A Zwitterionic Palladium(II) Complex as a Precatalyst for Neat-Water-Mediated Cross-Coupling Reactions of Heteroaryl, Benzyl, and Aryl Acid Chlorides with Organoboron Reagents

Article abstract of DOI:10.1002/ejoc.201701241

The Suzuki–Miyaura cross-coupling (SMC) reactions of several heteroaryl chlorides, benzyl chlorides, and aryl acid chlorides with (hetero)arylboron reagents have been investigated in the presence of [Pd(HL1)(PPh₃)Cl₂] (I) [HL1 = 3-[(2,6-diisopropylphenyl)-1-imidazolio]-2-quinoxalinide] as catalyst and K₂CO₃ as base in neat water. The synthesis of the heterocycle-containing biaryls required the addition of 2 mol-% of a phosphine ligand (PPh₃ or X-Phos). A combination of more than 115 substrates were screened and it was found that I is a versatile catalyst that can produce heterocycle-containing biaryls, diarylmethanes, and benzophenones in moderate-to-excellent yields.

Full text of DOI:10.1002/ejoc.201701241

A Journal of
Accepted Article
Title: A Zwitterionic Palladium(II) Complex as a Precatalyst for Neat
Water Mediated Cross-Coupling Reactions of Heteroaryl, Benzyl
and Aryl Acid Chlorides with Organoboron Reagents
Authors: Ramakrishna Visannagari, Jhansi Rani Morla, and Dastagiri
Reddy Nareddula
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201701241
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10.1002/ejoc.201701241
European Journal of Organic Chemistry
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A Zwitterionic Palladium(II) Complex as a Precatalyst for Neat
Water Mediated Cross-Coupling Reactions of Heteroaryl, Benzyl
and Aryl Acid Chlorides with Organoboron Reagents
V. Ramakrishna,[a] M. Jhansi Rani,[a] and N. Dastagiri Reddy*[a]
Abstract: The Suzuki-Miyaura cross coupling (SMC) reactions of
several heteroaryl chlorides, benzyl chlorides and aryl acid chlorides
with (hetero)arylboron reagents were investigated in the presence of
strategy, the catalyst was used in conjunction with a phase
transfer reagent like tetrabutylammonium bromide.[8b],[8c],[8e]
There is only one report, which describes the synthesis of
[Pd(HL1)(PPh3)Cl2] (I) as a catalyst and K2CO3 as a base in neat water. diarylmethanes in neat water, known in the literature.[10] N-
Synthesis of heterocycle-containing biaryls required the addition of 2
mol% of a phosphine ligand (PPh3 or X-Phos). A combination of more
than 115 substrates were screened and found that I was a versatile
Methylimidazole coordinated (NHC)PdCl2 [NHC–Pd(II)–Im] was
employed as a catalyst for bringing about cross coupling reaction
between benzyl chlorides and arylboronic acids. To the best of
our knowledge, water mediated SMC reactions leading to the
synthesis of heterocycle-containing diarylmethane units have not
yet been reported. In the only example, which demonstrates the
synthesis of diheteroarylmethanes, dioxane was used as the
solvent.[11] Water as a solvent is not only economically viable but
also environmental friendly. Moreover, the products, which are
mostly insoluble in water, can easily be separated from the
reaction mixture. Recently, we synthesized a zwitterionic complex
I (Figure 1), which is found to be highly efficient in carrying out
Suzuki-Miyaura coupling of (hetero)aryl bromides and benzyl
bromides with organoboron reagents in neat water in the
presence of K2CO3 as a base.[12] Heteroaryl/benzyl chlorides have
the advantages over bromides and iodides of being cheaper,
more stable and readily available. Hence, we investigated the
efficiency of I in catalyzing the C–C bond coupling reactions of
various combinations of (hetero)aryl/benzyl chlorides and
(hetero)aryl-boronic acids/trifluroborates in neat water and the
results are reported herein.
