10);
j
k
l
[a]
Yields of isolated products.
Table 10. Absorption and emission spectroscopic data of 3a,
3e and 3i (CH2Cl2, c=1·10À5 mol/L);
3a
3e
3i
l1abs [nm]
227
228
227
In order to clarify the differences observed in the
absorption spectra of 3, time-dependent density func-
tional theory (TD-DFT) calculations have been per-
formed using the B3LYP functional with a TVZP
basis set and PCM solvation model as implemented in
the Gaussian 09 program package.[20] Focusing on the
red part of the spectrum (280–320 nm) the calcula-
tions are in good agreement with the experiment. The
influence of the substitution pattern of 3 can be clear-
ly seen by comparison of the HOMO–LUMO and
HOMO–LUMO+1 energy gaps (Figure 3); In the
case of compound 3e, these gaps are decreased by
about 0.3 eV relative to those of 3a and 3i which the-
oretically explains the red-shift. Inspecting the molec-
ular orbitals, one might argue that the participation of
log e l1abs
l2abs [nm]
log e l2abs
l3abs [nm]
4.56
246
4.59
276
4.52
300
4.29
369 (1)
4.56
270
4.57
294
4.55
316
4.37
387 (4)
4.40
245
4.34
272
4.18
298
4.14
369 (2)
log e l3abs
l4abs(sh) [nm]
log e l4abs(sh)
l5,em [nm] (ffluo, %)[a]
[a]
Fluorescence quantum yield was determined using naph-
thalene as a reference (ffluo =0.23).[15] Corrections due to
molecular absorption and refractive index of DCM, used
for the measurement, were incorporated in the calcula-
tions.
(l1–4abs) (Figure 2); The absorption maxima of com- the methoxy groups results in an increased delocaliza-
pound 3e, bearing electron-donating methoxy sub- tion of the HOMO (Figure 3); The visualization of
stituents, are red-shifted, which indicates a more pro- the difference densities for the discussed transitions
nounced p-electron delocalization relative to unsub- supports this view (Figure 4); During the excitation
6
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Site Selective Synthesis of Pentaarylpyridines
Figure 3. HOMO–LUMO and HOMO–LUMO+1 energy gaps derived from molecular orbital energies for compounds 3a,
3e and 3i (from left to right);
Figure 4. Difference densities for HOMO–LUMO (bottom)
and HOMO–LUMO+1 (top) transitions for 3a, 3e and 3i
(dark gray=negative, i.e., density reduced upon excitation);
Figure 5. Reductive DPVs of 1, 3a, 3e and 3i in DMF
(0.1 molL<M->1 TBAPF6); working electrode: platinum; [Fc/
Fc+]=0.6 V.
the electron density is shifted from the outer sphere
to the inner pyridine core. This effect is much more
pronounced for compound 3e than for 3a and 3i.
DPV measurements were carried out to determine contrast, parent pentaphenylpyridine (3a) and tri-
the electrochemical activity and the potential values fluoromethyl-substituted pentaarylpyridine 3i are
of pentaaryl-substituted pyridines 3a, 3e and 3i. The anodically shifted, possessing potentials for the first
influence of the substitution pattern on the reduction reduction at À2.08 V and À1.82 V, respectively. Due
potential is shown in Figure 5. In the case of com- to the shift of 3i, two additional conspicuous poten-
pound 3e, the first reduction appears at À2.28 V. In
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Sebastian Reimann et al.
tet, m=multiplet. The spectra were measured with a stan-
dard number of scans (NS=32); In case of unclear assign-
ments all possible hydrogen atoms were stated.
tials of reduction appear at À2.11 V and À2.18 V
which were not detected for 3a and 3e. Furthermore,
no oxidations could be measured for 1 and 3a during
the anodic scan. However, in the cases of 3e and 3i
oxidation peaks could be observed at 1.65 V and
0.70 V (not shown); The electronic influence of the
para-substituents of products 3 on the potential can
13C NMR spectroscopy: Bruker AV 300 (75 MHz) and
Bruker AV 400 (100 MHz); All NMR spectra presented in
this work were recorded in CDCl3 solution. All chemical
shifts are given in ppm. All coupling constants are indicated
as J. References: TMS (d=0.00 ppm) or residual CHCl3
(d=70.00 ppm) were taken as internal standard. Peak char-
acterization: d=doublet, t=triplet, q=quartet. The DEPT
method was used for determining the presence of primary,
secondary, tertiary and quaternary carbon atoms. All spectra
were measured with a standard number of scans (NS=256);
In case of unclear assignments all possible carbon atoms
were stated. In some cases the number of scans was in-
creased to 2000–8000 scans in order to detect carbon-fluo-
rine couplings.
be estimated using Hammett substituent constants
[17]
spara
.
In comparison to unsubstituted 3a, the reduc-
tion peaks of 3e and 3i are consistent with the posi-
tion of the Hammett constants [MeO (À0.268)>H
(0)>CF3 (0.54)]. As a result, the reductions of pen-
taaryl-substituted pyridines bearing electron-donating
substituents are cathodically shifted whereas electron-
withdrawing substituents lead to an anodic shift.
19F NMR spectroscopy: Bruker AV 300 (282 MHz); Spec-
tra were measured with a standard number of scans (NS=
128);
Conclusions
Mass spectrometry (MS): Finnigan MAT 95 XP (electron
ionization EI, 70 eV); 6890 N/5973 (Agilent), 6210 Time-of-
Flight LC/MS (Agilent); Gas Chromatography MS
(GCMS): Agilent HP-5890 with an Agilent HP-5973 Mass
Selective Detector (EI) and HP-5 capillary column using
helium carrier gas. Only the measurements with an average
deviation from the theoretical mass of Æ2 mDa were ac-
counted as correct. High resolution MS [HR-MS (ESI)]:
Agilent 1969 A TOF. Only the measurements with an aver-
age deviation from the theoretical mass of Æ2 mDa were ac-
counted as correct.
In conclusion, we have developed the first synthesis
of various substituted pentaarylpyridines by palladi-
um-catalyzed cross-coupling reactions of pentachloro-
pyridine (1); Our highly efficient catalyst system
shows a very good functional group tolerance and al-
lowed the preparation of the desired pentaarylated
products in nearly quantitative yield in one step.
Moreover, we developed site selective arylations
using the Suzuki–Miyaura reaction. This protocol fa-
cilitates an easy access to a variety of substituted aryl-
pyridines starting from easily available starting mate-
rials. DFT calculations were performed to verify the
experimental results. Currently, further investigations
on the arylation of other polychlorinated aryl com-
pounds are underway in our laboratories.
Infrared spectroscopy (IR): Nicolet 550 FT-IR spectrome-
ter with ATR sampling technique for solids as well as liq-
uids. Signal characterization: w=weak, m=medium, s=
strong.
UV/Vis spectroscopy (UV/Vis): Lambda 5 (PerkinElmer);
Compounds were measured with solution concentrations of
1·10À5 mol·lÀ1 in DCM. Parameters selected: Interval=
0.20 nm; Slit=2.00 nm; Scan Speed=240 nmminÀ1.
Fluorescence spectroscopy: Hitachi F-4010. Compounds
were measured with solution concentrations of 1·10À5
mol·lÀ1 in DCM. Optimal excitation wavelengths of 275 nm
were chosen to be appropriate. A solution of naphthalene in
cyclohexane was applied as a standard for the measurement
of the fluorescence quantum yields (ffluo =0.23) (measuring
inaccuracy= Æ0.01); Accordingly, corrections due to molec-
ular absorption and refractive index of DCM used for the
measurement were incorporated in the calculation.
X-ray crystallography: Data were collected on a Bruker
Kappa APEX II Duo diffractometer. The structure was
solved by direct methods and refined by full-matrix least-
squares procedures on F2 with the SHELXTL software
package (G. M. Sheldrick, Acta Crystallogr. 2008, A64,
112.); XP (Bruker AXS) was used for graphical representa-
tion. CCDC 961487 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
Experimental Section
General
All reactions were carried out in oven-dried pressure tubes
under an argon atmosphere (Argon 4.6) in order to simulta-
neously exclude oxygen and water (Schlenk techniques were
applied); Solvents for reactions were dried and distilled by
standard methods or purchased in extra dry quality from
Sigma Aldrich. Solvents for liquid chromatography and ex-
traction were always distilled prior to use (n-heptane, n-
hexane, EtOAc, DCM); All chemicals employed, including
halogenated pyridines, ligands, boronic acids and bases,
were purchased from a commercial source (Sigma Aldrich,
Alfa Aesar) and used without further purification.
1H NMR spectroscopy: Bruker AV 300 (300 MHz) and
Bruker AV 400 (400 MHz); All NMR spectra presented in
this work were recorded in CDCl3 solution. All chemical
shifts are given in ppm. All coupling constants are indicated
as J. References: TMS (d=0.00 ppm) or residual CHCl3
(d=7.26 ppm) were taken as internal standard. Peak charac-
terization: s=singlet, brs=broad singlet, d=doublet, brd=
broad doublet, t=triplet, dd=doublet of doublet, q=quar-
Elemental analysis (EA): C/H/N/S – Microanalysator
TruSpec CHNS (Leco);
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Site Selective Synthesis of Pentaarylpyridines
Melting point determination (mp): Micro-Hot-Stage Ga-
lenTM III Cambridge Instruments. The melting points have
not been corrected.
Thin layer chromatography (TLC): Merck Silica 60 F254
on aluminum tin foil from Macherey–Nagel. Detection with
UV light at 254 nm and/or 366 nm without dipping reagent.
Column chromatography: Separation on Fluka silica gel
60 (0.063–0.200 mm, 70–320 mesh); Eluents were distilled
before use.
8.3 Hz, CH), 6.79–6.85 (m, 8H, CH), 7.01 (d, 4H, 3J=
8.4 Hz, CH), 7.35 (d, 4H, 3J=8.3 Hz, CH); 13C NMR
(75 MHz, CDCl3): d=15.4, 15.5, 15.6 (CH3), 28.5, 28.5, 28.6
(CH2), 126.3, 126.8, 126.9, 130.3, 130.5, 131.3 (CH), 133.4,
135.8, 136.1, 138.7, 141.8, 141.9, 143.1, 150.5, 156.0 (C); IR
˜
(ATR): n=3024 (w), 2962 (s), 2928 (m), 1531 (m), 1501 (m),
1454 (m), 1388 (m), 1185 (m), 1116 (m), 1020 (m), 847 (s),
825 (s), 746 cmÀ1 (m); MS (EI, 70 eV): m/z (%)=599 (M+,
76), 598 (100), 582 (5), 570 (4), 535 (2), 287 (11); HR-MS
(ESI): m/z=600.36294, calcd. for C45H45N ([M+H]+):
600.36248; anal. calcd. for C45H45N (599.85): C 90.10, H 7.56,
N 2.34; found: C 89.90, H 7.55, N 2.44.
Synthesis of 3a–m
Pentakis(4-tert-butylphenyl)pyridine (3d): Colorless solid;
yield: 89%; mp 340–3428C. 1H NMR (300 MHz, CDCl3):
d=1.11 (s, 9H, CH3 t-Bu), 1.17 (s, 18H, CH3 t-Bu), 1.24 (s, 9H,
CH3 t-Bu), 6.60–6.63 (m, 2H, CH), 6.76–6.80 (m, 4H, CH),
6.84–6.88 (m, 2H, CH), 6.95–6.99 (m, 4H, CH), 7.13–7.17
(m, 4H, CH), 7.32–7.36 (m, 4H, CH); 13C NMR (75 MHz,
CDCl3): d=31.1 (CH3 t-Bu), 31.2 (CH3 t-Bu), 31.3 (CH3 t-Bu),
34.1 (C t-Bu), 34.2 (C t-Bu), 34.4 (C t-Bu), 123.4 (CH), 123.9
(CH), 124.2 (CH), 129.8 (CH), 130.0 (CH), 130.9 (CH),
133.5 (C), 135.5 (C), 135.8 (C), 148.5 (C), 148.7 (C), 149.8
An oven-dried, argon-flushed sealable glass tube was
charged with pentachloropyridine
1 (0.2 mmol), PdCl2
ACHTUNGTRENNUNG(CH3CN)2 (5 mol%), SPhos (10 mol%), the appropriate bor-
onic acid 2a–m (2.0 mmol) and K3PO4 (2.0 mmol) followed
by anhydrous toluene (9.6 mL); The tube was sealed with
a Teflon valve and stirred at 1008C for 20 h. The cooled re-
action mixture was diluted with water and extracted with
CH2Cl2. The combined organic layers were dried with
Na2SO4, filtered and concentrated in vacuum. The residue
was purified by column chromatography.
Pentaphenylpyridine (3a): Colorless solid; yield: 99%; mp
248–2508C. 1H NMR (300 MHz, CDCl3): d=6.76–6.80 (m,
2H, CH), 6.89–6.92 (m, 7H, CH), 6.94–7.01 (m, 6H, CH),
7.16–7.20 (m, 6H, CH), 7.40–7.42 (m, 4H, CH); 13C NMR
(75 MHz, CDCl3): d=126.2 (CH), 126.2 (CH), 126.9 (CH),
127.3 (CH), 127.3 (CH), 127.5 (CH), 130.2 (CH), 130.4
(CH), 131.3 (CH) 133.7 (C), 138.1 (C), 138.4 (C), 140.8 (C),
˜
(C), 149.8 (C), 149.8 (C), 155.8 (C); IR (ATR): n=3053 (w),
2961 (s), 2902 (m), 2865 (m), 1610 (m), 1568 (w), 1531 (w),
1497 (m), 1460 (m), 1388 (m), 1361 (m), 1270 (m), 1201 (m),
1137 (m), 1107 (m), 1017 (m), 1002 (w), 970 (w), 922 (w),
851 (s), 832 (s), 815 (s), 779 (m), 758 (w), 736 (w), 675 (m),
638 (m), 626 (m), 597 (w), 580 (m), 547 (m), 481 (w), 445
(w), 445 (w), 407 (w), 386 cmÀ1 (w); MS (EI, 70 eV): m/z
(%)=740 (M+, 42), 739 (100), 738 (97), 737 (13), 736 (8),
725 (4), 722 (9), 708 (3), 707 (2), 706 (3), 682 (5), 668 (3),
666 (5), 652 (4), 650 (3), 626 (4), 540 (3), 414 (3), 391 (2),
366 (2), 362 (3), 355 (10), 352 (5), 341 (4), 338 (5), 281 (4),
206 (6), 57 (15), 44 (31), 43 (6); HR-MS (ESI): m/z=
740.51898, calcd. for C55H66N ([M+H]+): 740.51834; anal.
calcd. for C55H65N (740.11): C 89.26, H 8.85, N 1.89; found:
C 89.61, H 8.488, N 1.647.
˜
150.2 (C), 156.4 (C); IR (ATR): n=3101 (w), 3081 (w), 3054
(w), 3024 (w), 1599 (w), 1577 (w), 1486 (m), 1441 (m), 1393
(m), 1280 (w), 1131 (w), 1075 (m), 1024 (m), 1005 (w), 919
(m), 827 (w), 802 (m), 773 (m), 759 (m), 728 (m), 695 (s),
652 (m), 619 (m), 551 (m), 542 (m), 400 cmÀ1 (w); MS (EI,
70 eV): m/z (%)=460 (M+, 17), 459 (61), 458 (100), 456 (1),
380 (4), 379 (2), 378 (6), 377 (2), 352 (2), 350 (2), 302 (2),
276 (4), 230 (2), 222 (4), 220 (8), 214 (8), 201 (4), 183 (3),
178 (3), 77 (2); HR-MS (ESI): m/z=460.20598, calcd. for
C29H22N ([M+H]+): 460.20598; anal. calcd. for C35H25N
(459.58): C 91.47, H 5.48, N 3.05; found: C 91.46, H 5.548, N
2.968.
2,3,4,5,6-Pentakis(4-methoxyphenyl)pyridine (3e): Slightly
yellow solid; yield: 124 mg (99%); mp 2408C. 1H NMR
(300 MHz, CDCl3): d=3.66 (s, 3H, OCH3), 3.70, 3.74 (s,
3
3
6H, OCH3), 6.49 (d, 2H, J=8.9 Hz, CH), 6.58 (d, 4H, J=
3
3
8.9 Hz, CH), 6.66 (d, 2H, J=8.7 Hz, CH), 6.72 (d, 4H, J=
2,3,4,5,6-PentakisACHTUNGTRENNUNG(4-tolyl)pyridine (3b): Colorless solid;
3
3
1
8.8 Hz, CH), 6.80 (d, 4H, J=8.7 Hz, CH), 7.36 (d, 4H, J=
8.9 Hz, CH); 13C NMR (75 MHz, CDCl3): d=54.9, 54.9, 55.1
(OCH3), 112.5, 112.9, 112.9 (CH), 130.8, 131.2 (C), 131.4,
131.5, 132.3 (CH), 132.7, 133.8, 150.2, 155.7, 157.4, 157.6,
yield: 99%; mp 2538C. H NMR (300 MHz, CDCl3): d=2.15
(s, 3H, CH3), 2.20 (s, 6H, CH3), 2.28 (s, 6H, CH3), 6.63 (d,
3
2H, J=8.3 Hz, CH), 6.72–6.83 (m, 10H, CH), 6.98 (d, 4H,
3J=7.9 Hz, CH), 7.30 (d, 4H, 3J=7.9 Hz, CH); 13C NMR
(75 MHz, CDCl3): d=21.1, 21.2, 21.2 (CH3), 127.6, 128.1,
128.1, 130.1, 130.3, 131.1 (CH), 133.4, 135.3, 135.3, 135.4,
˜
158.7 (C); IR (ATR): n=2960 (w), 2935 (w), 2836 (w), 1607
(m), 1514 (m), 1388 (m), 1286 (m), 1242 (s), 1030 (s), 830
(s), 542 cmÀ1 (m); MS (EI, 70 eV): m/z (%)=609 (M+, 100),
564 (4), 550 (2), 262 (2), 238 (3), 223 (8), 195 (4); HR-MS
(ESI): m/z=610.25978, calcd. for C40H35NO5 ([M+H]+):
610.2588.
Penta(biphenyl-4-yl)pyridine (3f): Slightly yellow solid;
yield: 81%; mp 341–3438C. 1H NMR (400 MHz, CDCl3):
d=6.81–6.86 (m, 2H, CH), 6.98–6.99 (m, 3H, CH), 7.18–
7.51 (m, 40H, CH); 13C NMR (100 MHz, CDCl3): d=125.7
(CH), 126.1 (CH), 126.3 (CH), 126.7 (CH), 126.8 (CH),
127.6 (CH), 127.2 (CH), 127.2 (CH), 128.3 (CH), 128.6
(CH), 128.6 (CH), 128.6 (CH), 130.7 (CH), 130.9 (CH),
131.7 (CH), 133.5 (C), 137.0 (C), 137.3 (C), 138.7 (C), 138.8
(C), 139.4 (C), 140.1 (C), 140.3 (C), 140.3 (C), 140.6 (C),
˜
135.6, 136.8, 156.0 (C); IR (ATR): n=3025 (w), 2918 (w),
2863 (w), 1531 (w), 1501 (w), 1387 (m), 1183 (w), 1112 (w),
1021 (w), 913 (w), 813 (s), 735 (s), 652 (w), 554 (m), 526 (s),
491 cmÀ1 (m); MS (EI, 70 eV): m/z (%)=528 (M+, 100), 420
(2), 406 (2), 265 (2), 235 (3), 226 (3); HR-MS (ESI): m/z=
530.28469, calcd. for C40H36N ([M+H]+): 530.28423; anal.
calcd. for C40H35N (529.71): C 90.70, H 6.66; found: C 90.82,
H 7.024.