Apart from the aforementioned biaryl and diarylmethane
derivatives, carbonyl building blocks such as unsymmetrical 1,2-
diarylethanones, dienones, benzophenones and β-alkoxyimino
carbonyl compounds can also be synthesized from the SMC
reactions.[13] Ketones are used as starting materials for the
preparation of oximes, acetals, carbazones, cyanohydrins,
pinacols, etc and these compounds are frequently found in
pharmaceuticals and fine chemicals.[14] The most common route
for the synthesis of diarylketones is the reaction between a aryl
halide and a organoboron reagent in presence of carbon
monoxide.[15] This method suffers from the setback of handling
toxic carbon monoxide. Recently, aryl amides and esters have
been coupled with organoboron reagents eliminating the usage of
carbon monoxide.[16] Research groups of Štěpnička and Bora
reported coupling reactions between acid halides, which are
cheaper than amides and esters, and organoboron reagents in
biphasic medium.[17] So far there are no economically viable
methods reported in neat water. Hence, we further examined the
suitability of I as a catalyst in the SMC reactions of benzoyl
chlorides with organoboronic acids in neat water.
catalyst,
which
produced
heterocycle-containing
biaryls,
diarylmethanes and benzophenones in moderate to excellent yields.
Introduction
The Suzuki-Miyaura coupling (SMC) is one of the most powerful
tools in the organic synthesis and a widely preferred reaction in
laboratory as well as in industry for the preparation of heterocycle-
containing biaryls and diarylmethanes.[1] These moieties are
frequently found in natural products, agrochemicals,
pharmaceutically active compounds, fine chemicals and
engineering materials such as conjugate polymers and liquid
crystals, and also serve as ligand precursors in supramolecular
chemistry.[2] In spite of the possibility of catalyst poisoning, which
arises due to the ability of heteroatom strongly binding to the
metal center,[3] the syntheses of (hetero)biaryls and heterocycle-
containing diarylmethanes have been successfully carried out
under the SMC conditions.[4] In most cases, an organic solvent or
an aqueous-organic mixture has been used as a reaction medium.
There is a plethora of catalyst systems, which work in neat water,
known for aryl/benzyl bromide substrates.[5],[6] However, catalysts,
which can effect coupling reactions for less reactive chloride
analogues are less common.[7] Among them, only a handful of
reports describe the coupling reactions of heteroaryl chlorides in
neat water under SMC conditions.[8] When water is used as the
reaction medium, the heteroatom present in the heterocycle is
preferably engaged in hydrogen bonding thereby reducing the
poisoning of the catalyst.[9] Therefore, the efficiency of the catalyst
is expected to increase in water. However, due to poor solubility
of catalysts, water has been discouraged as solvent. To overcome
this problem, water soluble ligands such as double sulfonated
fluorenyldicyclohexylphosphine[8d]
indenyldicyclohexylphosphine[8a] were used as ligands. In another
and
[a]
Prof. Dr. N. Dastagiri Reddy, V. Ramakrishna, M. Jhansi Rani
Department of Chemistry
Pondicherry University (A Central University)
Puducherry 605014, India
E-mail: ndreddy.che@pondiuni.edu.in
Supporting information for this article is given via a link at the end of
the document.
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10.1002/ejoc.201701241
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Table 1. Suzuki reactions of heteroaryl chlorides with simple arylboronic acids[a]
Entry
Heteroaryl
chloride 1
Boronic acid 2
Product 3
[b]Yie
ld
(%)
Figure 1. Zwitterionic Pd(II) complex I.
1
92
Results and Discussion
2
3
88
92
The zwitterionic Pd(II) complex I was prepared by following the
method reported in our earlier communication.[12] Encouraged by
the successful application of complex I in the synthesis of
heterocycle-containing biaryls from (hetero)/aryl bromides and
(hetero)/aryl boronic acids, investigations into the similar
reactions of analogous chlorides were carried out. In a typical
reaction, as we reported earlier, (hetero)/arly bromides reacted
with (hetero)/aryl boronic acids in neat water at 70 oC in presence
of 0.5 mol% of I and 2 equiv of K2CO3 to afford the corresponding
cross-coupled products in excellent yields (>90%) within 3 h. In
the present work, however, the reaction of 2-chloropyridine (1a)
with phenylboronic acid (2a), under similar conditions, did not
produce any coupled products in 3 h and even after 18 h at 100
oC, it gave the expected cross coupled product only in 40% yield.