2,3,4,5,6-Pentakis(4-ethylphenyl)pyridine (3c): Colorless
1
solid; yield: 71%; mp 1668C. H NMR (300 MHz, CDCl3):
d=1.06 (t, 3H, 3J=7.6 Hz, CH3), 1.12 (t, 6H, 3J=7.6 Hz,
3
3
CH3), 1.20 (t, 6H, J=7.6 Hz, CH3), 2.44 (q, 2H, J=7.6 Hz,
CH2), 2.50 (q, 4H, 3J=7.6 Hz, CH2), 2.60 (q, 4H, 3J=
7.6 Hz, CH2), 6.65 (d, 2H, J=8.3 Hz, CH), 6.74 (d, 2H, J=
3
3
˜
155.1 (C), 156.0 (C); IR (ATR): n=3401 (w), 3055 (w), 3027
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(m), 1597 (m), 1524 (m), 1484 (m), 1382 (m), 1261 (w), 1177
(m), 1113 (m), 1075 (m), 1006 (m), 825 (m), 764 (m), 745
(m), 732 (m), 693 (s), 572 (m), 496 (m), 458 (w), 404 cmÀ1
(m); MS (EI, 70 eV): m/z (%)=840 (M+, 6), 839 (12), 838
(10), 432 (3), 308 (9), 276 (15), 250 (28), 225 (17), 212 (14),
211 (100), 209 (41), 208 (9), 207 (24), 196 (9), 195 (4), 194
(3), 183 (11), 182 (56), 181 (30), 180 (5), 166 (7), 165 (6), 153
(17), 152 (39), 151 (12), 150 (9), 139 (19), 138 (15), 119 (11),
98 (12), 97 (6), 91 (13), 69 (14), 66 (15), 65 (10), 55 (10), 44
(37), 43 (16), 41 (14), 39 (12); HR-MS (ESI): m/z=
840.3637, calcd. for C65H46N ([M+H]+): 840.3625; anal.
calcd. for C65H45N (840.06): C 92.93, H 5.40, N 1.67; found:
C 92.83, H 5.555, N 1.484.
813 (s), 756 (m), 727 (w), 680 (m), 648 (m), 618 (m), 552
(m), 525 (s), 502 (m), 467 (w), 387 cmÀ1 (w); MS (EI,
70 eV): m/z (%)=550 (M+, 17), 549 (68), 548 (100), 452 (6),
450 (3), 432 (2), 431 (2), 411 (1), 332 (2), 330 (4), 312 (1),
254 (2), 253 (2), 247 (5), 244 (3), 243 (3), 234 (4), 215 (2),
214 (7), 213 (2), 212 (3), 207 (2), 194 (3), 193 (2), 188 (2),
168 (1), 32 (1); HR-MS (ESI): m/z=550.15851, calcd. for
C35H21F5N ([M+H]+): 550.15887.
2,3,4,5,6-Pentakis[4-(trifluormethyl)phenyl]pyridine (3i):
1
Colorless solid; yield: 77%; mp 2828C. H NMR (300 MHz,
3
3
CDCl3): d=6.89 (d, 4H, J=7.9 Hz, CH), 7.02 (d, 2H, J=
3
3
8.0 Hz, CH), 7.28 (d, 2H, J=8.3 Hz, CH), 7.35 (d, 4H, J=
8.3 Hz, CH), 7.45–7.52 (m, 8H, CH); 13C NMR (75 MHz,
1
1
Pentakis(4-vinylphenyl)pyridine (3g): Colorless solid;
CDCl3): d=123.6 (q, J=272 Hz, CF3), 123.7 (q, J=272 Hz,
yield: 42%; mp 376–3788C. 1H NMR (400 MHz, CDCl3):
CF3), 124.0 (q, 1J=124.0 CF3), 124.7 (q, 4J=3.7 Hz, CH),
3
2
4
4
d=5.12 (dd, JH,H,cis =10.9 Hz, JH,H,gem =1.0 Hz, 1H, CH=H-
125.0 (q J=3.7 Hz, CH), 125.1 (q, J=3.7 Hz, CH), 129.7
(q, 2J=33.4 Hz, CAr), 129.7 (q, 2J=32.9 Hz, CAr), 130.4,
130.4, 131.3 (CH), 133.0, 140.4, 140.7, 143.0 149.3, 156.0 (C);
3
2
Hcis and CH=CH-Hgem), 5.15 (dd, JH,H,cis =11.3 Hz, JH,H,gem
=
0.8 Hz, 2H, CH=CH-Hcis and CH=CH-Hgem), 5.19 (dd,
2
3JH,H,cis =10.7 Hz, JH,H,gem =1.0 Hz, 2H, CH=H-Hcis and CH=
˜
IR (ATR): n=1617 (w), 1535 (w), 1407 (w), 1320 (s), 1160
H-Hgem), 5.57 (dd, 3JH,H,trans =17.2 Hz, 2JH,H,gem =1.0 Hz, 1H,
(m), 1120 (s), 1106 (s), 1064 (s), 1017 (m), 846 (m), 829 (m),
609 cmÀ1 (w); MS (EI, 70 eV): m/z (%)=798 (M+, 100), 780
(6), 688 (4), 111 (2), 97 (2); HR-MS (ESI): m/z=800.14218,
calcd. for C40H20F15N ([M+H]+): 800.1429; anal. calcd. for
C40H20F15N (799.57): C 60.23, H 2.52, N 1.75; found: C
60.23, H 2.379, N 1.914.
3
CH=CH-Htrans and CH=CH-Hgem), 5.62 (dd, JH,H,trans
=
2
17.2 Hz, JH,H,gem =1.0 Hz, 2H, CH=CH-Htrans and CH=CH-
Hgem), 5.68 (dd, 3JH,H,trans =17.2 Hz, 2JH,H,gem =1.0 Hz, 2H,
3
CH=CH-Htrans and CH=CH-Hgem), 6.50 (dd, JH,H,trans
=
3
17.9 Hz, JH,H,cis =11.1 Hz, 1H, CH2=CHtrans and CH2=CHcis),
6.55 (dd, 3JH,H,trans =18.3 Hz, 3JH,H,cis =11.1 Hz, 2H, CH2=
CHtrans and CH2=CHcis), 6.63 (dd, 3JH,H,trans =18.3 Hz,
3JH,H,cis =11.1 Hz, 2H, CH2=CHtrans and CH2=CHcis), 6.69–
6.71 (m, 2H, CH), 6.83–6.85 (m, 4H, CH), 6.98–6.99 (m,
2H, CH), 7.05–7.07 (m, 4H, CH), 7.20–7.22 (m, 4H, CH),
7.34–7.37 (m, 4H, CH); 13C NMR (100 MHz, CDCl3): d=
113.5 (CH2), 113.5 (CH2), 113.9 (CH2), 125.1 (CH), 125.5
(CH), 125.5 (CH), 130.4 (CH), 130.6 (CH), 131.4 (CH),
133.1 (C), 135.3 (C), 135.4 (C), 136.5 (CH), 136.5 (CH),
136.6 (C), 136.6 (CH), 137.5 (C), 137.9 (C), 140.3 (C), 149.9
Pentakis[4-(trifluoromethoxy)phenyl]pyridine (3j): Color-
1
less solid; yield: 89%; mp 164–1668C. H NMR (300 MHz,
CDCl3): d=6.73–6.76 (m, 2H, CH), 6.84–6.94 (m, 10H,
CH), 7.04–7.07 (m, 4H, CH), 7.37–7.40 (m, 4H, CH);
13C NMR (75 MHz, CDCl3): d=120.3 (CH), 120.8 (CH),
120.3 (q, 1JC,F =258.6 Hz, CF3), 120.3 (q, 1JC,F =258.5 Hz,
CF3), 120.3 (q, 1JC,F =258.4 Hz, CF3), 120.4 (CH), 131.4
(CH), 131.5 (CH), 132.3 (CH), 132.7 (C), 135.8 (C), 136.1
3
3
(C), 138.3 (C), 147.9 (q, JC,F =2.2 Hz, C), 148.1 (q, JC,F
=
3
2.1 Hz, C), 148.9 (q, JC,F =2.2 Hz, C), 149.4 (C), 155.7 (C);
˜
(C), 156.0 (C); IR (ATR): n=3083 (w), 3059 (w), 3033 (w),
19F NMR (282.4 MHz, CDCl3): d=À57.5 (CF3), À57.8
2973 (w), 2851 (w), 1626 (m), 1606 (w), 1528 (m), 1498 (w),
1401 (w), 1386 (s), 1272 (m), 1247 (w), 1131 (w), 1116 (m),
1030 (w), 1015 (m), 992 (s), 953 (w), 905 (s), 830 (s), 777
(m), 732 (m), 694 (m), 667 (m), 621 (m), 545 (m), 486 (m),
393 cmÀ1 (w); MS (EI, 70 eV): m/z (%)=590 (M+, 39), 589
(91), 588 (100), 484 (3), 252 (2), 245 (2), 181 (3), 169 (3), 139
(3), 135 (3), 125 (5), 123 (4), 119 (3), 111 (7), 109 (6), 97
(11), 95 (8), 85 (8), 84 (4), 83 (11), 82 (4), 81 (9), 71 (11), 69
(16), 57 (18), 55 (13), 44 (10), 43 (11), 39 (4); HR-MS (EI,
70 eV): m/z=589.274025, calcd. for C45H35N: 589.27640;
anal. calcd. for C45H35N (589.77): C 91.64, H 5.98, N 2.37;
found: C 91.73, H 5.996, N, 2.163.
˜
(CF3), À58.0 (CF3); IR (ATR): n=1609 (w), 1533 (w), 1511
(m), 1394 (w), 1251 (s), 1203 (s), 1147 (s), 1017 (m), 1005
(m), 921 (m), 845 (m), 807 (m), 762 (w), 657 (m), 635 (m),
613 (w), 520 (m), 475 (w), 383 cmÀ1 (w); MS (EI, 70 eV): m/
z (%)=880 (M+, 20), 879 (65), 878 (100), 794 (3), 355 (2),
281 (2), 221 (2), 147 (2), 111 (2), 97 (4), 95 (3), 85 (3), 84
(2), 83 (4), 81 (3), 71 (5), 70 (3), 69 (7), 67 (2), 63 (2), 57 (8),
56 (3), 55 (5), 45 (2), 44 (5), 43 (6), 42 (2), 41 (5), 40 (2);
HR-MS (ESI): m/z=878.100825, calcd. for C40H19F15NO5:
878.10182; anal. calcd. for C40H20F15NO5 (879.57): C 54.62,
H 2.29, N 1.59; found: C 54.67, H 2.358, N 1.647.
2,3,4,5,6-Pentakis(3-methoxyphenyl)pyridin (3k): Yellow
oil; yield: 60%. 1H NMR (300 MHz, CDCl3): d=3.48 (s,
3H, OCH3), 3.50 (s, 6H, OCH3), 3.60 (s, 6H, OCH3), 6.38–
6.61 (m, 9H, CH), 6.75–6.79 (m, 2H, CH), 6.85–6.98 (m,
5H, CH), 7.06–7.15 (m, 4H, CH); 13C NMR (75 MHz,
CDCl3): d=55.1, 55.1 (OCH3), 112.8, 114.1, 114.9, 115.6,
116.3, 122.7, 123.0, 123.8, 128.0, 128.4, 128.5 (CH), 133.4,
139.2, 139.6, 141.9, 149.9, 156.0, 158.4, 158.7, 158.8 (C); IR
Pentakis(4-fluorophenyl)pyridine (3h): Colorless solid;
yield: 46%; mp 286–2888C. 1H NMR (300 MHz, CDCl3):
d=6.66–6.92 (m, 16H, CH), 7.29–7.36 (m, 4H, CH);
13C NMR (75 MHz, CDCl3): d=114.5 (d, 2JC,F =21.7 Hz,
2
2
CH), 114.7 (d, JC,F =21.1 Hz, CH), 114.9 (d, JC,F =21.9 Hz,
CH), 131.7 (d, 3JC,F =8.0 Hz, CH), 131.8 (d, 3JC,F =8.4 Hz,
3
4
CH), 132.6 (d, JC,F =7.6 Hz, CH), 132.8 (C), 133.5 (d, JC,F
=
=
4.0 Hz, CH), 133.8 (d, 4JC,F =4.0 Hz, CH), 136.3 (d, JC,F
4
1
˜
(ATR): n=2936 (w), 2832 (w), 1577 (s), 1531 (m), 1423 (m),
3.3 Hz, CH), 149.7 (C), 155.8 (C), 161.2 (d, JC,F =247.4 Hz,
1
1
1385 (m), 1284 (m), 1236 (s), 1160 (m), 1040 (s), 858 (m),
735 (s), 701 cmÀ1 (s); MS (EI, 70 eV): m/z (%)=609 (M+,
79), 608 (100), 592 (5), 578 (4), 564 (2), 536 (7), 502 (3);
HR-MS (EI, 70 eV): m/z=609.250275, calcd. for
C40H35O5N: 609.25097.
CF), 161.4 (d, JC,F =246.8 Hz, CF), 162.2 (d, JC,F =248.0 Hz,
CF); 19F NMR (282.4 MHz, CDCl3): d=À113.6 (F), À114.3
˜
(F), À114.4 (F); IR (ATR): n=3080 (w), 1596 (m), 1539
(m), 1501 (s), 1413 (m), 1389 (m), 1299 (w), 1218 (s), 1156
(s), 1125 (w), 1096 (m), 1014 (m), 960 (w), 849 (m), 831 (s),
10
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FULL PAPERS
Site Selective Synthesis of Pentaarylpyridines
Pentakis(3-nitrophenyl)pyridine (3l): Colorless solid;
yield: 57%; mp 237–2398C. 1H NMR (300 MHz, CDCl3):
d=7.25–7.46 (m, 8H, CH), 7.67–7.72 (m, 3H, CH), 7.83
(brs, 2H, CH), 7.89–7.92 (m, 1H, CH), 7.97–8.00 (m, 2H,
CH), 8.13–8.16 (m, 2H, CH); 13C NMR (75 MHz, CDCl3):
d=122.9 (CH), 123.0 (CH), 123.6 (CH), 125.1 (CH), 125.4
(CH), 125.5 (CH), 129.3 (CH), 129.4 (CH), 129.7 (CH),
129.9 (CH), 135.7 (CH), 135.7 (CH), 132.7 (C), 137.5 (C),
137.8 (C), 140.2 (C), 147.5 (C), 147.9 (C), 148.0 (C), 149.0
(w), 483 (m), 456 (w), 401 cmÀ1 (w);; MS (EI, 70 eV): m/z
(%)=335 (M+, 66), 334 (16), 333 (68), 302 (11), 301 (12),
300 (66), 299 (20), 298 (100), 263 (13), 228 (15), 227 (30),
200 (4), 160 (25), 149 (11), 114 (8), 77 (6); HR-MS (EI,
70 eV): m/z=332.98725, calcd. for C17H10Cl3N: 332.98733;
anal. calcd. for C17H10Cl3N (334.63): C 61.02, H 3.01, N 4.19;
found: C 61.35, H 3.237, N 3.889.
3,4,5-Trichloro-2,6-(para-tolyl)pyridine (4b): Colorless
solid; yield: 74%; mp 139–1418C. 1H NMR (300 MHz,
CDCl3): d=2.42 (s, 6H, CH3), 7.26–7.29 (m, 4H, CH), 7.65
(d, 4H, 3J=8.1 Hz, CH); 13C NMR (75 MHz, CDCl3): d=
21.3 (CH3), 127.7 (C), 128.8, 129.4 (CH), 135.0, 139.3, 142.8,
˜
(C), 155.7 (C); IR (ATR): n=3083 (w), 2924 (w), 2865 (w),
1521 (s), 1436 (w), 1394 (w), 1344 (s), 1276 (w), 1147 (w),
1082 (m), 1001 (w), 900 (m), 868 (m), 836 (w), 806 (m), 785
(w), 759 (w), 736 (m), 711 (m), 687 (s), 619 (w), 537 cmÀ1
(w); MS (EI, 70 eV): m/z (%)=685 (M+, 6), 684 (16), 683
(9), 667 (2), 655 (2), 654 (5), 637 (7), 591 (5), 342 (4), 281
(5), 267 (3), 220 (3), 219 (6), 208 (4), 207 (13), 193 (6), 183
(5), 181 (5), 152 (5), 151 (5), 149 (4), 143 (3), 135 (9), 131
(6), 125 (10), 123 (8), 121 (7), 119 (9), 111 (15), 109 (12), 97
(22), 95 (16), 91 (11), 85 (15), 83 (22), 81 (18), 71 (22), 70
(13), 69 (42), 67 (15), 66 (23), 65 (16), 57 (36), 55 (31), 45
(10), 44 (100), 43 (43), 41 (26), 40 (13), 39 (17); HR-MS
(ESI): m/z=685.13137, calcd. for C35H21N6O10 ([M+H]+):
685.13055.
˜
155.1 (C); IR (ATR): n=3033 (w), 2919 (m), 2854 (m), 1612
(m), 1493 (s), 1368 (s), 1300 (m), 1272 (m), 1184 (m), 1089
(m), 1019 (m), 958 (m), 880 (m), 819 (s), 776 (s), 674 cmÀ1
(s); MS (EI, 70 eV): m/z (%)=361 (M+, 100), 326 (78), 291
(9), 275 (3), 255 (8), 240 (9); HR-MS (EI, 70 eV): m/z=
361.018050, calcd for C19H14Cl3N: 361.01863; anal. calcd. for
C19H14Cl3N (362.68): C 62.92, H 3.89, N 3.86; found: C
62.97, H 3.943, N 3.705.
3,4,5-Trichloro-2,6-bis(4-ethylphenyl)pyridine (4c): Color-
less solid; yield: 42%; mp 81–838C. 1H NMR (400 MHz,
3
3
CDCl3): d=1.27 (t, JH-H=7.7 Hz, 6H, CH3), 2.71 (q, J=
3
3
2,3,4,5,6-Penta(thiophen-2-yl)pyridine (3m): Dark yellow
7.7 Hz, 4H, CH2), 7.28 (d, J=8.5 Hz, 4H, CH), 7.67 (d, J=
8.5 Hz, 4H, CH); 13C NMR (100 MHz, CDCl3): d=15.3
(CH3), 28.7 (CH2), 127.5 (CH), 127.7 (C), 129.5 (CH), 135.2
1
solid; 79%; mp 300–3028C. H NMR (300 MHz, CDCl3): d=
3
4
3
6.60 (dd, 1H, J=3.6 Hz, J=1.3 Hz, CH), 6.63 (dd, 2H, J=
3.9 Hz, 4J=1.2 Hz, CH), 6.70 (dd, 1H, 3J=5.2 Hz, 3J=
3.6 Hz, CH), 6.87–6.89 (m, 4H, CH), 6.96 (dd, 2H, 3J=
5.1 Hz, 3J=3.4 Hz, CH), 7.11 (dd, 1H, 3J=4.9 Hz, 4J=
˜
(C), 142.7 (C), 145.5 (C), 155.2 (C); IR (ATR): n=3032 (w),
2966 (m), 2919 (m), 2879 (w), 1900 (w), 1611 (m), 1492 (m),
1457 (m), 1367 (s), 1186 (m), 1099 (m), 1018 (m), 977 (w),
836 (s), 818 (s), 779 (m), 755 (m), 665 (m), 624 (m), 585 (m),
529 (m), 490 (m), 475 (m), 428 (w), 401 cmÀ1 (w); MS (EI,
70 eV): m/z (%)=391 (M+, 97), 390 (52), 389 (100), 388
(32), 378 (16), 377 (12), 376 (48), 375 (12), 374 (54), 361 (9),
360 (6), 180 (11), 179 (14), 173 (7), 144 (4), 138 (4), 120 (4),
105 (4), 77 (5); HR-MS (ESI): m/z=390.05771, calcd. for
C21H19Cl3N ([M+H]+): 390.05776.