The formation of a good amount of palladium black, which was
observed during the course of the reaction, indicated the
decomposition of the complex. Phosphine ligands have been
known to stabilize palladium thereby improving the longevity of
the active center in the reaction medium.[18] Hence a 2 mol% of
triphenylphosphine was added to the reaction mixture, which
produced the cross coupled product 2-phenylpyridine (3aa) in
excellent yield (92%). Once the reaction conditions were
optimized, the catalyst was explored for its scope in catalyzing the
reactions of various combinations of hetroaryl chlorides and
arylboronic acids. Based on partners, the results are categorized
into three sets viz. the reactions between i) heteroaryl chlorides
and arylboronic acids (Table 1), ii) aryl chloride (4-
chloroacetophenone) and heteroaryl boronic acids (Table 2), and
iii) heteroaryl chlorides and heteroarylboronic acids (Tables 3 and
4).
4
5
88
79
6
90
7
8
9
88
92
94
10
11
93
92
The cross-coupling of phenylboronic acid (2a) with a series of N-
heteroaryl chlorides resulted in the desired N-heteroaryl-
containing biaryls in good yields in 18 h (Table 1, entries 1–7).
Similarly, the corresponding coupled products were obtained in
excellent yields from various combinations of N-heteroaryl
chlorides and arylboronic acids (Table 1, entries 8–13).
Successful outcome of these reactions prompted us to explore
the efficiency of I for S-heteroaryl chloride substrates. Carrying
out coupling reactions on thiophene substrates is highly
challenging as thiophene, which is generally used as a reagent in
the poisoning test for Pd catalysts, has the great potential to
poison the catalyst compared to N-heteroaryl substrates.[19]
However, the SMC reactions of 2-acetyl-5-chlorothiophene (1i)
afforded the desired products in excellent yields surprisingly
within 3 h (Table 1, entries 14–17).
12
13
80
93
95
14[c]
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15[c]
87
92
88
2
3
82
71
16[c]
4
5
72
62
17[c]
[a]Reaction conditions: heteroaryl chloride (1.00 mmol), boronic acids (1.20
mmol), K2CO3 (2.00 mmol), water (3 mL), [Pd] (0.5 mol%), PPh3 (2 mol%),
reaction time 18 h, in air. [b]Isolated yields after column chromatography. [c]Time
3 h.
6
51
While biaryls containing one heteroaryl moiety and one aryl
moiety can be synthesized by a reaction between i) heteroaryl
halides and arylboronic acids or ii) aryl halides and
heteroarylboronic acids, the later method is yet to be reported in
water. Hence, we investigated the coupling of 4-
chloroacetophenone (1j) with various heteroarylboronic acids in
neat water (Table 2). Initial attempts to synthesize these biaryls
by employing 4-chloroacetophenone (1j) and 3-thiopheneboronic
acid (2f) or 4-dibenzofuranboronic acid (2g) were unsuccessful
and the reactions resulted in very low yields of the desired
products (<10% in case of 2f and 40% in case of 2g). It has been
demonstrated in the literature that sterically demanding and
electronically rich phosphines enhance catalytic ability of Pd
complexes.[20] Consequently, PPh3 was replaced by 2-
dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (X-Phos). The
yields were tremendously improved (Table 2, entries 1 and 2).
Under these conditions, four different types of heteroarylboronic
acids underwent coupling with 4-chloroacetophenone (1j) (Table
2, entries 3–6) and produced corresponding cross coupled
products in moderate to good yields. The reactions of 3-
thiopheneboronic acid (2f) and benzofuranboronic acid (2k) with
4-chloroacetophenone (1j) gave less yields presumably due to
protodeboronation (Table 2, entries 1 and 6).[21] Hence, the
heteroarylboronic acids were used in excess (1.5 equiv). Indole-
5-boronic acid (Table 2, entry 3) also underwent coupling without
requiring a protection to the N-H group.
[a]Reaction conditions: 4-chloroacetophenone (0.50 mmol), boronic acid (0.75
mmol), K2CO3 (1.00 mmol), water (2 mL), [Pd] (0.5 mol%), X-Phos (2 mol%),
reaction time 8 h, in air. [b]Isolated yields after column chromatography.
Table 3 lists the reactions of 2-acetyl-5-chlorothiophene (1i) with
a series of heteroaryl boronic acids in the presence of I/X-Phos.
The targeted molecules, heteroaryl-substituted thiophenes, are
often found in drug candidates, conjugate polymers and functional
materials.[22],[23] The heteroarylboronic acids such as 4-
dibenzofuranboronic acid (2g), 4-dibenzothiopheneboronic acid
(2i), 1-thianthrenylboronic acid (2j) and indole-5-boronic acid (2h)
were effectively coupled with 2-acetyl-5-chlorothiophene (1i) to
produce the heteroaryl-substituted thiophene products in good
yields (Table 3, entries 1, 2, 5 and 6). It was observed that 2-
benzofuranboronic acid (2k) and 2-benzothiopheneboronic acid
(2l) afforded the cross coupled products in somewhat low yields
(Table 3, entries 3 and 4).
Table 3. Suzuki reactions of various heteroarylboronic acids with 2-acetyl-5-
chlorothiophene in water[a]
Entr
y
Heteroaryl
chloride 1
Boronic acid 2
Product 3
[b]Yie
ld
Table 2. Suzuki reactions of 4-chloroacetophenone with various
heteroarylboronic acids in water[a]
(%)
1
2
3
72
71
51
Entr
y
Aryl chloride
Boronic acid 2
Product 3
[b]Yie
ld
(%)
1
1
40
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4
48
3
4
55
60
5
6
64
62
5
6
62
65
[a]Reaction conditions: 2-acetyl-5-chlorothiophene (0.50 mmol), boronic acid
(0.75 mmol), K2CO3 (1.00 mmol), water (2 mL), [Pd] (0.5 mol%), X-Phos (2
mol%), reaction time 3 h, in air. [b]Isolated yields after column chromatography.
Heterobiaryl structures are present in drugs like Gleevec, an
anticancer drug, PDE-IV inhibitor and bioactive natural products,
such as diazonamide A, dragmacidin D and F.[24] To the best of
our knowledge, there are no reports on Suzuki–Miyaura coupling
of heteroaryl chlorides with heteroarylboron reagents in neat
water present in the literature. In the present study, a total of nine
heterobiaryls were synthesized using I/XPhos catalyst system in
moderate to good yields (Table 4). These heterobiaryls are also
used as supporting ligands in organometallic complexes of
heavier transition metals.[25] The cross-coupling of six-membered
N-heteroaryl chlorides such as 2-chloro-5-methylpyridine (1d), 2-
chloropyrazine (1f) and 1-chloroisoquinoline (1h) with 4-
dibenzofuranboronic acid (2g) were carried out successfully and
the corresponding hetrobiaryls were obtained in good yields
(Table 4, entries 1–3). Sulfur containing boronic acids 4-
dibenzothiopheneboronic acid (2i) and 1-thianthrenylboronic acid
(2j) also afforded coupled products with 2-chloro-5-nitropyridine
(1e), 2-chloropyrazine (1f), 2-chloropyridine (1a) and 2-
chloroquinoline (1g) in good yields (Table 4, entries 4–9).
However, surprisingly, 2-benzofuranboronic acid, indole-5-
boronic acid, 3-thiopheneboronic acid and 2-methoxy-5-
pyridineboronic acid did not react with 2-chloropyridine (1a) under
similar conditions.
7
8
75
78
9
72
[a]Reaction conditions: heteroaryl chloride (0.50 mmol), boronic acid (0.75
mmol), K2CO3 (1.00 mmol), water (2 mL), [Pd] (0.5 mol%), X-Phos (2 mol%),
reaction time 18 h, in air. [b]Isolated yields after column chromatography.
Potassium organotrifluoroborates are promising alternatives to
organoboronic acids. The advantages of these salts are easy
preparation, air/moisture stability, long shelf life at room
temperature and no formation of cyclic dimers or trimers.[26]
Hence, we explored the reactions of organotrifluoroborates with
heteroaryl chlorides using I/X-Phos in water and the results are
summarized in Table 5. 2-Chloropyrazine (1f), 2-chloroquinoline
(1g) and 3-chloropyridine (1b) were successfully coupled with
various potassium aryltrifluoroborates to afford the desired
products in excellent yields (Table 5, entries 1–3). The I/X-Phos
system in water was also found to be effective in bringing about
the cross coupling reaction between potassium dibenzofuran-4-
trifluoroborate (4g) and heteroaryl chlorides. The corresponding
coupled products are furnished in Table 5 (entries 4–6).