3
4
1.2 Hz, CH), 7.33 (dd, 2H, J=5.1 Hz, J=1.2 Hz, CH), 7.35
(dd, 2H, 3J=5.1 Hz, 4J=1.2 Hz, CH); 13C NMR (75 MHz,
CDCl3): d=124.5 (C), 125.8, 126.6, 127.1, 127.3, 127.7, 128.4,
128.9, 129.2, 129.4 (CH), 137.1, 138.2, 144.3, 147.9, 151.0
˜
(C); IR (ATR): n=3097 (w), 3067 (w), 1509 (m), 1426 (m),
1381 (m), 1215 (m), 1108 (m), 1063 (m), 1037 (m), 846 (m),
755 (m), 696 cmÀ1 (s); MS (EI, 70 eV): m/z (%)=489 (M+,
100), 456 (12), 444 (4), 422 (4), 411 (3), 371 (2), 228 (3), 205
(3), 190 (5); HR-MS (ESI): m/z=489.989, calcd. for
C25H15NS5 ([M+H]+): 489.988; anal. calcd. for C25H15NS5
(489.72): C 61.31, H 3.09, N 2.86, S 32.74; found: C 60.89, H
3.127, N 2.817, S 32.93.
3,4,5-Trichloro-2,6-bis(4-tert-butylphenyl)pyridine
(4d):
Colorless solid; yield: 42%; mp 134–1368C. 1H NMR
3
(400 MHz, CDCl3): d=1.34 (s, 18H, CH3 t-Bu), 7.46 (d, J=
3
8.6 Hz, 4H, CH), 7.68 (d, J=8.6 Hz, 4H, CH); 13C NMR
(100 MHz, CDCl3): d=31.2 (CH3 t-Bu), 34.8 (C t-Bu), 125.0
(CH), 127.7 (C), 129.2 (CH), 135.0 (C), 124.8 (C), 152.3 (C),
˜
155.1 (C); IR (ATR): n=2961 (s), 2866 (m), 1610 (m), 1527
Synthesis of 3,4,5-Trichloro-2,6-diarylpyridines 4a–h
(m), 1493 (m), 1369 (s), 1267 (m), 1161 (m), 1087 (m), 1017
(m), 967 (w), 881 (w), 839 (s), 813 (s), 771 (m), 736 (w), 719
(s), 633 (m), 561 (m), 540 (s), 467 (m), 397 cmÀ1 (w); MS
(EI, 70 eV): m/z (%)=447 (M+, 30), 446 (10), 445 (30), 434
(33), 433 (26), 432 (97), 431 (26), 430 (100), 416 (6), 414 (6),
376 (4), 374 (5), 208 (10), 207 (9), 194 (5), 179 (16), 57 (17),
41 (12); HR-MS (ESI): m/z=446.12064, calcd. for
C25H27Cl3N ([M+H]+): 446.12036.
An oven-dried and argon-flushed pressure tube was charged
with pentachloropyridine
1
(1.0 equiv.), PdACTHNGUTERNNU(G PPh3)4
(5.0 mol%), the appropriate boronic acid (3.0 equiv.) and
K3PO4 (3.5 equiv.) followed by anhydrous CH3CN (3.5 mL);
The tube was sealed with a Teflon valve and the reaction
mixture was stirred at 808C for 20 h. The cooled reaction
mixture was diluted with water and extracted with DCM.
The combined organic layers were dried (Na2SO4), filtered
and the filtrate was concentrated under vacuum. The residue
was purified by column chromatography.
3,4,5-Trichloro-2,6-diphenylpyridine (4a): Colorless solid;
yield: 56%; mp 159–1618C. 1H NMR (300 MHz, CDCl3):
d=7.43–7.48 (m, 6H, CH), 7.64–7.70 (m, 4H, CH);
13C NMR (75 MHz, CDCl3): d=128.2 (CH), 128.8 (C), 129.3
(CH), 129.7 (CH), 136.3 (C), 144.1 (C), 155.0 (C); IR
3,4,5-Trichloro-2,6-(4-methoxyphenyl)pyridine (4e): Color-
1
less solid; yield: 59%; mp 195–1968C. H NMR (300 MHz,
CDCl3): d=3.84 (s, 6H, OCH3), 6.95 (d, 4H, 3J=8.9 Hz,
CH), 7.47 (d, 4H, 3J=8.9 Hz, CH); 13C NMR (75 MHz,
CDCl3): d=55.3 (OCH3), 114.1, 127.6 (CH), 129.5, 133.3,
˜
144.6, 146.3, 158.6 (C); IR (ATR): n=2957 (w), 2914 (w),
2839 (w), 1604 (m), 1498 (m), 1326 (w), 1274 (m), 1245 (m),
1039 (m), 820 (s), 681 cmÀ1 (m); MS (EI, 70 eV): m/z (%)=
393 (M+, 100), 358 (12), 343 (12), 315 (4), 308 (5), 272 (4);
HR-MS (EI, 70 eV): m/z=393.007989, calcd. for
C19H14Cl3NO2: 393.00846.
˜
(ATR): n=3026 (w), 2920 (m), 2851 (m), 1729 (m), 1600
(w), 1514 (m), 1486 (m), 1446 (m), 1355 (m), 1287 (m), 1072
(m), 816 (m), 750 (s), 686 (s), 662 (m), 631 (m), 617 (m), 542
Adv. Synth. Catal. 0000, 000, 0 – 0
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11
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Sebastian Reimann et al.
3,4,5-Trichloro-2,6-(3-methoxyphenyl)pyridine (4f): Color-
MeO), 6.47–6.56 (m, 6H, CH), 6.64–6.67 (m, 2H, CH),
6.75–6.78 (m, 4H, CH), 7.15–7.18 (m, 6H, CH), 7.36–7.39
(m, 4H, CH); 13C NMR (75 MHz, CDCl3): d=54.9 (MeO),
55.0 (MeO), 112.6 (CH), 112.9 (CH), 127.1 (CH), 127.5
(CH), 130.2 (CH), 130.6 (C), 130.8 (C), 131.6 (CH), 132.3
(CH), 133.6 (C), 141.1 (C), 150.3 (C), 156.4 (C), 157.6 (C),
1
less solid; yield: 71%; mp 122–1238C. H NMR (300 MHz,
3
CDCl3): d=3.75 (s, 6H, OCH3), 6.90 (ddd, 2H, J=8.1 Hz,
4
4
4
4J=2.6 Hz, J=1.1 Hz, CH), 7.16 (dd, 2H, J=2.4 Hz, J=
1.7 Hz, CH), 7.21 (ddd, 2H, 3J=7.7 Hz, 4J=1.5 Hz, 4J=
1.3 Hz, CH), 7.29 (dd, 2H, 3J=7.9 Hz, 3J=7.9 Hz, CH);
13C NMR (75 MHz, CDCl3): d=55.3 (CH3), 114.9, 115.0,
121.8 (CH), 128.3 (C), 129.1 (CH), 138.9, 143.0, 155.0, 159.2
˜
157.7 (C); IR (ATR): n=3000 (w), 2933 (w), 2836 (w), 1883
(w), 1606 (m), 1509 (m), 1491 (m), 1461 (m), 1443 (w), 1388
(m), 1285 (m), 1242 (s), 1175 (m), 1075 (w), 1030 (m), 917
(w), 831 (m), 796 (m), 777 (w), 750 (m), 695 (s), 658 (m),
633 (m), 559 (m), 538 (m), 410 cmÀ1 (w); MS (EI, 70 eV): m/
z (%)=550 (M+, 29), 549 (97), 548 (100), 534 (7), 490 (6),
431 (4), 259 (8), 250 (5), 239 (13), 238 (15), 235 (8), 234 (7),
229 (11), 227 (8), 222 (18), 221 (14), 214 (21), 213 (16), 208
(21), 182 (13), 181 (4), 177 (5), 157 (8); HR-MS (ESI):
˜
(C); IR (ATR): n=3060 (w), 3004 (w), 2936 (w), 2834 (w),
1596 (m), 1529 (w), 1486 (m), 1374 (m), 1310 (m), 1232 (s),
1031 (s), 774 cmÀ1 (s); MS (EI, 70 eV): m/z (%)=393 (M+,
67), 365 (28), 334 (3), 321 (3), 284 (4), 272 (4); HR-MS
(ESI): m/z=394.01641, calcd. for C19H15Cl3NO2 ([M+H]+):
394.01629.
3,4,5-Trichloro-2,6-di-m-tolylpyridine
(4g):
Colorless
solid; yield: 38%); mp 82–848C. 1H NMR (400 MHz,
CDCl3): d=2.40 (s, 6H, CH3), 7.22–7.25 (m, 2H, CH), 7.31–
7.36 (m, 2H, CH), 7.49–7.51 (m, 4H, CH); 13C NMR
(100 MHz, CDCl3): d=21.4 (CH3), 126.5 (CH), 127.9 (CH),
m/z=550.23808,
calcd.
for
C38H32NO3 ([M+H]+):
550.23767; anal. calcd. for C38H31NO3 (549.66): C 83.03, H
5.68, N 2.55; found: C 83.27, H 5.526, N 2.115.
2,6-Diphenyl-3,4,5-tris(4-(trifluoromethyl)phenyl)pyridine
1
128.1 (C), 129.6 (CH), 129.6 (C), 130.0 (CH), 137.7 (C),
(5b): Colorless solid; yield: 79%; mp 305–3078C. H NMR
À1
˜
137.9 (C), 155.8 (C); IR (ATR, cm ): n=2918 (w), 1606
(300 MHz, CDCl3): d=6.86–6.89 (m, 2H, CH), 6.98–7.01
(m, 4H, CH), 7.16–7.35 (m, 16H, CH); 13C NMR (75 MHz,
(w), 1586 (m), 1512 (m), 1485 (m), 1366 (s), 1271 (w), 1143
(m), 1100 (m), 969 (m), 877 (w), 773 (m), 755 (m), 701 (s),
642 (w), 610 (m), 563 (m), 523 (m), 511 (w), 492 (m),
429 cmÀ1 (m); MS (EI, 70 eV): m/z (%): 363 (M+, 76), 362
(22), 361 (77), 330 (12), 329 (15), 328 (67), 327 (23), 326
(100), 291 (10), 290 (8), 240 (11), 180 (11), 139 (16), 138 (8),
91 (7), 89 (5); HR-MS (ESI): m/z=362.02678, calcd. for
C19H15Cl3N ([M+H]+): 362.02646.
1
1
CDCl3): d=123.6 (q, JC,F =271.6 Hz, CF3), 123.7 (q, JC,F
=
=
=
3
3
271.6 Hz, CF3), 124.5 (q, JC,F =3.9 Hz, CH), 124.7 (q, JC,F
3.9 Hz, CH), 127.8 (CH), 128.0 (CH), 129.0 (q, JC,F
32.6 Hz, C), 129.3 (q, JC,F =32.6 Hz, C), 130.1 (CH), 130.5
(CH), 131.4 (CH), 132.1 (C), 139.7 (C), 141.1 (C), 141.6 (C),
148.5 (C), 157.2 (C); 19F NMR (282.4 MHz, CDCl3): d=
2
2
˜
À62.3 (CF3), À62.4 (CF3); IR (ATR): n=1617 (m), 1538
3,4,5-Trichloro-2,6-bis(2-methoxyphenyl)pyridine
(4h):
(w), 1410 (w), 1392 (w), 1320 (s), 1162 (m), 1108 (s), 1067
(m), 1017 (m), 850 (m), 778 (m), 695 (m), 677 (m), 662 (w),
642 (m), 635 (m), 608 (w), 499 cmÀ1 (w); MS (EI, 70 eV): m/
z (%)=664 (M+, 15), 663 (58), 662 (100), 644 (5), 276 (2),
255 (2), 245 (2), 242 (2), 227 (3), 226 (3); HR-MS (ESI):
m/z=664.16814, calcd. for C38H23F9N ([M+H]+): 664.16813.
3,4,5-Tris(para-tolyl)-2,6-phenylpyridine (5c): Colorless
solid; yield: 67%; mp 184–1858C. 1H NMR (300 MHz,
Colorless solid; yield: 29%; mp 191–1938C. 1H NMR
(300 MHz, CDCl3): d=3.81 (s, 6H, MeO), 6.94–7.04 (m,
4H, CH), 7.30–7.42 (m, 4H, CH); 13C NMR (75 MHz,
CDCl3): d=55.5 (MeO), 111.0 (CH), 120.6 (CH), 127.5
(CH), 130.3 (C), 130.4 (C), 130.5 (CH), 141.2 (C), 154.1 (C),
˜
156.7 (C); IR (ATR): n=2930 (w), 2831 (w), 1600 (m), 1582
(m), 1491 (m), 1460 (m), 1161 (m), 1113 (m), 1092 (m), 1020
(m), 821 (m), 793 (s), 758 (s), 705 (m), 655 (m), 552 (m), 512
(m), 488 (w), 466 cmÀ1 (w); MS (EI, 70 eV): m/z (%)=395
(M+, 5), 394 (3), 362 (12), 361 (14), 360 (65), 359 (22), 358
(100), 328 (5), 308 (19), 243 (4), 227 (4), 214 (3), 154 (3), 147
(4), 139 (4), 125 (3); HR-MS (ESI): m/z=394.0167, calcd.
for C19H15Cl3NO2 ([M+H]+): 394.0163; anal. calcd. for
C19H14Cl3NO2 (394.67): C 57.82, H 3.58, N 3.55; found: C
57.85, H 3.700, N, 3.789.
3
3
CDCl3): d=1.07 (t, 3H, J=7.5 Hz, CH3), 1.12 (t, 6H, J=
7.5 Hz, CH3), 2.41–2.54 (m, 6H, CH2), 6.67 (d, 2H, 3J=
8.1 Hz, CH) 6.75–6.85 (m, 10H, CH), 7.16–7.21 (m, 6H,
CH), 7.42–7.45 (m, 4H, CH); 13C NMR (75 MHz, CDCl3):
d=15.4, 15.5 (CH3), 28.4 (CH2), 126.3, 126.7, 127.1, 127.4,
130.2, 130.4, 131.2 (CH), 133.8, 135.5, 135.7, 141.1, 141.8,
˜
142.0, 150.6, 156.1 (C); IR (ATP): n=2958 (m), 2922 (m),
2852 (m), 1491 (w), 1446 (w), 1389 (m), 1183 (w), 1115 (w),
1059 (w), 1021 (w), 914 (w), 825 (m), 775 (m), 694 (s),
659 cmÀ1 (m); MS (EI, 70 eV): m/z (%)=543 (M+, 69), 542
(100), 526 (6), 514 (6), 484 (2); HR-MS (ESI): m/z=
544.3002, calcd. for C41H38N ([M+H]+): 544.29988.
Synthesis of Pentaarylpyridines 5a–g Starting from 4
An oven-dried and argon-flushed pressure tube was charged
3,4,5-Tris(4-methoxyphenyl)-2,6-di(para-tolyl)pyridine
with the appropriate 3,4,5-trichloro-2,6-diarylpyridines
4
1
(5d): Slightly yellow solid; yield: 85%; mp 2038C. H NMR
(1.0 equiv.), PdCl2A(CH3CN)2 (5.0 mol%), SPhos
CTHUNGTRENNUNG
(300 MHz, CDCl3): d=2.29 (s, 6H, CH3), 3.66 (s, 3H,
(10.0 mol%), boronic acid (6.0 equiv.) and K3PO4
(6.0 equiv.) followed by anhydrous toluene (3.0 mL); The
tube was sealed with a Teflon valve and the reaction mixture
was stirred at 1008C for 20 h. The cooled reaction mixture
was diluted with water and extracted with DCM. The com-
bined organic layers were dried (Na2SO4), filtered and the
filtrate was concentrated under vacuum. The residue was
purified by column chromatography.
3
OCH3), 3.70 (s, 6H, OCH3), 6.50 (d, 2H, J=8.9 Hz, CH),
3
3
6.57 (d, 4H, J=8.9 Hz, CH), 6.66 (d, 2H, J=8.9 Hz, CH),
3
3
6.80 (d, 4H, J=8.9 Hz, CH), 7.00 (d, 4H, J=8.1 Hz, CH),
3
7.30 (d, 4H, J=8.1 Hz, CH); 13C NMR (75 MHz, CDCl3):
d=21.2 (CH3), 54.9, 55.0 (OCH3), 112.5, 112.9, 128.2, 130.1
(CH), 130.8, 131.1 (C), 131.6, 132.3 (CH), 133.1, 136.8,
˜
150.2, 156.1, 157.5, 157.7 (C); IR (ATR): n=2917 (w), 2835
(w), 1608 (m), 1514 (m), 1386 (m), 1287 (m), 1244 (s), 1174
(s), 1032 (m), 826 (m), 809 (m), 756 (m), 728 (m), 558 cmÀ1
(m); MS (EI, 70 eV): m/z (%)=577 (M+, 85), 576 (100), 532
2,6-Diphenyl-3,4,5-tris(4-methoxyphenyl)pyridine
(5a):
Colorless solid; yield: 83%; mp 219–2218C. 1H NMR
(300 MHz, CDCl3): d=3.64 (s, 3H, MeO), 3.67 (s, 6H,
12
asc.wiley-vch.de
ꢂ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
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FULL PAPERS
Site Selective Synthesis of Pentaarylpyridines
(6), 489 (2), 337 (2), 289 (4); HR-MS (ESI): m/z=
578.26951, calcd. for C40H36NO3 ([M+H]+) 578.26897.
2,6-Bis(4-ethylphenyl)-3,4,5-triphenylpyridine (5e): Color-
(2), 60 (5), 57 (2), 44 (9), 43 (5), 41 (2); HR-MS (ESI):
m/z=606.30033, calcd. for C42H40NO3 ([M+H]+): 606.30027.
1
less solid; yield: 92%; mp 223–2258C. H NMR (300 MHz,
Synthesis of Tetraarylpyridines from 1 (Regioisomeric
Mixtures 6/7)
3
3
CDCl3): d=1.18 (t, JH,H =7.7 Hz, 6H, CH3), 2.58 (q, JH,H
=
7.8 Hz, 4H, CH2), 6.76–6.79 (m, 2H, CH), 6.89–6.95 (m, 7H,
CH), 6.99–7.02 (m, 10H, CH), 7.33–7.36 (m, 4H, CH);
13C NMR (75 MHz, CDCl3): d=15.3 (CH3), 28.5 (CH2),
126.0 (CH), 126.1 (CH), 126.9 (CH), 127.0 (CH), 127.3
(CH), 130.2 (CH), 130.4 (CH), 131.3 (CH), 133.2 (C), 138.2
(C), 138.3 (C), 138.6 (C), 143.2 (C), 150.2 (C), 156.1 (C); IR
An oven-dried and argon-flushed pressure tube was charged
with pentachloropyridine
1
(1 equiv.), PdCl2ACTHNGUTERNNU(G CH3CN)2
(5.0 mol%), SPhos (10.0 mol%), boronic acid (4.5 equiv.)
and K3PO4 (6.5 equiv.) followed by anhydrous toluene
(7.0 mL); The tube was sealed with a Teflon valve and the
reaction mixture was stirred at 1008C for 20 h. The cooled
reaction mixture was diluted with water and extracted with
DCM. The combined organic layers were dried (Na2SO4),
filtered and the filtrate was concentrated under vacuum.
The residue was purified by column chromatography afford-
ing isomeric mixtures of 5-chloro-2,3,4,6-tetraaryl-substitut-
ed pyridines 6 and 4-chloro-2,3,5,6-tetraaryl-substituted pyri-
dines 7 which could not be separated preparatively by
column chromatography. The products were confirmed by
GC-MS und HR-MS data. A detailed analysis of the NMR
spectra (1 H, 13C NMR) could not be performed due to sev-
eral overlapping signals. The ratio of regioisomers was deter-
mined by inverse gated-decoupling 13C NMR spectroscopy
(13C igd).
˜
(ATR): n=3032 (w), 2958 (m), 2926 (w), 2866 (m), 1889
(w), 1531 (m), 1509 (w), 1413 (w), 1391 (m), 1279 (w), 1186
(w), 1022 (m), 1007 (m), 845 (m), 820 (m), 739 (s), 711 (s),
697 (s), 658 (m), 629 (m), 594 (m), 559 (m), 526 (m),
488 cmÀ1 (m); MS (EI, 70 eV): m/z (%)=516 (M+, 20), 515
(65), 514 (100), 486 (6), 393 (2), 227 (1), 226 (1), 220 (5), 214
(2), 213 (2), 189 (2); HR-MS (ESI): m/z=516.2686, calcd.
for C39H34N ([M+H]+): 516.26858; anal. calcd. for C39H33N
(515.69): C 90.83, H 6.45, N 2.72; found: C 90.93, H 6.141, N
2.389.
2,6-Bis(4-ethylphenyl)-3,4,5-tris[4-(trifluoromethyl)phe-
nyl]pyridine (5f): Colorless solid; yield: 96%; mp 207–
3
2088C. 1H NMR (300 MHz, CDCl3): d=1.18 (t, JH,H
=
7.7 Hz, 6H, CH3), 2.59 (q, 3JH,H =7.6 Hz, 4H, CH2), 6.85–
6.88 (m, 2H, CH), 7.00–7.04 (m, 8H, CH), 7.22–7.31 (m,
10H, CH); 13C NMR (75 MHz, CDCl3): d=15.2 (CH3), 28.5
Synthesis of 3,5-Dichloro-2,4,6-triarylpyridines 9a–k
1
(CH2), 123.7 (q, 1JC,F =274.1 Hz, CF3), 123.8 (q, JC,F
=
=
=
An oven-dried and argon-flushed pressure tube was charged
with 2,3,5,6-tetrachloro-4-(4-(aryl)pyridine 8a or 8b
(1.0 equiv.), PdACTHUNTRGNE(UNG PPh3)4 (5.0 mol%), the appropriate boronic
3
3
272.0 Hz, CF3), 124.4 (q, JC,F =3.9 Hz, CH), 124.7 (q, JC,F
2
3.9 Hz, CH), 128.9 (q, 2JC,F =33.3 Hz, C), 129.1 (q, JC,F
32.9 Hz, C), 130.1 (CH), 130.6 (CH), 131.5 (CH), 131.6 (C),
137.2 (C), 141.3 (C), 141.9 (C), 144.2 (C), 148.5 (C), 157.1
(C); 19F NMR (282.4 MHz, CDCl3): d=À62.2 (CF3), À62.4
acid (3.0 equiv.) and K3PO4 (3.0 equiv.) followed by anhy-
drous toluene (4.0 mL); The tube was sealed with a Teflon
valve and the reaction mixture was stirred at 1008C for 20 h.
The cooled reaction mixture was diluted with water and ex-
tracted with DCM. The combined organic layers were dried
(Na2SO4), filtered and the filtrate was concentrated under
vacuum. The residue was purified by column chromatogra-
phy.
˜
(CF3); IR (ATR): n=2967 (w), 1616 (m), 1534 (w), 1407
(w), 1321 (s), 1164 (m), 1108 (s), 1065 (s), 1017 (m), 857
(m), 827 (m), 794 (w), 768 (w), 755 (w), 704 (w), 635 (w),
610 (m), 593 (m), 550 (w), 475 cmÀ1 (w); MS (EI, 70 eV): m/
z (%)=720 (M+, 15), 719 (57), 718 (100), 703 (5), 277 (3),
276 (13), 275 (16), 207 (33), 197 (4), 183 (7), 165 (6), 133 (4),
109 (3), 108 (4), 107 (3), 97 (4), 96 (4), 91 (7), 78 (4), 73 (6),
69 (7), 57 (7), 45 (7), 44 (7), 43 (8), 41 (5); HR-MS (EI,
70 eV): m/z=718.21443, calcd. for C42H29NF9: 718.21508;
anal. calcd. for C42H30F9N (719.68): C 70.09, H 4.20, N 1.95;
found: C 70.52, H 3.940, N 1.594.
3,5-Dichloro-2,6-diphenyl-4-[4-(trifluoromethyl)phenyl]-
pyridine (9a): Colorless solid; yield: 47%; mp 162–1648C.
1H NMR (300 MHz, CDCl3): d=7.43–7.50 (m, 8H, CH),
7.74–7.81 (m, 6H, CH); 13C NMR (75 MHz, CDCl3): d=
1
3
124.1 (q, JC,F =272.6 Hz, CF3), 125.7 (q, JC,F =4.0 Hz, CH),
128.1 (CH), 128.2 (C), 129.1 (CH), 129.3 (CH), 129.5 (CH),
2
2,6-Bis(4-ethylphenyl)-3,4,5-tris(3-methoxyphenyl)pyri-
130.8 (q, JC,F =32.4 Hz, C), 137.8 (C), 139.9 (C), 148.0 (C),
dine (5g): Colorless oil; yield: 92%. 1H NMR (300 MHz,
155.0 (C); 19F NMR (282.4 MHz, CDCl3): d=À62.2 (CF3);
IR (ATR): n˜ =3054 (w), 1935 (w), 1615 (w), 1541 (w), 1523
(w), 1493 (m), 1365 (m), 1323 (s), 1169 (m), 1158 (s), 1128
(s), 1083 (m), 1066 (m), 1037 (w), 1019 (m), 960 (w), 870
(w), 849 (m), 775 (w), 757 (m), 744 (w), 691 (s), 677 (m),
658 (m), 640 (m), 623 (w), 562 (m), 528 (m), 479 (w), 403
(w), 383 cmÀ1 (m); MS (EI, 70 eV): m/z (%)=444 (M+, 33),
443 (100), 426 (5), 410 (33), 409 (27), 408 (96), 406 (5), 372
(13), 332 (7), 270 (18), 227 (6), 204 (9), 200 (7), 152 (5), 151
(7), 51 (4); HR-MS (EI, 70 eV): m/z=443.04483, calcd. for
C24H14Cl2F3N: 443.04499, m/z=445.04232, calcd. for
C24H14Cl37ClF3N: 445.04204; anal. calcd. for C24H14Cl2F3N
(444.28): C 64.88, H 3.18, N 3.15; found: C 65.07, H 3.005, N
3.070.
3
3
CDCl3): d=1.18 (t, JH,H =7.7 Hz, 6H, CH3), 2.61 (q, JH,H
=
7.6 Hz, 4H, CH2), 3.45 (brs, 3H, MeO), 3.47 (s, 6H, MeO),
6.35–6.59 (m, 9H, CH), 6.83–7.00 (m, 3H, CH), 7.00–7.03
(m, 4H, CH), 7.34–7.37 (m, 4H, CH); 13C NMR (75 MHz,
CDCl3): d=15.3 (CH3), 28.5 (CH2), 55.0 (MeO), 55.0
(MeO), 112.8 (CH), 115.5 (CH), 116.4 (CH), 123.0 (CH),
124.0 (CH), 127.0 (CH), 127.9 (CH), 128.3 (CH), 130.0
(CH), 130.0 (CH), 132.8 (C), 138.1 (C), 139.5 (C), 139.8 (C),
143.3 (C), 149.6 (C), 156.2 (C), 158.4 (C), 158.7 (C); IR
˜
(ATR): n=2961 (w), 2931 (m), 2871 (w), 2832 (w), 1906
(w), 1598 (s), 1578 (s), 1531 (m), 1489 (m), 1451 (m), 1387
(m), 1315 (m), 1284 (m), 1234 (m), 1215 (s), 1180 (m), 1122
(w), 1048 (s), 1022 (m), 995 (m), 838 (s), 816 (m), 781 (m),
727 (s), 696 (m), 633 (w), 563 (w), 471 cmÀ1 (w); MS (EI,
70 eV): m/z (%)=606 (M+, 23), 605 (75), 604 (100), 603 (5),
590 (5), 588 (6), 287 (2), 226 (1), 97 (1), 85 (2), 73 (4), 71
3,5-Dichloro-2,6-di-para-tolyl-4-[4-(trifluoromethyl)phe-
nyl]pyridine (9b): Colorless solid; yield: 41%; mp 124–
1
1268C. H NMR (300 MHz, CDCl3): d=2.40 (s, 6H, CH3),
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢂ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
13
ÞÞ
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FULL PAPERS
Sebastian Reimann et al.
7.26 (d, 3J=7.3 Hz, 4H, CH), 7.46 (d, 3JH,H =8.0 Hz, 2H,
113.9 (CH), 128.3, 128.9 (C), 130.1 (CH), 130.8 (C), 131.7
3
3
˜
CH), 7.67 (d, J=8.0 Hz, 4H, CH), 7.78 (d, JH,H =8.1 Hz,
(CH), 149.1, 154.2, 159.6, 160.1 (C); IR (ATR): n=2930 (w),
2H, CH); 13C NMR (75 MHz, CDCl3): d=21.4 (CH3), 124.1
2835 (w), 1606 (m), 1502 (s), 1457 (m), 1364 (m), 1290 (m),
1247 (s), 1173 (s), 1028 (s), 826 (s), 783 (m), 551 (m),
535 cmÀ1 (m); MS (EI, 70 eV): m/z (%)=465 (M+, 100), 430
(10), 414 (6), 387 (3), 372 (2), 262 (3); HR-MS (EI, 70 eV):
m/z=465.08910, calcd, for C26H21Cl2NO3: 465.08930; anal.
calcd. for C26H21Cl2NO3 (466.36): C 66.96, H 4.54, N 3.00;
found: C 67.02, H 4.503, N 3.107.
1
3
(q, JC,F =273.2 Hz, CF3), 125.6 (q, JC,F =3.8 Hz, CH), 126.8
(C), 127.8 (C), 128.7 (CH), 129.3 (CH), 129.5 (CH), 130.8
2
(q, JCÀF =32.7 Hz, C), 135.1 (C), 139.1 (C), 147.9 (C), 154.9
(C); 19F NMR (282.4 MHz, CDCl3): d=À62.2 (CF3); IR
˜
(ATR): n=3053 (w), 3034 (w), 2919 (m), 2858 (w), 1908
(w), 1613 (m), 1543 (w), 1507 (m), 1408 (m), 1367 (m), 1324
(s), 1186 (m), 1159 (m), 1120 (s), 1108 (s), 1083 (m), 1066
(s), 1019 (m), 908 (w), 876 (m), 851 (m), 821 (s), 776 (m),
752 (m), 674 (m), 663 (m), 618 (m), 525 (m), 490 (m), 377
(m); MS (EI, 70 eV): m/z (%)=472 (M+, 30), 471 (100), 438
(20), 437 (15), 436 (49), 402 (4), 386 (4), 346 (2), 284 (6), 283
(7), 262 (3), 240 (4), 235 (9), 213 (5), 200 (3), 158 (3), 157
(6), 151 (4), 115 (5), 91 (6), 65 (4); HR-MS (ESI): m/z=
472.08485, calcd. for C26H19Cl2F3N ([M+H]+): 472.08412;
anal. calcd. for C26H18Cl2F3N (472.33): C 66.11, H 3.84, N
2.97; found: C 66.06, H 3.955, N 3.149.
3,5-Dichloro-4-(4-methoxyphenyl)-2,6-bis(4-vinylphenyl)-
pyridine (9f): Colorless solid; yield: 45%; mp 95–978C.
1H NMR (300 MHz, CDCl3): d=3.90 (s, 3H, OCH3), 5.33
2
3
(dd, 2H, J=0.9 Hz, J=10.9 Hz, HC=CH2), 5.84 (dd, 2H,
2J=0.8 Hz, 3J=17.6 Hz, HC=CH2), 6.79 (dd, 2H, 3J=
17.6 Hz, 3J=10.7 Hz, HC=CH2), 7.07 (d, 2H, 3J=8.8 Hz,
3
3
CH), 7.30 (d, 2H, J=8.8 Hz, CH), 7.52 (d, 4H, J=8.3 Hz,
CH), 7.80 (d, 4H 3J=8.3 Hz, CH); 13C NMR (75 MHz,
CDCl3): d=55.2, (OCH3), 113.9 (CHvinyl), 114.8 (CH2), 125.8
(CH), 128.6, 128.9 (C), 129.9, 130.1, 136.4 (CH), 137.6,
˜
3,5-Dichloro-2,6-bis(3-methoxyphenyl)-4-[4-(trifluorome-
thyl)phenyl]pyridine (9c): Colorless solid; yield: 52%; mp
165–1668C. 1H NMR (300 MHz, CDCl3): d=3.84 (s, 6H,
138.1, 149.2, 154.3, 159.7 (C); IR (ATR): n=2954 (w), 2917
(w), 2834 (w), 1607 (m), 1500 (s), 1361 (s), 1246 (s), 1177
(m), 1039 (m), 987 (m), 907 (m), 830 cmÀ1 (s); MS (EI,
70 eV): m/z (%)=447 (M+, 100), 422 (28), 407 (4), 379 (7),
343 (4), 315 (3); HR-MS (ESI): m/z=458.10801, calcd. for
C28H22Cl2NO ([M+H]+): 458.1073; anal. calcd. for
C28H21Cl2NO (458.38): C 73.37, H 4.62, N 3.06; found: C
72.99, H 4.807, N 2.935.
3
4
4
MeO), 6.98 (ddd, JH,H =7.7 Hz, JH,H =2.7 Hz, JH,H =2.2 Hz,
3
2H, CH), 7.28–7.40 (m, 6H, CH), 7.47 (brd, JH,H =7.6 Hz,
2H, CH), 7.79 (brd, 3JH,H =7.7 Hz, 2H, CH); 13C NMR
(75 MHz, CDCl3): d=55.4 (MeO), 114.8 (CH), 115.2 (CH),
1
3
122.0 (CH), 124.1 (q, JC,F =272.2 Hz, CF3), 125.7 (q, JC,F
=
4.0 Hz, CH), 128.3 (C), 129.1 (CH), 129.3 (CH), 130.9 (q,
2JC,F =33.1 Hz, C), 130.1 (C), 139.8 (C), 148.1 (C), 154.8 (C),
159.3 (C); 19F NMR (282.4 MHz, CDCl3): d=À62.2 (CF3);
3,5-Dichloro-2,6-bis[4-(trifluoromethyl)phenyl]-4-(4-me-
thoxyphenyl)pyridine (9g): Colorless solid; yield: 40%; mp
119–1218C. 1H NMR (300 MHz, CDCl3): d=3.90 (s, 3H,
OCH3), 7.08 (d, 2H, 3J=8.8 Hz, CH), 7.30 (d, 2H, 3J=
˜
IR (ATR): n=3002 (w), 2928 (w), 2834 (m), 1596 (m), 1579
3
3
(m), 1489 (m), 1407 (w), 1358 (m), 1321 (s), 1287 (m), 1275
(m), 1253 (m), 1229 (s), 1161 (s), 1119 (s), 1109 (s), 995 (m),
933 (m), 846 (m), 776 (s), 754 (m), 705 (s), 691 (m), 658 (m),
562 (m), 509 (w), 446 (w), 382 cmÀ1 (m); MS (EI, 70 eV): m/
z (%)=504 (M+, 84), 503 (80), 502 (100), 476 (12), 475 (21),
474 (22), 473 (27), 472 (7), 430 (4), 395 (4), 346 (5), 251 (12),
207 (6), 163 (5), 145 (7), 137 (3), 63 (3); HR-MS (EI,
70 eV): m/z=503.06484, calcd. for C26H18Cl2F3NO2:
503.06612, m/z=505.06218, calcd. for C26H18Cl37ClF3NO2:
505.06317.
3,5-Dichloro-2,6-bis[4-(trifluoromethyl)phenyl]-4-(4-me-
thoxyphenyl)pyridine (9d): Colorless solid; yield: 71%; mp
164–1668C. 1H NMR (300 MHz, CDCl3): d=3.90 (s, 3H,
OCH3), 7.07 (d, 2H, 3J=8.9 Hz, CH), 7.31 (d, 2H, 3J=
8.9 Hz, CH), 7.43–7.51 (m, 6H, CHPh), 7.78–7.81 (m, 4H,
CH); 13C NMR (75 MHz, CDCl3): d=55.2 (OCH3), 113.9,
128.6 (CH), 128.6 (C), 128.8 (CH), 129.1 (C), 129.6, 130.1
8.8 Hz, CH), 7.74 (d, 4H, J=8.3 Hz, CH), 7.90 (d, 4H, J=
8.3 Hz, CH); 13C NMR (75 MHz, CDCl3): d=55.3 (OCH3),
114.1 (CH), 124.0 (q, 1J=272.3 Hz, CF3), 125.1 (q, 3J=
3.7 Hz CH), 127.9, 129.9 (C), 130.0, 130.1 (CH), 131.0 (q,
2J=32.9 Hz, C-CF3), 141.4, 149.8, 153.7, 160.0 (C); IR
˜
(ATR): n=2918 (w), 1611 (m), 1506 (m), 1366 (m), 1322 (s),
1252 (m), 1163 (m), 1106 (s), 1065 (s), 1016 (s), 829 (m),
705 cmÀ1 (m); MS (EI, 70 eV): m/z (%)=541 (M+, 100), 526
(8), 522 (8), 506 (40), 463 (12), 428 (5); HR-MS (ESI):
m/z=542.05092, calcd. for C26H16Cl2F6NO ([M+H]+):
542.05077.
3,5-Dichloro-2,6-bis(4-isopropylphenyl)-4-(4-methoxyphe-
nyl)pyridine (9h): Colorless solid; yield: 69%; mp 81–838C.
1H NMR (400 MHz, CDCl3): d=1.31 (d, 12H, 3J=6.9 Hz,
CH3), 2.99 (sept, 2H, 3J=6.9 Hz, CHi-Pr), 3.89 (s, 3H,
OCH3), 7.06–7.09 (m, 2H, CH), 7.29–7.35 (m, 6H, CH),
7.74–7.77 (m, 4H, CH); 13C NMR (100 MHz, CDCl3): d=
23.8 (CH3), 33.9 (CHi-Pr), 55.1 (OCH3), 113.8, 126.0 (CH),
128.6, 128.7 (C), 129.5, 130.1 (CH), 135.8, 148.9, 149.5, 154.6,
˜
(CH), 138.3, 149.1, 154.8, 159.7 (C); IR (ATR): n=3026 (w),
2918 (w), 2836 (w), 1613 (w), 1514 (m), 1358 (m), 1250 (m),
1027 (m), 892 (m), 762 (m), 692 (s), 569 cmÀ1 (m); MS (EI,
70 eV): m/z (%)=405 (M+, 100), 390 (8), 370 (61), 355 (5),
327 (13), 291 (12); HR-MS (EI, 70 eV): m/z=405.06800,
calcd. for C24H17Cl2NO: 405.06817; anal. calcd. for
C24H17Cl2NO (406.30): C 70.95, H 4.22, N 3.45; found: C
71.02, H 4.123, N 3.467.
˜
159.5 (C); IR (ATR): n=2957 (m), 2868 (w), 2835 (w), 1609
(m), 1500 (s), 1460 (m), 1361 (s), 1290 (m), 1246 (s), 1018
(m), 828 (s), 731 (m), 657 (m), 557 cmÀ1 (s); MS (EI, 70 eV):
m/z (%)=489 (M+, 100), 474 (73), 458 (6), 432 (4), 230 (23),
215 (4), 158 (4); HR-MS (EI, 70 eV): m/z=489.16144, calcd.
for C30H29Cl2NO: 489.16207; anal. calcd. for C30H29Cl2NO
(490.46): C 73.47, H 5.96, N 2.86; found: C 73.25, H 5.90, N
2.75.
3,5-Dichloro-2,4,6-(4-methoxyphenyl)pyridine (9e): Color-
1
less solid; yield: 69%; mp 136–1388C. H NMR (300 MHz,
CDCl3): d=3.86 (s, 6H, OCH3), 3.89 (s, 3H, OCH3), 6.99 (d,
3,5-Dichloro-2,6-bis(4-fluorophenyl)-4-(4-methoxyphe-
nyl)pyridine (9i): Colorless solid; yield: 63%; mp 224–
2268C. H NMR (300 MHz, CDCl3): d=3.86 (s, 3H, OCH3),
3
3
4H, J=8.8 Hz, CH), 7.06 (d, 2H, J=8.8 Hz, CH), 7.28 (d,
2H, 3J=8.8 Hz, CH), 7.78 (d, 4H, 3J=8.8 Hz, CH);
13C NMR (75 MHz, CDCl3): d=55.2, 55.3 (OCH3), 113.3,
1
7.01–7.06 (m, 2H, CH), 7.08–7.16 (m, 4H, CH), 7.22–7.27
14
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Site Selective Synthesis of Pentaarylpyridines
3
(m, 2H, CH), 7.71–7.78 (m, 4H, CH); 13C NMR (75 MHz,
3.64 (s, 3H, OCH3), 6.47 (d, 2H, J=8.9 Hz, CH), 6.67 (d,
3 3
2
CDCl3): d=55.2 (OCH3), 113.9 (CH), 115.0 (d, JC,F
=
=
2H, J=8.9 Hz, CH), 6.82 (d, 4H, J=8.3 Hz, CH), 7.04 (d,
3
3
21.8 Hz, CH), 128.3, 129.1 (C), 130.0 (CH), 131.5 (d, JC,F
4H, J=8.3 Hz, CH), 7.15–7.20 (m, 6H, CH), 7.40–7.44 (m,
4
4H, CH); 13C NMR (75 MHz, CDCl3): d=31.2 (CH3), 34.3
(Ct-Bu), 55.0 (OCH3), 112.3, 124.2, 127.1, 127.3, 130.2 (CH),
130.6 (C), 130.9, 131.7 (CH), 133.9, 135.5, 141.1, 149.0, 150.0,
8.3 Hz, CH), 134.1 (d, JC,F =3.2 Hz, C), 149.4, 153.7, 159. 7
(C), 163.1 (d, 1JC,F =249.0 Hz, CF); 19F NMR (282 MHz,
˜
CDCl3): d=À111.7 (s, 2F, CF); IR (ATR): n=3004 (w),
2939 (w), 2838 (w), 1603 (m), 1504 (s), 1359 (m), 1292 (m),
1230 (s), 1156 (s), 834 (s), 529 cmÀ1 (s); MS (EI, 70 eV): m/z
(%)=441 (M+, 100), 406 (34), 363 (10), 327 (8), 207 (14);
HR-MS (EI, 70 eV): m/z=441.04912, calcd. for
C24H15Cl2F2NO: 441.04933; anal. calcd. for C24H15Cl2F2NO
(442.28): C 65.17, H 3.42, N 3.17; found: C 65.20, H 3.56, N
3.19.
˜
156.2, 157.6 (C); IR (ATR): n=2956 (m), 2903 (w), 2864
(w), 2832 (w), 1610 (m), 1510 (m), 1387 (m), 1248 (s), 1172
(m), 1107 (m), 1022 (w), 828 (m), 779 (m), 699 cmÀ1 (s); MS
(EI, 70 eV): m/z (%)=601 (M+, 91), 600 (100), 586 (9), 544
(11), 530 (6), 488 (6); HR-MS (ESI): m/z=602.34224, calcd.
for C44H44NO ([M+H]+): 602.34174; anal. calcd. for
C44H43NO (601.82): C 87.81, H 7.20, N 2.33; found: C 87.47,
H 7.082, N 2.279.
4-(4-Methoxyphenyl)-2,6-diphenyl-3,5-di-para-tolylpyri-
dine (10b): Colorless solid; yield: 84%; mp 238–2398C.
1H NMR (300 MHz, CDCl3): d=2.17 (s, 6H, CH3), 3.63 (s,
3H, OCH3), 6.47 (d, 2H, J=8.9 Hz, CH), 6.66 (d, 2H, J=
8.9 Hz, CH), 6.74–6.81 (m, 8H, CH), 7.15–7.17 (m, 6H,
CH), 7.37–7.40 (m, 4H, CH); 13C NMR (75 MHz, CDCl3):
d=21.1 (CH3), 54.0 (OCH3), 112.4, 127.1, 127.4, 128.1, 130.2
(CH), 130.6 (C), 131.1, 131.5 (CH), 133.9, 135.5, 135.5,
3,5-Dichloro-2,6-di(meta-tolyl)-4-(4-methoxyphenyl)pyri-
dine (9j): Colorless solid; yield: 47%; mp 130–1328C.
1H NMR (300 MHz, CDCl3): d=2.40 (s, 6H, CH3), 3.87 (s,
3H, OCH3), 7.01–7.06 (m, 2H, CH), 7.20–7.36 (m, 6H, CH),
7.52–7.54 (m, 4H, CH); 13C NMR (75 MHz, CDCl3): d=
21.4 (CH3), 55.2 (OCH3), 113.8, 126.6, 127.8 (CH), 128.6,
129.0 (C), 129.6, 130.1 (CH), 137.7, 138.2, 148.9, 155.0, 159.6
3
3
˜
(C); IR (ATR): n=3040 (w), 2921 (w), 2830 (w), 1605 (m),
1507 (s), 1356 (s), 1285 (m), 1243 (s), 1178 (m), 1022 (m),
790 (s), 774 (s), 698 (s), 586 cmÀ1 (s); MS (EI, 70 eV): m/z
(%)=433 (M+, 100), 398 (66), 355 (8), 202 (10), 152 (9);
HR-MS (EI, 70 eV): m/z=433.09915, calcd. for
C26H21Cl2NO: 433.09947; anal. calcd. for C26H21Cl2NO
(434.36): C 71.89, H 4.87, N 3.22; found: C 71.81, H 5.13, N
3.22.
˜
141.1, 150.0, 156.3, 157.6 (C); IR (ATR): n=2919 (m), 2850
(w), 1606 (w), 1508 (m), 1389 (m), 1288 (m), 1243 (m), 1172
(m), 1028 (m), 915 (w), 816 (m), 776 (m), 695 cmÀ1 (s); MS
(EI, 70 eV): m/z (%)=517 (M+, 73), 516 (100), 472 (7), 408
(1), 259 (1), 220 (7); HR-MS (ESI): m/z=518.24876, calcd
for C38H32NO 518.24784.
3,5-Bis[4-(trifluoromethyl)phenyl]-2,4,6-tris(4-methoxy-
phenyl)pyridine (10c): Colorless solid; yield: 79%; mp
3,5-Dichloro-2,6-bis(4-isopropoxyphenyl)-4-(4-methoxy-
phenyl)pyridine (9k): Colorless solid; yield: 71%; mp 173–
1
3
1
1758C. H NMR (300 MHz, CDCl3): d=1.37 (d, 12H, J=
6.0 Hz, CH3), 3.87 (s, 3H, OCH3), 4.61 (sept, 2H, 3J=
6.0 Hz, CHi-Pr), 6.94–6.99 (m, 4H, CH), 7.02–7.07 (m, 2H,
CH), 7.25–7.30 (m, 2H, CH), 7.74–7.79 (m, 4H, CH);
13C NMR (75 MHz, CDCl3): d=21.9 (CH3), 55.1 (OCH3),
69.7 (CHi-Pr), 113.8, 114.9 (CH), 128.0, 128.9 (C), 130.0
(CH), 130.4 (C), 131.0 (CH), 149.0, 154.1, 158.4, 159.5 (C);
2038C. H NMR (300 MHz, CDCl3): d=3.66 (s, 3H, OCH3),
3
3.77 (s, 6H, OCH3), 6.50 (d, 2H, J=8.9 Hz, CH), 6.60 (d,
3
3
2H, J=8.9 Hz, CH), 6.73 (d, 4H, J=8.9 Hz, CH), 7.03 (d,
4H, 3J=8.9 Hz, CH), 7.28–7.35 (m, 8H, CH); 13C NMR
(75 MHz, CDCl3): d=55.0, 55.1 (OCH3), 112.9, 113.1 (CH),
1
3
124.1 (d, J=272 Hz, CF3), 124.5 (d, J=4.2 Hz, CH), 128.3
(d, J=32.2 Hz, C-CF3), 129.3 (C), 131.3, 131.5, 131.6 (CH),
131.9, 132.6, 142.7, 149.8, 156.3, 158.1, 159.2 (C); IR (ATR):
2
˜
IR (ATR): n=2974 (w), 2934 (w), 2831 (w), 1607 (m), 1500
(s), 1363 (m), 1291 (m), 1247 (s), 1104 (s), 1040 (m), 950
(m), 830 (s), 785 (m), 638 cmÀ1 (m); MS (EI, 70 eV): m/z
(%)=521 (M+, 37), 437 (100), 402 (15), 219 (8), 43 (17);
HR-MS (EI, 70 eV): m/z=521.15137, calcd. for
C30H29Cl2NO3: 521.15190; anal. calcd. for C30H29Cl2NO3
(522.46): C 68.97, H 5.59, N 2.68; found: C 68.83, H 5.76, N
2.64.
˜
n=1606 (w), 1503 (w), 1321 (s), 1248 (m), 1160 (m), 1106
(s), 1065 (s), 1016 (m), 833 cmÀ1 (m); MS (EI, 70 eV): m/z
(%)=685ACHTUNGTRNEUNG
(M+, 95), 684 (100), 666 (4), 640 (8), 597 (2), 343
(3), 276 (2); HR-MS (ESI): m/z=686.21244, calcd for
C40H30F6NO3 ([M+H]+): 686.21244.
2,4,6-Tris(4-methoxyphenyl)-3,5-diphenylpyridine (10d):
Colorless solid; yield: 91%; mp 92–948C. 1H NMR
(300 MHz, CDCl3): d=3.62 (s, 3H, OCH3), 3.76 (s, 6H,
OCH3), 6.47 (d, 2H, 3J=8.9 Hz, CH), 6.66 (d, 2H, 3J=
8.9 Hz, CH), 6.72 (d, 4H, 3J=8.9 Hz, CH), 6.91–6.94 (m,
Synthesis of Pentaarylpyridines 10a–h Starting from 9
3
4H, CH), 7.03–7.05 (m, 6H, CH), 7.37 (d, 4H, J=8.9 Hz,
An oven-dried and argon-flushed pressure tube was charged
with 3,5-dichloro-2,4,6-triarylpyridine 9 (1.0 equiv.), PdCl2
ACHTUNGTRENNUNG(CH3CN)2 (5.0 mol%), SPhos (10.0 mol%), boronic acid
CH); 13C NMR (75 MHz, CDCl3): d=54.9, 55.1 (OCH3),
112.4, 112.9, 126.0, 127.5 (CH), 130.5 (C), 131.3, 131.5 (CH),
133.1, 133.4, 138.9, 150.0, 155.6, 157.6, 158.8 (C); IR (ATR):
(4.0 equiv.) and K3PO4 (4.0 equiv.) followed by anhydrous
toluene (3.5 mL); The tube was sealed with a Teflon valve
and the reaction mixture was stirred at 1008C for 20 h. The
cooled reaction mixture was diluted with water and extract-
ed with DCM. The combined organic layers were dried
(Na2SO4), filtered and the filtrate was concentrated under
vacuum. The residue was purified by column chromatogra-
phy.
˜
n=2932 (w), 2834 (w), 1604 (m), 1503 (m), 1389 (m), 1290
(m), 1241 (s), 1173 (s), 1027 (m), 907 (w), 832 (m), 764 (m),
698 cmÀ1 (s); MS (EI, 70 eV): m/z (%)=549 (M+, 77), 548
(100), 504 (7), 461 (2), 354 (2), 275 (11), 251 (10), 239 (10);
HR-MS (ESI): m/z=550.23797, calcd for C38H32NO3 ([M+
H]+): 550.23767.
2,6-Bis(4-fluorophenyl)-4-(4-methoxyphenyl)-3,5-di-para-
tolyl-pyridine (10e): Colorless solid; yield: 99%; mp 234–
3,5-Bis(4-tert-butylphenyl)-4-(4-methoxyphenyl)-2,6-di-
phenyl)pyridine (10a): Colorless solid; yield: 85%; mp 231–
1
2368C. H NMR (300 MHz, CDCl3): d=2.18 (s, 6H, CH3),
3.63 (s, 3H, OCH3), 6.44–6.48 (m, 2H, CH), 6.61–6.66 (m,
1
2328C. H NMR (300 MHz, CDCl3): d=1.22 (s, 18H, CH3),
Adv. Synth. Catal. 0000, 000, 0 – 0
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15
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Sebastian Reimann et al.
2H, CH), 6.70–6.74 (m, 4H, CH), 6.80–6.88 (m, 8H, CH),
271.9 Hz, CF3), 123.8 (q, 1JC,F =273.1 Hz, CF3), 124.5 (q,
3
7.30–7.37 (m, 4H, CH); 13C NMR (75 MHz, CDCl3): d=
3JC,F =3.9 Hz, CH), 124.7 (q, JC,F =4.0 Hz, CH), 127.9 (CH),
2
128.1 (CH), 129.0 (q, 2JC,F =32.4 Hz, C), 129.2 (q, JC,F
=
2
21.1 (CH3), 54.9 (OCH3), 112.4 (CH), 114.4 (d, JC,F
=
32.4 Hz, C), 130.1 (CH), 130.5 (CH), 131.4 (CH), 132.1 (C),
139.6 (C), 141.1 (C), 141.6 (C), 148.6 (C), 157.2 (C);
19F NMR (282.4 MHz, CDCl3): d=À62.3 (CF3), À62.4
21.2 Hz, CH), 128.3 (CH), 130.3 (C), 131.0, 131.4 (CH),
3
131.8 (d, JC,F =7.8 Hz, CH), 134.0, 135.1, 135.8 (C), 136.9 (d,
1
4JC,F =3.2 Hz, C), 150.4, 155.2, 157.6 (C), 162.1 (d, JC,F
=
246.6 Hz, CF); 19F NMR (282 MHz, CDCl3): d=À114.4 (s,
˜
(CF3); IR (ATR): n=3063 (w), 3035 (w), 1615 (m), 1576
(w), 1537 (m), 1410 (m), 1393 (w), 1320 (s), 1161 (m), 1107
(m), 1066 (S), 1017 (m), 916 (w), 850 (m), 831 (m), 779 (m),
758 (w), 695 (m), 662 (w), 608 (m), 465 (m), 394 cmÀ1 (w);
MS (EI, 70 eV): m/z (%)=664 (M+, 15), 663 (57), 662 (100),
645 (2), 644 (5), 420 (2), 350 (1), 322 (5), 287 (2), 276 (1),
254 (3), 242 (2), 226 (3), 220 (4); HR-MS (EI, 70 eV): m/z=
662.15249, calcd. for C38H21F9N: 662.15248; anal. calcd. for
C38H22F9N (663.57): C 68.78, H 3.34, N 2.11; found: C 68.71,
H 3.058, N 2.106.
˜
2F, CF); IR (ATR): n=2923 (w), 1596 (m), 1498 (s), 1389
(m), 1287 (m), 1220 (s), 1155 (s), 1038 (m), 834 (m), 806 (s),
524 cmÀ1 (s); MS (EI, 70 eV): m/z (%)=552 (M+, 100), 167
(20), 149 (51), 107 (13), 97 (14), 84 (15), 71 (23), 66 (11), 57
(32), 43 (18); HR-MS (EI, 70 eV): m/z=552.21339, calcd.
for C38H28F2NO: 552.21335; anal. calcd. for C38H29F2NO
(553.64): C 82.44, H 5.28, N 2.53; found: C 82.54, H 5.34, N
2.43.
3,5-Bis(4-methoxyphenyl)-2,6-diphenyl-4-[4-(trifluorome-
thyl)phenyl]pyridine (10f): Colorless solid; yield: 82%; mp
279–2818C. 1H NMR (300 MHz, CDCl3): d=3.67 (s, 6H,
MeO), 6.53–6.58 (m, 4H, CH), 6.72–6.78 (m, 4H, CH), 6.90
Synthesis of 3-Chloro-2,4,5,6-tetraarylpyridines 11a–h
Starting from 8a and 8b
3
(brd, JH,H =8.2 Hz, 2H, CH), 7.18–7.24 (m, 8H, CH), 7.38–
7.44 (m, 4H, CH); 13C NMR (75 MHz, CDCl3): d=54.9
An oven-dried and argon-flushed pressure tube was charged
with 2,3,5,6-tetrachloro-4-arylpyridine 8a or 8b (1.0 equiv.),
PdCl2ACHTNUGTRENUNG(CH3CN)2 (5.0 mol%), SPhos (10.0 mol%), boronic
3
(MeO), 113.1 (CH), 124.0 (q, JC,F =3.9 Hz, CH), 124.1 (q,
1JC,F =272.8 Hz, CF3), 127.3 (CH), 127.6 (CH), 128.2 (q,
2JC,F =32.4 Hz, C), 130.0 (C), 130.1 (CH), 130.8 (CH), 132.2
(CH), 133.0 (C), 140.6 (C), 142.5 (C), 149.1 (C), 156.6 (C),
158.0 (C); 19F NMR (282.4 MHz, CDCl3): d=À62.1 (CF3);
acid (3.0 equiv.) and K3PO4 (3.0 equiv.), followed by anhy-
drous toluene (3.5 mL). The tube was sealed with a Teflon
valve and the reaction mixture was stirred at 1008C for 20 h.
Afterwards, the cooled reaction mixture was diluted with
water and extracted with DCM. The combined organic
layers were dried (Na2SO4), filtered and the filtrate was con-
centrated under vacuum. The residue was purified by
column chromatography.
˜
IR (ATR): n=3040 (w), 3001 (w), 2955 (w), 2835 (w), 1609
(m), 1576 (w), 1533 (m), 1510 (s), 1388 (m), 1319 (s), 1289
(m), 1245 (s), 1175 (m), 1158 (s), 1106 (s), 1065 (m), 1034
(m), 1019 (m), 919 (w), 850 (m), 825 (m), 756 (m), 697 (s),
555 (m), 537 (m), 440 (m), 386 cmÀ1 (m); MS (EI, 70 eV):
m/z (%))=588 (M+, 23), 587 (80), 586 (100), 542 (11), 498
(3), 294 (2), 242 (4), 236 (3), 227 (3), 221 (6), 214 (7), 207
(8), 201 (5), 165 (5), 163 (2); HR-MS (EI, 70 eV): m/z=
586.19874, calcd. for C38H27F3NO2: 586.19884; anal. calcd.
for C38H28F3NO2 (587.21): C 77.67, H 4.80, N 2.38; found: C
77.49, H 4.658, N 2.089.
3-Chloro-2,5,6-triphenyl-4-[4-(trifluoromethyl)phenyl]pyr-
idine (11a): Colorless solid; yield: 43%; mp 164–1668C.
1H NMR (300 MHz, CDCl3): d=6.83–6.86 (m, 2H, CH),
6.98–7.05 (m, 3H, CH), 7.13–7.34 (m, 7H, CH), 7.44–7.52
(m, 5H, CH), 7.84–7.87 (m, 2H, CH); 13C NMR (75 MHz,
1
3
CDCl3): d=124.1 (q, JC,F =272.6 Hz, CF3), 124.7 (q, JC,F
=
3,5-Di(biphenyl-4-yl)-2,6-diphenyl-4-[4-(trifluoromethyl)-
phenyl]pyridine (10g): Colorless solid; yield: 73%; mp 281–
4.0 Hz, CH), 127.1 (CH), 127.7 (CH), 127.8 (CH), 127.8
2
(CH), 128.0 (CH), 128.8 (CH), 129.6 (q, JC,F =32.7 Hz, C),
1
2838C. H NMR (300 MHz, CDCl3): d=6.97–7.03 (m, 6H,
129.7 (CH), 129.9 (CH), 130.1 (CH), 130.8 (CH), 135.0 (C),
136.9 (C), 138.8 (C), 139.6 (C), 140.9 (C), 148.5 (C), 155.8
(C), 155.8 (C); 19F NMR (282.4 MHz, CDCl3): d=À62.1
CH), 7.23–7.56 (m, 26H, CH); 13C NMR (75 MHz, CDCl3):
d=124.0 (q, 1JC,F =273.4 Hz, CF3), 124.1 (q, 3JC,F =4.0 Hz,
CH), 126.1 (CH), 126.7 (CH), 127.3 (CH), 127.5 (CH), 127.6
˜
(CF3); IR (ATR): n=3056 (w), 3031 (w), 2927 (w), 1617
2
(CH), 128.6 (CH), 130.1 (q, JC,F =32.4 Hz, C), 130.2 (CH),
(w), 1543 (m), 1520 (w), 1491 (w), 1441 (w), 1395 (m), 1352
(w), 1319 (s), 1165 (m), 1128 (s), 1107 (m), 1067 (m), 1038
(w), 1020 (m), 957 (w), 926 (w), 847 (s), 786 (m), 758 (m),
750 (m), 697 (s), 664 (m), 651 (m), 624 (w), 600 (m), 561
(m), 533 (m), 461 (w), 433 (w), 403 cmÀ1 (w); MS (EI,
70 eV): m/z (%)=486 (M+, 47), 485 (61), 484 (100), 448
(10), 378 (4), 276 (8), 201 (5), 189 (6), 182 (6), 175 (2), 138
(2), 77 (3); HR-MS (ESI): m/z=486.12291, calcd. for
C30H20ClF3N ([M+H]+): 486.12309; anal. calcd. for
C30H19ClF3N (485.93): C 74.15, H 3.94, N 2.88; found: C
74.16, H 4.150, N 2.717.
130.8 (CH), 131.6 (CH), 133.0 (C), 136.8 (C), 139.0 (C),
140.2 (C), 140.4 (C), 142.1 (C), 148.8 (C), 156.6 (C);
19F NMR (282.4 MHz, CDCl3): d=À62.2 (CF3); IR (ATR):
˜
n=3081 (w), 3030 (w), 1615 (w), 1599 (w), 1487 (m), 1389
(m), 1318 (s), 1155 (m), 1123 (m), 1066 (m), 1019 (m), 1065
(m), 847 (m), 759 (s), 734 (m), 694 (s), 660 (m), 638 (w), 618
(m), 573 (w), 538 (w), 522 (w), 485 (w), 399 cmÀ1 (w); MS
(EI, 70 eV): m/z (%)=680 (M+, 26), 679 (82), 678 (100), 340
(2), 281 (2), 207 (2), 169 (2), 147 (12), 115 (2), 111 (2), 101
(2), 97 (3), 95 (2), 83 (4), 82 (4), 81 (2), 78 (6), 75 (23), 73
(9), 69 (12), 66 (16), 63 (7), 60 (11), 57 (8), 56 (3), 55 (7), 44
(35), 43 (15), 40 (12), 39 (8); HR-MS (ESI): m/z=
680.25619, calcd. for C48H33NF3 ([M+H]+): 680.25596.
3-Chloro-2,5,6-tri-para-tolyl-4-[4-(trifluoromethyl)phe-
nyl]pyridine (11b): Colorless solid; yield: 49%; mp 129–
1
1318C. H NMR (300 MHz, CDCl3): d=2.18 (s, 3H, CH3),
2,6-Diphenyl-3,4,5-tris[4-(trifluoromethyl)phenyl]pyridine
(10h): Colorless solid; yield: 70 mg (74%); mp 303–3058C.
1H NMR (300 MHz, CDCl3): d=6.82 (brd, 3JH,H =8.3 Hz,
2.24 (s, 3H, CH3), 2.41 (s, 3H, CH3), 6.69–6.72 (m, 2H, CH),
6.80–6.83 (m, 2H, CH), 6.94–6.96 (m, 2H, CH), 7.17–7.22
3
(m, 4H, CH), 7.28 (brd, JH,H =8.0 Hz, 2H, CH), 7.48 (brd,
3
2H, CH), 6.94 (brd, JH,H =8.3 Hz, 4H, CH), 7.12–7.29 (m,
3JH,H =7.8 Hz, 2H, CH), 7.73–7.77 (m, 2H, CH); 13C NMR
(75 MHz, CDCl3): d=21.1 (CH3), 21.2 (CH3), 21.4 (CH3),
1
16H, CH); 13C NMR (75 MHz, CDCl3): d=123.7 (q, JC,F
=
16
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Site Selective Synthesis of Pentaarylpyridines
1
3
˜
124.1 (q, JC,F =271.8 Hz, CF3), 124.7 (q, JC,F =3.9 Hz, CH),
IR (ATR): n=2994 (w), 2959 (w), 2835 (w), 1581 (m), 1547
127.3 (C), 128.3 (CH), 128.5 (CH), 128.6 (CH), 129.4 (q,
2JC,F =33.1 Hz, C), 129.6 (CH), 129.8 (CH), 130.0 (CH),
130.6 (CH), 134.0 (C), 134.6 (C), 136.0 (C), 136.6 (C), 136.9
(C), 137.5 (C), 138.7 (C), 141.2 (C), 148.4 (C), 155.4 (C),
155.6 (C); 19F NMR (282.4 MHz, CDCl3): d=À62.1 (CF3);
(m), 1513 (w), 1490 (m), 1460 (m), 1424 (m), 1350 (w), 1326
(s), 1289 (m), 1234 (m), 1171 (m), 1133 (w), 1118 (s), 1108
(s), 1069 (m), 1042 (s), 1027 (m), 992 (w), 942 (w), 873 (m),
842 (m), 786 (s), 755 (m), 702 (s), 602 (m), 560 (m), 524 (w),
486 (w), 454 (w), 432 (w), 409 (w), 382 cmÀ1 (w); MS (EI,
70 eV): m/z (%)=576 (M+, 54), 575 (76), 574 (100), 546 (5),
545 (7), 544 (6), 530 (4), 421 (2), 420 (2), 262 (3), 254 (3),
225 (2), 215 (3), 207 (4), 198 (2), 191 (3), 183 (4), 176 (6),
175 (4), 163 (3); HR-MS (ESI): m/z=576.15573, calcd. for
C33H26ClF3NO3 ([M+H]+): 576.15478; anal. calcd. for
C33H25ClF3NO3 (576.00): C 68.81, H 4.37, N 2.43; found: C
68.42; H 4.606, N 2.164.
˜
IR (ATR): n=3028 (w), 2923 (w), 2861 (w), 1907 (w), 1615
(w), 1503 (w), 1351 (m), 1319 (s), 1185 (m), 1165 (m), 1130
(s), 1107 (s), 1066 (s), 1019 (m), 956 (w), 878 (w), 849 (m),
830 (m), 813 (m), 795 (m), 754 (m), 730 (m), 720 (m), 680
(w), 650 (w), 633 (w), 537 (m), 526 (m), 480 (m), 448 (m),
407 cmÀ1 (w); MS (EI, 70 eV): m/z (%)=528 (M+, 46), 527
(66), 526 (100), 508 (2), 490 (5), 476 (3), 344 (1), 255 (2), 245
(2), 243 (2), 240 (2), 222 (3), 214 (3), 202 (5), 201 (3), 196
(6), 188 (5), 181 (2), 165 (2), 116 (2); HR-MS (ESI): m/z=
528.17098, calcd. for C33H26ClF3N ([M+H]+): 528.17004;
anal. calcd. for C33H25ClF3N (528.01): C 75.07, H 4.77, N
2.65; found: C 74.86, H 4.744, N 2.425.
3-Chloro-4-(4-methoxyphenyl)-2,5,6-triphenylpyridine
1
(11e): Colorless solid; yield: 54%; mp 206–2088C. H NMR
(300 MHz, CDCl3): d=3.74 (s, 3H, OCH3), 6.73–6.78 (m,
2H, CH), 6.85–6.87 (m, 2H, CH), 6.98–7.03 (m, 5H, CH),
7.14–7.16 (m, 3H, CH), 7.28–7.31 (m, 2H, CH), 7.39–7.50
(m, 3H, CH), 7.85–7.88 (m, 2H, CH); 13C NMR (75 MHz,
CDCl3): d=55.0 (OCH3), 113.1, 126.6, 127.5, 127.6 (CH),
127.9, 128.5 (CH), 128.7, 129.3 (C), 129.7, 129.9, 130.9, 131.0
(CH), 135.5, 137.6, 139.2, 140.0, 149.6, 155.5, 155.6, 158.7
3-Chloro-2,5,6-tris(4-methoxyphenyl)-4-[4-(trifluorome-
thyl)phenyl]pyridine (11c): Colorless solid; yield: 53%; mp
97–998C. 1H NMR (300 MHz, CDCl3): d=3.68 (s, 3H,
MeO), 3.73 (s, 3H, MeO), 3.85 (s, 3H, MeO), 6.54–6.59 (m,
2H, CH), 6.67–6.75 (m, 4H, CH), 6.97–7.02 (m, 2H, CH),
˜
(C); IR (ATR): n=3029 (w), 2924 (w), 2851 (w), 1608 (m),
3
7.19 (brd, JH,H =8.2 Hz, 2H, CH), 7.25–7.28 (m, 2H, CH),
1507 (m), 1396 (m), 1357 (m), 1289 (m), 1244 (s), 1172 (m),
1149 (m), 1030 (m), 838 (m), 743 (m), 695 (s), 562 (m),
537 cmÀ1 (m); MS (EI, 70 eV): m/z (%)=446 (M+, 33), 400
(19), 369 (91), 317 (100), 287 (67), 220 (22), 205 (71); HR-
MS (ESI): m/z=448.14655, calcd. for C30H23ClNO ([M+
H]+): 448.14627.
7.50 (brd, 3JH,H =8.2 Hz, 2H, CH); 13C NMR (75 MHz,
CDCl3): d=55.0 (MeO), 55.1 (MeO), 55.3 (MeO), 113.1
1
(CH), 113.4 (CH), 124.1 (q, JC,F =274.1 Hz, CF3), 124.7 (q,
2
3JC,F =3.9 Hz, CH), 126.9 (C), 129.4 (C), 129.4 (q, JC,F
=
33.0 Hz, C), 130.0 (CH), 131.1 (CH), 131.3 (CH), 131.9
(CH), 131.9 (CH), 132.2 (C), 133.8 (C), 141.3 (C), 148.6 (C),
154.9 (C), 155.3 (C), 158.3 (C), 159.2 (C), 156.0 (C);
19F NMR (282.4 MHz, CDCl3): d=À62.1 (CF3); IR (ATR):
3-Chloro-4-(4-methoxyphenyl)-2,5,6-tri-para-tolylpyridine
1
(11f): Colorless solid; yield: 34%; mp 142–1448C. H NMR
(300 MHz, CDCl3): d=2.19, (s, 3H, CH3), 2.25 (s, 3H, CH3),
2.40 (s, 3H, CH3), 3.75 (s, 3H, OCH3), 6.71–6.77 (m, 4H,
CH), 6.81–6.83 (m, 2H, CH), 7.17–7.21 (m, 2H, CH), 7.25–
7.28 (m, 2H, CH), 7.74–7.77 (m, 2H, CH); 13C NMR
(75 MHz, CDCl3): d=21.1 (CH3), 21.3 (CH3), 55.0 (OCH3),
113.1, 128.2, 128.3, 128.5, 129.6 (CH), 129.7 (C), 129.8, 130.8,
130.9 (CH), 134.7, 135.1, 136.0, 136.4, 137.1, 137.3, 138.3,
˜
n=3063 (w), 3003 (w), 2957 (w), 2935 (w), 2911 (w), 2837
(w), 1607 (m), 1578 (w), 1543 (w), 1515 (s), 1461 (m), 1393
(m), 1321 (s), 1288 (m), 1245 (s), 1174 (s), 1123 (s), 1108 (s),
1067 (s), 1023 (s), 911 (w), 826 (s), 802 (m), 780 (w), 732
(m), 649 (w), 636 (w), 609 (w), 551 (m), 537 (m), 407 cmÀ1
(w); MS (EI, 70 eV): m/z (%)=576 (M+, 62), 575 (93), 574
(100), 560 (5), 530 (3), 453 (3), 288 (6), 252 (4), 245 (4), 223
(3), 212 (3), 210 (2), 191 (5), 187 (3), 186 (3), 177 (3), 169
(7), 73 (2); HR-MS (ESI): m/z=576.15513, calcd. for
C33H26ClF3NO3 ([M+H]+): 576.15478.
˜
149.5, 155.2, 155.4, 158.5 (C); IR (ATR): n=3026 (w), 2918
(w), 2856 (w), 1610 (m), 1499 (m), 1391 (m), 1347 (m), 1293
(m), 1244 (s), 1183 (m), 1034 (m), 813 (s), 532 cmÀ1 (s); MS
(EI, 70 eV): m/z (%)=488 (M+, 61), 167 (26), 149 (75), 111
(24), 97 (36), 83 (38), 71 (64), 57 (100), 43 (85); HR-MS (EI,
70 eV): m/z=488.17753, calcd. for C33H27ClNO: 488.17757.
3-Chloro-2,5,6-tris(4-fluorophenyl)-4-(4-methoxyphenyl)-
pyridine (11g): Colorless solid; yield: 62%; mp 181–1838C.
1H NMR (300 MHz, CDCl3): d=3.75 (s, 3H, OCH3), 6.73–
6.79 (m, 6H, CH), 6.81–6.89 (m, 2H, CH), 6.92–6.97 (m,
2H, CH), 7.11–7.18 (m, 2H, CH), 7.21–7.21 (m, 2H, CH);
13C NMR (75 MHz, CDCl3): d=55.1 (OCH3), 113.3 (CH),
3-Chloro-2,5,6-tris(3-methoxyphenyl)-4-[4-(trifluorome-
thyl)phenyl]pyridine (11d): Colorless solid; yield: 38%; mp
130–1328C. 1H NMR (300 MHz, CDCl3): d=3.50 (s, 3H,
MeO), 3.57 (s, 3H, MeO), 3.86 (s, 3H, MeO), 6.39 (dd,
3
4JH,H =2.6 Hz, 4JH,H =2.4 Hz, 1H, CH), 6.46 (ddd, JH,H
=
7.5 Hz, 4JH,H =1.8 Hz, 4JH,H =1.1 Hz, 1H, CH), 6.59 (ddd,
3JH,H =8.3 Hz, 4JH,H =2.7 Hz, 4JH,H =1.1 Hz, 1H, CH), 6.74
3
4
4
(ddd, JH,H =8.2 Hz, JH,H =2.7 Hz, JH,H =1.2 Hz, 1H, CH),
6.86 (dd, 4JH,H =2.7 Hz, 4JH,H =2.1 Hz, 1H, CH), 6.91–7.00
(m, 3H, CH), 7.08 (dd, 3JH,H =7.7 Hz, 3JH,H =8.0 Hz, 1H,
CH), 7.23–7.25 (m, 2H, CH), 7.36–7.44 (m, 3H, CH), 7.51
2
2
114.7 (d, JC,F =21.6 Hz, CH), 114.9 (d, JC,F =21.6 Hz, CH),
2
115.0 (d, JC,F =21.6 Hz, CH), 128.8, 129.0 (C), 130.7 (CH),
131.6 (d, 3JC,F =8.1 Hz, CH), 132.5 (d, 3JC,F =8.1 Hz, CH),
(d, JH,H =8.0 Hz, 2H, CH); 13C NMR (75 MHz, CDCl3): d=
133.3 (d, JC,F =3.7 Hz, C), 134.5 (C), 134.9 (d, JC,F =3.7 Hz,
3
4
4
4
55.0 (MeO), 55.1 (MeO), 55.3 (MeO), 113.1 (CH), 114.3
C), 135.7 (d, JC,F =3.1 Hz, C), 150.0, 154.5, 154.8, 158.8 (C),
1
1
(CH), 114.5 (CH), 114.8 (CH), 115.2 (CH), 116.3 (CH),
161.5 (d, JC,F =247.3 Hz, CF), 162.3 (d, JC,F =248.1 Hz, CF),
1
1
122.1 (CH), 122.4 (CH), 123.4 (CH), 124.0 (q, JC,F
=
163.0 (d, JC,F =248.1 Hz, CF); 19F NMR (282 MHz, CDCl3):
3
273.4 Hz, CF3), 124.8 (q, JC,F =3.8 Hz, CH), 127.8 (C), 128.7
(CH), 128.9 (CH), 129.0 (CH), 129.6 (q, JC,F =32.5 Hz, C),
d=À112.1 (s, 1F, CF), À113.3 (s, 1F, CF), À114.0 (s, 1F,
2
˜
CF); IR (ATR): n=2922 (w), 2841 (w), 1601 (m), 1498 (s),
130.0 (CH), 134.9 (C), 138.1 (C), 139.9 (C), 140.7 (C), 140.8
(C), 148.4 (C), 155.4 (C), 155.6 (C), 158.9 (C), 159.0 (C),
159.2 (C); 19F NMR (282.4 MHz, CDCl3): d=À62.2 (CF3);
1391 (m), 1290 (m), 1218 (s), 1157 (s), 1033 (m), 831 (s), 752
(m), 539 (s); MS (EI, 70 eV): m/z (%)=500 (M+, 90), 223
(19), 179 (18), 160 (18), 149 (23), 112 (61), 109 (19), 105
Adv. Synth. Catal. 0000, 000, 0 – 0
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17
ÞÞ
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Sebastian Reimann et al.
(80), 97 (48), 83 (63), 77 (28), 69 (60), 57 (100), 43 (84);
HR-MS (ESI): m/z=502.1185, calcd. for C30H20ClF3NO
([M+H]+): 502.118.
137.5, 137.9, 143.0, 149.8, 155.8, 156.8, 157.8 (C); 19F NMR
(282 MHz, CDCl3): d=À61.9 (s, 3F, CF3); IR (ATR): n˜ =
2921 (w), 2853 (w), 1611 (m), 1501 (m), 1387 (m), 1320 (s),
1291 (m), 1246 (s), 1163 (s), 1123 (s), 1065 (s), 1015 (m), 817
(s), 666 cmÀ1 (m); MS (EI, 70 eV): m/z (%)=598 (M+, 100),
454 (12), 149 (16), 111 (19), 97 (28), 91 (18), 83 (25), 71 (38),
57 (54), 43 (26); HR-MS (EI, 70 eV): m/z=598.23489, calcd.
for C40H31Cl2F3NO: 598.23523.
3-Chloro-2,4,5,6-tetrakis(4-methoxyphenyl)pyridine (11h):
1
Slightly Yellow solid; yield: 40%; mp 171–1738C. H NMR
(300 MHz, CDCl3): d=3.62, (s, 3H, OCH3), 3.66 (s, 3H,
OCH3), 3.69 (s, 3H, OCH3), 3.78 (s, 3H, OCH3), 6.48–6.53
(m, 2H, CH), 6.60–6.64 (m, 2H, CH), 6.66–6.72 (m, 4H,
CH), 6.88–6.95 (m, 4H, CH), 7.16–7.21 (m, 2H, CH), 7.75–
7.80 (m, 2H, CH); 13C NMR (75 MHz, CDCl3): d=54.9,
55.0, 55.1, 55.2 (OCH3), 113.0, 113.1 (CH), 113.2 (CH),
127.9, 129.8, 130.2 (C), 130.8, 131.1, 131.2 (CH), 131.8 (C),
132.1 (CH), 132.7, 134.4, 149.7, 154.7, 155.0, 158.0, 158.5,
3-(4-Methoxyphenyl)-2,5,6-triphenyl-4-[4-(trifluorome-
thyl)phenyl]pyridine (12c): Colorless solid; yield: 77%; mp
236–2388C. 1H NMR (400 MHz, CDCl3): d=3.67 (s, 3H,
MeO), 6.54–6.57 (m, 2H, CH), 6.71–6.79 (m, 2H, CH),
6.85–6.91 (m, 4H, CH), 6.99–7.02 (m, 3H, CH), 7.15–7.22
(m, 8H, CH), 7.38–7.42 (m, 4H, CH); 13C NMR (100 MHz,
˜
159.0, 159.8 (C); IR (ATR): n=2920 (m), 2849 (w), 1718
3
(w), 1607 (m), 1497 (m), 1461 (m), 1395 (m), 1289 (m), 1243
(s), 1173 (s), 1030 (s), 828 (s), 801 (s), 728 (m), 546 cmÀ1 (s);
MS (EI, 70 eV): m/z (%)=537 (M+, 100), 539 (16), 313 (15),
149 (14), 99 (23), 85 (14), 71 (24), 57 (39); HR-MS (EI,
70 eV): m/z=537.16831, calcd. for C33H28ClNO4: 537.17014.
CDCl3): d=55.0 (MeO), 113.1 (CH), 123.9 (q, JC,F =4.0 Hz,
CH), 124.0 (q, 2JC,F =272.8 Hz, CF3), 126.6 (CH), 127.4
(CH), 127.5 (CH), 127.5 (CH), 127.5 (CH), 127.6 (CH),
128.2 (q, 2JC,F =32.6 Hz, C), 129.9 (C), 130.2 (CH), 130.2
(CH), 130.7 (CH), 131.1 (CH), 132.2 (CH), 133.0 (C), 133.4
(C), 137.9 (C), 140.4 (C), 140.6 (C), 142.3 (C), 149.0 (C),
156.3 (C), 156.8 (C), 158.1 (C); 19F NMR (282.4 MHz,
Synthesis of Pentaarylpyridines 12a–e Starting from
11
˜
CDCl3): d=À62.1 (CF3); IR (ATR): n=3044 (w), 3016 (w),
2970 (w), 2843 (w), 1605 (m), 1531 (m), 1458 (m), 1391 (m),
1326 (s), 1247 (m), 1159 (m), 1123 (s), 1067 (s), 1029 (m),
910 (w), 791 (w), 756 (m), 698 (m), 655 (m), 559 (m), 537
(m), 428 (w), 404 cmÀ1 (w); MS (EI, 70 eV): m/z (%)=558
(M+, 20), 557 (73), 556 (100), 512 (14), 281 (2), 278 (2), 268
(3), 256 (2), 254 (2), 249 (3), 241 (4), 233 (4), 220 (14), 214
(8), 208 (4), 194 (5), 168 (3), 157 (3), 77 (2); HR-MS (EI,
70 eV): m/z=556.18833, calcd. for C37H25F3NO: 556.18828.
3-(Biphenyl-4-yl)-2,5,6-triphenyl-4-[4-(trifluoromethyl)-
phenyl]pyridine (12d): Colorless solid; yield: 78%; mp 227–
An oven-dried and argon-flushed pressure tube was charged
with 3-chloro-2,4,5,6-tetraarylpyridine 11 (1.0 equiv.), PdCl2
ACHTUNGTRENNUNG(CH3CN)2 (5.0 mol%), SPhos (10.0 mol%), boronic acid
(2.5 equiv.) and K3PO4 (2.5 equiv.) followed by anhydrous
toluene (3.0 mL). The tube was sealed with a Teflon valve
and the reaction mixture was stirred at 1008C for 20 h. The
cooled reaction mixture was diluted with water and extract-
ed with DCM. The combined organic layers were dried
(Na2SO4), filtered and the filtrate was concentrated under
vacuum. The residue was purified by column chromatogra-
phy.
1
2298C. H NMR (400 MHz, CDCl3): d=6.87–6.90 (m, 2H,
CH), 6.92–6.96 (m, 4H, CH), 7.00–7.04 (m, 3H, CH), 7.17–
7.23 (m, 7H, CH), 7.26–7.31 (m, 3H, CH), 7.35–7.50 (m,
3-(4-Isopropylphenyl)-4-(4-methoxyphenyl)-2,5,6-triphen-
yl-pyridine (12a): Slightly yellow solid; yield: 98%; mp 189–
1918C. 1H NMR (300 MHz, CDCl3): d=1.12 (d, 6H, 3J=
1
8H, CH); 13C NMR (100 MHz, CDCl3): d=124.0 (q, JC,F
=
272.6 Hz, CF3), 124.0 (q, 3JC,F =3.6 Hz, CH), 126.2 (CH),
3
126.6 (CH), 126.8 (CH), 127.3 (CH), 127.5 (CH), 127.5 (C),
6.9 Hz, CH3), 2.74 (sept, 1H, J=6.9 Hz, CHi-Pr), 3.61 (s, 3H,
2
127.6 (CH), 127.6 (CH), 127.6 (CH), 128.4 (q, JC,F
=
OCH3), 6.42–6.47 (m, 2H, CH), 6.63–6.67 (m, 2H, CH),
6.76–6.79 (m, 2H, CH), 6.84–6.92 (m, 4H, CH), 6.98–7.02
(m, 3H, CH), 7.13–7.18 (m, 6H, CH), 7.35–7.42 (m, 4H,
CH); 13C NMR (75 MHz, CDCl3): d=23.8 (CH3), 33.5
(CHi-Pr), 54.9 (OCH3), 112.3, 125.4, 126.0 (CH), 127.1 (CH),
127.3 (CH), 127.4, 130.1, 130.2 (CH), 130.4 (C), 131.1, 131.3,
131.6, 133.8, 134.0, 135.7, 138.6, 141.0, 146.7, 149.8, 156.2,
32.2 Hz, C), 128.7 (CH), 130.2 (CH), 130.2 (CH), 130.8
(CH), 131.2 (CH), 131.6 (CH), 132.9 (C), 133.4 (C), 136.9
(C), 137.9 (C), 139.0 (C), 140.3 (C), 140.5 (C), 142.1 (C),
148.8 (C), 156.6 (C), 156.7 (C); 19F NMR (282.4 MHz,
˜
CDCl3): d=À62.1 (CF3); IR (ATR): n=3081 (w), 3051 (w),
3028 (w), 1617 (w), 1530 (w), 1388 (m), 1324 (s), 1166 (m),
1118 (m), 1067 (m), 1020 (w), 850 (m), 761 (m), 752 (m),
736 (m), 696 (s), 677 (m), 660 (m), 627 (w), 597 (w), 569
(w), 458 (w), 400 cmÀ1 (w); MS (EI, 70 eV): m/z (%)=604
(M+, 23), 603 (73), 602 (100), 524 (2), 404 (3), 377 (2), 354
(3), 352 (2), 345 (2), 301 (3), 292 (12), 291 (4), 281 (4), 264
(5), 259 (4), 252 (19), 250 (3), 245 (6), 227 (7), 226 (4), 208
(7), 207 (6), 191 (3), 176 (3), 163 (2), 149 (2), 146 (3), 118
(4); HR-MS (ESI): m/z=604.225, calcd. for C42H29F3N
([M+H]+): 604.22466; anal. calcd. for C42H28F3N (603.67): C
83.56, H 4.68, N 2.32; found: C 83.30, H 4.83, N 1.966.
˜
156.4, 157.6 (C); IR (ATR): n=2956 (w), 2923 (w), 2852
(w), 1731 (w), 1607 (w), 1510 (m), 1387 (m), 1244 (s), 1174
(m), 1028 (m), 835 (m), 753 (m), 693 (s), 671 (s), 564 cmÀ1
(m); MS (EI, 70 eV): m/z (%)=530 (M+, 92), 281 (15), 155
(100), 127 (43), 111 (23), 97 (40), 85 (51), 71 (90), 57 (98), 43
(57); HR-MS (ESI): m/z=532.2641, calcd. for C39H34NO
([M+H]+): 532.26349.
4-(4-Methoxyphenyl)-5-[4-(trifluoromethyl)phenyl]-2,3,6-
tri-para-tolylpyridine (12b): Colorless solid; yield: 93%; mp
188–1908C. 1H NMR (300 MHz, CDCl3): d=2.19, (s, 3H,
CH3), 2.27 (s, 6H, CH3), 3.63 (s, 3H, OCH3), 6.44–6.48 (m,
2H, CH), 6.58–6.63 (m, 2H, CH), 6.74–6.83 (m, 4H, CH),
6.95–7.01 (m, 6H, CH), 7.21–7.30 (m, 6H, CH); 13C NMR
(75 MHz, CDCl3): d=21.1 (CH3), 21.2 (CH3), 54.9 (OCH3),
2,3,6-Triphenyl-4,5-bis[4-(trifluoromethyl)phenyl]pyridine
1
(12e): Colorless solid; yield: 89%; mp 236–2388C. H NMR
(400 MHz, CDCl3): d=6.86–6.90 (m, 4H, CH), 6.99–7.06
(m, 5H, CH), 7.16–7.28 (m, 10H, CH), 7.33–7.40 (m, 4H,
1
CH); 13C NMR (100 MHz, CDCl3): d=123.6 (q, JC,F
=
1
3
112.6 (CH), 124.1 (q, JC,F =271.9 Hz, CF3), 124.3 (q, JC,F
=
3.7 Hz, CH), 128.2 (CH), 128.3 (CH), 130.1(CH), 131.0,
131.4, 131.6 (CH), 132.1, 133.5, 135.3, 135.6, 137.0, 137.2,
272.7 Hz, CF3), 124.1 (q, 1JC,F =272.6 Hz, CF3), 124.2 (q,
3JC,F =3.9 Hz, CH), 124.6 (q, JC,F =3.9 Hz, CH), 126.8 (CH),
3
18
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Adv. Synth. Catal. 0000, 000, 0 – 0
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Site Selective Synthesis of Pentaarylpyridines
3
127.6 (CH), 127.7 (CH), 127.7 (CH), 127.8 (CH), 127.8
6.1 Hz, CH3), 1.30 (d, 12H, J=6.1 Hz, CH3), 3.65 (s, 3H,
2
2
(CH), 128.7 (q, JC,F =32.7 Hz, C), 128.8 (q, JC,F =32.7 Hz,
C), 130.1 (CH), 130.1 (CH), 130.6 (CH), 131.1 (CH), 131.5
(CH), 131.9 (C), 133.5 (C), 137.5 (C), 140.0 (C), 140.2 (C),
141.6 (C), 142.0 (C), 148.7 (C), 156.6 (C), 157.3 (C);
19F NMR (282.4 MHz, CDCl3): d=À62.1 (CF3), À62.3
OCH3), 4.42 (sept, 2H, 3J=6.1 Hz, CH-CH3), 4.50 (sept,
2H, 3J=6.1 Hz, CH-CH3), 6.48 (d, 2H, 3J=8.8 Hz, CH),
6.57 (d, 4H, J=8.5 Hz, CH), 6.65 (d, 2H, J=8.8 Hz, CH),
3
3
3
3
6.69 (d, 4H, J=8.8 Hz, CH), 6.76 (d, 4H, J=8.8 Hz, CH),
7.34 (d, 4H, J=8.8 Hz, CH); 13C NMR (75 MHz, CDCl3):
3
˜
(CF3); IR (ATR): n=3085 (w), 3057 (w), 3033 (w), 1617
d=21.9, 22.0 (CH3), 54.9 (OCH3), 69.6, 69.8 (OCH), 112.4,
114.7, 115.4, (CH), 130.9, 131.2 (C), 131.5, 131.6 (CH), 131.6
(C), 132.4 (CH), 132.9, 155.6, 155.9, 157.1, 157.5 (C); IR
(m), 1534 (m), 1494 (w), 1392 (m), 1321 (s), 1165 (m), 1108
(m), 1067 (s), 1020 (m), 850 (m), 754 (m), 698 (s), 659 (m),
596 (w), 551 (w), 462 (w), 397 cmÀ1 (w); MS (EI, 70 eV): m/
z (%)=596 (M+, 16), 595 (61), 594 (100), 576 (4), 448 (2),
276 (2), 242 (1), 226 (2), 221 (3), 220 (3), 214 (2); HR-MS
(ESI): m/z=596.18118, calcd. for C37H24F6N ([M+H]+):
596.18075; anal. calcd. for C37H23F6N (595.58): C 74.62, H
3.89, N 2.35; found: C 74.23, H 3.609, N 2.192.
˜
(ATR): n=2974 (m), 2931 (w), 2836 (w), 1605 (m), 1510
(m), 1383 (m), 1284 (m), 1239 (s), 1179 (s), 1105 (s), 953 (s),
832 (s); MS (EI, 70 eV): m/z (%)=721 (M+, 100), 678 (17),
636 (10), 617 (11), 552 (20), 508 (3); HR-MS (ESI): m/z=
744.36595, calcd for C48H51NO5Na ([M+Na]+): 744.36594.
2,3,5,6-Tetrakis(4-fluorophenyl)-4-(4-methoxyphenyl)pyri-
dine (13d): Colorless solid; yield: 78%; mp 252–2548C.
1H NMR (400 MHz, CDCl3): d=3.65 (s, 3H, OCH3), 6.47–
6.51 (m, 2H, CH), 6.58–6.61 (m, 2H, CH), 6.70–6.75 (m,
4H, CH), 6.78–6.83 (m, 4H, CH), 6.84–6.90 (m, 4H, CH),
7.29–7.34 (m, 4H, CH); 13C NMR (100 MHz, CDCl3): d=
54.9 (OCH3), 112.8 (CH), 114.6 (d, 2JC,F =21.1 Hz, CH),
Synthesis of Pentaarylpyridines 13a–l Starting from 8
An oven-dried and argon-flushed pressure tube was charged
with 2,3,5,6-tetrachloro-4-arylpyridine 8a or 8b (1.0 equiv.),
PdCl2ACHTUNGTRENNUNG(CH3CN)2 (5.0 mol%), SPhos (10.0 mol%), boronic
2
114.7 (d, JC,F =21.9 Hz, CH), 129.6 (C), 131.3 (CH), 131.8
acid (8.0 equiv.) and K3PO4 (8.0 equiv.) followed by anhy-
drous toluene (6 mL); The tube was sealed with a Teflon
valve and the reaction mixture was stirred at 1008C for 20 h.
The cooled reaction mixture was diluted with water and ex-
tracted with DCM. The combined organic layers were dried
(Na2SO4), filtered and the filtrate was concentrated under
vacuum. The residue was purified by column chromatogra-
phy.
(d, 3JC,F =8.2 Hz, CH), 132.7 (d, 3JC,F =7.8 Hz, CH), 133.1
4
4
(C), 134.1 (d, JC,F =3.6 Hz, C), 136.4 (d, JC,F =2.8 Hz, C),
1
150.5, 155.6, 157.9 (C), 161.3 (d, JC,F =246.7 Hz, CF), 162.2
(d, 1JC,F =247.6 Hz, CF); 19F NMR (282 MHz, CDCl3): d=
˜
À113.8 (s, 2F, CF), À114.8 (s, 2F, CF); IR (ATR): n=2932
(w), 2832 (w), 1603 (m), 1510 (s), 1389 (m), 1247 (s), 1220
(s), 1156 (s), 1040 (m), 815 (s), 533 cmÀ1 (s); MS (EI,
70 eV): m/z (%)=560 (M+, 100), 516 (12), 244 (4), 183 (4);
HR-MS (EI, 70 eV): m/z=560.16315, calcd. for
C36H22F4NO: 560.16320; anal. calcd. for C36H23F4NO
(561.57): C 77.0, H 4.13, N 2.49; found: C 77.25, H 4.48, N
2.51.
4-(4-Methoxyphenyl)-2,3,5,6-tetraphenylpyridine
(13a):
1
Colorless solid; yield: 66%; mp 2218C. H NMR (300 MHz,
CDCl3): d=3.64 (s, 3H, OCH3), 6.45 (d, 2H, 3J=8.9 Hz,
3
CH), 6.69 (d, 2H, J=8.9 Hz, CH), 6.91–6.94 (m, 4H, CH),
7.01–7.06 (m, 6H, CH), 7.17–7.21 (m, 6H, CH), 7.39–7.43
(m, 4H, CH); 13C NMR (75 MHz, CDCl3): d=54.9 (OCH3),
112.5, 126.1, 127.2, 127.4, 127.4, 130.2 (CH), 130.3 (C), 131.3,
131.5 (CH), 134.0, 138.5, 140.8, 150.0, 156.4, 157.7 (C); IR
4-(4-Methoxyphenyl)-2,3,5,6-tetra-para-tolylpyridine
(13e): Colorless solid; yield: 61%; mp 234–2368C. H NMR
1
(300 MHz, CDCl3): d=2.18 (s, 6H, CH3), 2.26 (s, 6H, CH3),
3.63 (s, 3H, OCH3), 6.42–6.47 (m, 2H, CH), 6.60–6.64 (m,
2H, CH), 6.71–6.75 (m, 4H, CH), 6.79–6.81 (m, 4H, CH),
6.94–6.97 (m, 4H, CH), 7.25–7.29 (m, 4H, CH); 13C NMR
(75 MHz, CDCl3): d=21.1, 21.2 (CH3), 54.9 (OCH3), 112.3,
128.1, 130.1 (CH), 130.7 (C), 131.1, 131.5 (CH), 133.6, 135.4,
˜
(ATR): n=3056 (w), 2917 (m), 2869 (m), 1608 (w), 1510
(m), 1392 (m), 1290 (w), 1244 (s), 1179 (m), 1107 (s), 1029
(m), 756 (m), 697 cmÀ1 (s); MS (EI, 70 eV): m/z (%)=489
(M+, 66), 488 (100), 444 (13), 365 (3), 245 (2), 228 (2); HR-
MS (EI, 70 eV): m/z=488.20078, calcd for C36H26NO:
488.20089.
˜
136.9, 155.8, 157.5 (C); IR (ATR): n=3025 (w), 2918 (w),
1611 (m), 1499 (m), 1242 (s), 1171 (m), 1049 (m), 808 (s),
748 (m), 521 cmÀ1 (m); MS (EI, 70 eV): m/z (%)=544 (M+,
100), 529 (5), 500 (7), 234 (4), 227 (4), 220 (4), 69 (10), 44
(7); HR-MS (EI, 70 eV): m/z=544.26318, calcd. for
C40H34NO: 544.26349; anal. calcd. for C40H35NO (545.71): C
88.04, H 6.46, N 2.57; found: C 88.26, H 6.48, N 2.45.
2,3,5,6-Tetrakis(4-tert-butylphenyl)-4-(4-methoxyphenyl)-
pyridine (13b): Colorless solid; yield: 62%; mp 266–2678C.
1H NMR (300 MHz, CDCl3): d=1.22 (s, 18H, CH3), 1.26 (s,
18H, CH3), 3.64 (s, 3H, OCH3), 6.47 (d, 2H, 3J=8.9 Hz,
3
3
CH), 6.69. (d, 2H, J=8.9 Hz, CH), 6.80 (d, 4H, J=8.3 Hz,
3
3
CH), 7.02 (d, 4H, J=8.3 Hz, CH), 7.16 (d, 4H, J=8.7 Hz
CH), 7.31 (d, 4H, 3J=8.7 Hz, CH); 13C NMR (75 MHz,
CDCl3): d=31.2, 31.2 (CH3), 34.3, 34.4 (Ct-Bu), 55.0 (OCH3),
112.3, 124.1, 124.2, 129.8, (CH), 130.8 (C), 131.0, 131.7
(CH), 133.6, 135.8, 138.2, 148.8, 149.7, 156.2, 157.5 (C); IR
4-(4-Methoxyphenyl)-2,3,5,6-tetrakis[4-(trifluoromethyl)-
phenyl]pyridine (13f): Colorless solid; yield: 81%; mp 240–
1
2428C. H NMR (300 MHz, CDCl3): d=3.65 (s, 3H, OCH3),
6.47–6.52 (m, 2H, CH), 6.56–6.61 (m, 2H, CH), 7.00 (d, 4H,
3
3J=8.1 Hz, CH), 7.32 (d, 4H, J=8.1 Hz, CH), 7.41–7.47 (m,
˜
(ATR): n=2953 (m), 2902 (m), 2866 (m), 1609 (w), 1984
8H, CH); 13C NMR (75 MHz, CDCl3): d=55.0 (OCH3),
(m), 1460 (m), 1388 (m), 1362 (m), 1241 (s), 1176 (s), 1109
(m), 1016 (m), 827 cmÀ1 (s); MS (EI, 70 eV): m/z (%)=713
(M+, 100), 696 (5), 615 (27), 580 (42), 566 (5), 502 (4), 342
(5); HR-MS (ESI): m/z=714.46724, calcd for ([M+H]+)
C52H60NO: 714.46694.
1
1
113.1 (CH), 123.8 (q, JC,F =272.3 Hz, CF3), 123.9 (q, JC,F
=
272.1 Hz, CF3), 124.8 (q, 3JC,F =3.8 Hz, CH), 128.3 (CH),
2
129.5 (q, JC,F =32.9 Hz, C), 130.3, 131.2, 131.4 (CH), 133.5,
141.4, 143.4, 150.5, 155.7, 158.4 (C); 19F NMR (282 MHz,
CDCl3): d=À62.1 (s, 3F, CF3), À62.2 (s, 3F, CF3); IR
2,3,5,6-Tetrakis(4-isopropoxyphenyl)-4-(4-methoxyphen-
yl)-pyridine (13c): Colorless solid; yield: 93%; mp 181–
1838C. H NMR (300 MHz, CDCl3): d=1.25 (d, 12H, J=
˜
(ATR): n=2936 (w), 1616 (m), 1516 (m), 1321 (s), 1163 (s),
1
3
1106 (s), 1065 (s), 1015 (s), 853 (s), 833 (s), 669 (m); MS
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢂ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
19
ÞÞ
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FULL PAPERS
Sebastian Reimann et al.
1
(EI, 70 eV): m/z (%)=760 (M+, 100), 742 (5), 716 (10), 381
(5); HR-MS (EI, 70 eV): m/z=760.14943, calcd. for
C40H22F12NO: 760.15043; anal. calcd. for C40H23F12NO
(761.60): C 63.08, H 3.04, N 1.84; found: C 63.34, H 3.36, N
1.85.
1938C. H NMR (300 MHz, CDCl3): d=3.68 (s, 6H, MeO),
3.75 (s, 6H, MeO), 6.53–6.58 (m, 4H, CH), 6.69–6.76 (m,
8H, CH), 6.85–6.88 (m, 2H, CH), 7.19–7.22 (m, 2H, CH),
7.31–7.37 (m, 4H, CH); 13C NMR (75 MHz, CDCl3): d=
55.0 (MeO), 55.1 (MeO), 113.0 (CH), 113.2 (CH), 123.9 (q,
1
2,3,5,6-Tetrakis(4-ethoxyphenyl)-4-(4-methoxyphenyl)pyr-
idine (13g): Colorless solid; yield: 79%; mp 231–2338C.
1H NMR (300 MHz, CDCl3): d=1.30–1.37 (m, 12H, CH3),
3JC,F =3.8 Hz, CH), 124.1 (q, JC,F =271.2 Hz, CF3), 128.0 (q,
2JC,F =32.2 Hz, C), 130.4 (C), 130.7 (CH), 131.5 (CH), 132.1
(C), 132.2 (CH), 133.3 (C), 142.7 (C), 149.1 (C), 155.9 (C),
3
3.63 (s, 3H, OCH3), 3.88 (q, 4H, J=7.0 Hz, CH2), 3.96 (q,
158.0 (C), 159.0 (C); 19F NMR (282.4 MHz, CDCl3): d=
3
À1
˜
4H, J=7.0 Hz, CH2), 6.44–6.48 (m, 2H, CH), 6.51–6.56 (m,
À62.1 (CF3); IR (ATR, cm ): n=2999 (w), 2931 (m), 2834
4H, CH), 6.59–6.64 (m, 2H, CH), 6.65–6.70 (m, 4H, CH),
6.72–6.76 (m, 4H, CH), 7.29–7.34 (m, 4H, CH); 13C NMR
(75 MHz, CDCl3): d=14.7, 14.8 (CH3), 54.9 (OCH3), 63.0,
63.1 (CH2), 112.4, 113.4, 113.5 (CH), 130.8, 131.0 (C), 131.4,
131.5, 132.3 (CH), 132.8, 155.6, 157.0, 157.4, 158.1 (C); IR
(w), 1742 (m), 1604 (w), 1509 (m), 1440 (m), 1322 (m), 1245
(s), 1174 (s), 1023 (s), 962 (w), 840 (m), 824 (m), 805 (m),
765 (w), 668 (m), 648 (m), 630 (m), 541 (m), 389 cmÀ1 (m);
MS (EI, 70 eV): m/z (%)=648 (M+, 34), 647 (100), 646 (99),
603 (4), 602 (9), 324 (49), 299 (5), 293 (6), 274 (5), 272 (7),
269 (5), 249 (4), 248 (7), 245 (8), 228 (11), 214 (9), 213 (9),
200 (8), 156 (6); HR-MS (ESI): m/z=648.23596, calcd. for
C40H33F3NO4 ([M+H]+): 648.23562.
˜
(ATR): n=2979 (w), 2923 (w), 1605 (m), 1514 (m), 1388
(m), 1239 (s), 1172 (s), 1112 (s), 1040 (s), 824 (s), 655 (m),
553 cmÀ1 (s); MS (EI, 70 eV): m/z (%)=665 (M+, 100), 636
(8), 575 (11), 99 (14), 44 (10); HR-MS (EI, 70 eV): m/z=
665.31230, calcd. for C44H43NO5: 665.31357; anal. calcd. for
C44H43NO5 (665.82): C 79.37, H 6.51, N 2.10; found: C 78.89,
H 6.86, N 2.09.
2,3,5,6-Tetrakis(4-phenoxyphenyl)-4-[4-(trifluoromethyl)-
phenyl]pyridine (13k): Colorless solid; yield: 59%; mp 227–
1
2298C. H NMR (300 MHz, CDCl3): d=6.62–6.81 (m, 16H,
CH), 6.86–7.04 (m, 10H, CH), 7.15–7.27 (m, 10H, CH),
7.33–7.38 (m, 4H, CH); 13C NMR (75 MHz, CDCl3): d=
117.7 (CH), 118.2 (CH), 118.8 (CH), 119.2 (CH), 123.1
(CH), 123.4 (CH), 124.0 (q, 3JC,F =4.1 Hz, CH), 124.1 (q,
1JC,F =272.6 Hz, CF3), 128.5 (q, 2JC,F =32.6 Hz, C), 129.6
(CH), 129.7 (CH), 130.8 (CH), 131.5 (CH), 131.7 (CH),
132.5 (CH), 132.5 (C), 133.1 (C), 135.3 (C), 142.3 (C), 149.3
(C), 155.6 (C), 156.0 (C), 156.8 (C), 157.0 (C), 157.2 (C);
19F NMR (282.4 MHz, CDCl3): d=À62.1 (CF3); IR (ATR):
2,3,5,6-Tetraphenyl-4-[4-(trifluoromethyl)phenyl]pyridine
1
(13h): Colorless solid; yield: 68%; mp 237–2398C. H NMR
(300 MHz, CDCl3): d=6.85–6.91 (m, 6H, CH), 6.99–7.03
(m, 6H, CH), 7.15–7.19 (m, 8H, CH), 7.38–7.41 (m, 4H,
3
CH); 13C NMR (75 MHz, CDCl3): d=123.9 (q, JC,F =4.0 Hz,
CH), 123.9 (q, 1JC,F =272.6 Hz, CF3), 126.6 (CH), 127.5
2
(CH), 127.5 (CH), 127.6 (CH), 128.3 (q, JC,F =32.7 Hz, C),
130.2 (CH), 130.7 (CH), 131.1 (CH), 133.3 (C), 137.8 (C),
140.5 (C), 142.1 (C), 148.7 (C), 156.6 (C); 19F NMR
n=3042 (m), 1883 (w), 1608 (m), 1586 (m), 1508 (s), 1488
˜
˜
(282.4 MHz, CDCl3): d=À62.2 (CF3); IR (ATR): n=3056
(s), 1418 (w), 1390 (m), 1324 (m), 1286 (w), 1233 (s), 1198
(m), 1120 (m), 1108 (m), 1068 (m), 1014 (w), 913 (w), 869
(m), 812 (m), 765 (m), 691 (s), 633 (w), 553 (m), 496 (s),
408 cmÀ1 (w); MS (EI, 70 eV): m/z (%)=896 (M+, 47), 895
(100), 894 (66), 800 (2), 448 (3), 445 (2), 401 (2), 368 (5), 240
(3), 207 (2), 44 (1), 36 (2); HR-MS (ESI): m/z=896.29854,
calcd. for C60H41F3NO4 ([M+H]+): 896.29822.
(w), 1600 (w), 1533 (w), 1493 (w), 1442 (w), 1315 (m), 1167
(m), 1135 (m), 1106 (m), 1065 (m), 1019 (w), 846 (m), 755
(m), 697 (s), 656 (m), 626 (m), 598 (w), 532 (w), 487 (m),
431 cmÀ1 (w); MS (EI, 70 eV): m/z (%)=528 (M+, 16), 527
(62), 526 (100), 448 (3), 380 (2), 276 (3), 253 (3), 219 (4), 213
(3), 207 (4), 189 (4), 176 (3), 151 (2); HR-MS (ESI): m/z=
528.19391, calcd. for C36H25F3N ([M+H]+): 528.19336.
2,3,5,6-Tetra-para-tolyl-4-[4-(trifluoromethyl)phenyl]pyri-
dine (13i): Colorless solid; yield: 56%; mp 208–2108C.
1H NMR (300 MHz, CDCl3): d=2.19 (s, 6H, CH3), 2.27 (s,
6H, CH3), 6.72–6.75 (m, 4H, CH), 6.79–6.82 (m, 4H, CH),
6.86–6.89 (m, 2H, CH), 6.97–6.99 (m, 4H, CH), 7.17–7.20
(m, 2H, CH), 7.29–7.32 (m, 4H, CH); 13C NMR (75 MHz,
2,3,5,6-Tetrakis(3-methoxyphenyl)-4-[4-(trifluoromethyl)-
phenyl]pyridine (13l): Slightly yellow oil; yield: 69%).
1H NMR (300 MHz, CDCl3): d=3.55 (s, 6H, MeO), 3.65 (s,
6H, MeO), 6.48–6.50 (m, 2H, CH), 6.54–6.57 (m, 2H, CH),
6.65 (ddd, 3JH,H =8.1 Hz, 3JH,H =2.8 Hz, 3JH,H =0.9 Hz, 2H,
3
3
3
CH), 6.65 (ddd, JH,H =7.9 Hz, JH,H =2.8 Hz, JH,H =1.1 Hz,
2H, CH), 7.00–7.03 (m, 6H, CH), 7.10–7.23 (m, 4H, CH),
7.29–7.31 (m 2H, CH); 13C NMR (75 MHz, CDCl3): d=55.0
(MeO), 55.0 (MeO), 112.8 (CH), 114.2 (CH), 115.0 (CH),
3
CDCl3): d=21.1 (CH3), 21.2 (CH3), 123.8 (q, JC,F =4.0 Hz,
1
2
CH), 124.1 (q, JC,F =272.3 Hz, CF3), 128.1 (q, JC,F =33.7 Hz,
C), 128.2 (CH), 128.3 (CH), 130.1 (CH), 130.8 (CH), 131.0
(CH), 132.8 (C), 135.0 (C), 136.0 (C), 137.1 (C), 137.9 (C),
142.6 (C), 148.8 (C), 156.2 (C); 19F NMR (282.4 MHz,
3
116.6 (CH), 121.7 (CH), 123.8 (CH), 124.0 (q, JC,F =3.9 Hz,
1
2
CH), 124.1 (q, JC,F =273.0 Hz, CF3), 128.5 (q, JC,F =33.7 Hz,
C), 128.6 (CH), 128.7 (CH), 130.6 (CH), 133.2 (C), 139.1
(C), 141.6 (C), 142.2 (C), 148.6 (C), 156.2 (C), 158.8 (C),
158.9 (C); 19F NMR (282.4 MHz, CDCl3): d=À62.2 (CF3);
˜
CDCl3): d=À62.0 (CF3); IR (ATR): n=2919 (w), 1614 (w),
1532 (w), 1389 (m), 1350 (w), 1322 (s), 1184 (m), 1164 (m),
1127 (m), 1107 (s), 1067 (s), 1034 (m), 1019 (m), 850 (m),
830 (m), 811 (m), 757 (m), 734 (m), 669 (m), 652 (m), 637
(w), 572 (m), 553 (w), 523 (w), 494 (w), 443 cmÀ1 (m); MS
(EI, 70 eV): m/z (%)=584 (M+, 18), 583 (67), 582 (100), 460
(1), 363 (1), 292 (1), 282 (4), 281 (2), 276 (2), 262 (2), 256
(2), 241 (2), 234 (2), 228 (3), 226 (3), 207 (3), 189 (3); HR-
MS (ESI): m/z=584.25614, calcd. for C40H33F3N ([M+H]+):
584.25596.
˜
IR (ATR): n=3001 (w), 2937 (w), 2834 (w), 1598 (m), 1578
(s), 1534 (m), 1489 (w), 1453 (w), 1425 (m), 1407 (m), 1386
(m), 1322 (s), 1285 (m), 1238 (m), 1160 (m), 1119 (w), 1041
(s), 995 (w), 951 (w), 879 (m), 838 (m), 780 (s), 756 (m), 725
(m), 702 (s), 673 (w), 603 (w), 554 (m), 480 (w), 432 cmÀ1
(w); MS (EI, 70 eV): m/z (%)=648 (M+, 20), 647 (68), 646
(100), 631 (3), 630 (4), 588 (2), 111 (1), 97 (2), 95 (1), 83 (2),
81 (1), 71 (1), 70 (1), 69 (2), 57 (2), 55 (2), 44 (2), 43 (3);
HR-MS (ESI): m/z=648.23568, calcd. for C40H33F3NO4
([M+H]+): 648.23562.
2,3,5,6-Tetrakis(4-methoxyphenyl)-4-[4-(trifluoromethyl)-
phenyl]pyridine (13j): Colorless solid; yield: 68%; mp 191–
20
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Financial support by the State of Mecklenburg-Vorpommern
(scholarship of the interdisciplinary faculty of the University
of Rostock/Dept. LLM for S. R.) and by the Volkswagenstif-
tung (Project-lD Az 86 223) is gratefully acknowledged.
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Suzuki–Miyaura Cross-Coupling Reactions
Adv. Synth. Catal. 2014, 356, 1 – 23
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Stefanie Kohse, Anke Spannenberg, Annette E. Surkus,
Tariel V. Ghochikyan, Ashot S. Saghyan,
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