Table 4. Suzuki reactions of N-heteroaryl chlorides with heteroarylboronic
acids[a]
Entr
y
Heteroaryl
chloride 1
Boronic acid 2
Product 3
[b]Yie
ld
Table 5. The couplings between potassium (hetero)aryltrifluoroborates and
heteroaryl chlorides[a]
(%)
1
2
65
75
Entr
y
Heteroaryl
chloride 1
Trifluoroborate
Product 3
[b]Yie
ld
4
(%)
1
85
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2
92
Entr
y
Benzyl
chloride 5
Boronic acid 2
Methylene linked
[b]Yie
ld
diaryl 6
(%)
3
4
93
1
2
95
92
68[c]
5
6
62
61
3
4
86
88
5
75
[a]Reaction conditions: heteroaryl chloride (0.50 mmol), potassium
aryltrifluoroborate (0.75 mmol), K2CO3 (1.00 mmol), water (2 mL), [Pd] (0.5
mol%), X-Phos (2 mol%), reaction time 18 h, in air. [b]Isolated yields after column
chromatography, [c]reaction time 3 h.
6
7
77
86
The versatility of the zwitterionic complex I in effecting the cross-
coupling for a wide variety of aryl halides prompted us to
investigate whether the noticed high activity was applicable to
sp3(C)−sp2(C) cross-coupling reactions too. The SMC reactions
of various combinations of benzyl chlorides (5) and arylboronic
acids (2) were carried out in neat water using I as a catalyst and
K2CO3 as a base at 100 oC. A facile sp3(C)−sp2(C) coupling
occurred and diarylmethanes (6) were obtained in excellent yields
within 3 h (Table 6). The coupling reactions of benzyl chloride (5a)
and 1-chloromethylnaphthalene (5b) with phenylboronic acid (2a),
which were conducted as probe reactions, afforded
diphenylmethane (6aa) and 1-benzylnaphthalene (6ba)
respectively in excellent yields (Table 6, entries 1 and 2). Similarly,
the reactions of benzyl chlorides bearing functional groups such
as methyl (−CH3), fluoro (−F) and methoxy (−OCH3), and 1/2-
(chloromethyl)naphthalene with 4-ethylpheylboronic acid (2e)
resulted in the cross-coupled products in good to excellent yields
(Table 6, entries 3−8). 2-Methylbenzyl chloride (5g) reacted with
phenylboronic acids possessing methyl (−CH3), aldehyde (−CHO)
and methoxy (−OCH3) groups, and 1-naphthaleneboronic acid
(2o) to give the corresponding cross-coupled products in
excellent yields (Table 6, entries 9−12). Similarly, reactions of 1
and 2-(chloromethyl)naphthalenes (5b and 5f) with 1-
naphthaleneboronic acid (2o) and phenylboronic acids having
fluorine and aldehyde functional groups resulted in the
corresponding cross-coupled diarylmethanes in good yields
(Table 6, entries 13−15). It is noteworthy that sterically
encumbered ortho substituted 2-methoxybenzyl chloride (5e) and
2,4,6-trimethylbenzyl chloride (5h) also produced cross-coupled
products in good yields (Table 6, entries 6 and 16−19).
8
9
88
78
10
11
87
92
12
13
85
83
14
82
Table 6. Suzuki-Miyaura sp3(C)−sp2(C) cross coupling of benzyl chlorides with
arylboronic acids in neat water[a]
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15
92
1
2
95
92
16
17
18
81
78
88
3
4
93
72
5
6
90
88
19
86
[a]Reaction conditions: benzyl chloride (1.00 mmol), boronic acid (1.20 mmol),
K2CO3 (2.00 mmol), water (3 mL), [Pd] (0.5 mol%), reaction time 3 h, in air.
[b]Isolated yields after column chromatography.
7
8
85
86
The Suzuki-Miyaura reaction of equimolar mixtures of
chlorobenzyl chlorides, which contain chlorine atoms on both sp3
and sp2 carbons, and arylboronic acids resulted in selective cross-
coupling at sp3 carbon with high yields. The reactions of 4/3-
chlorobenzyl chloride (5i and 5j) with arylboronic acids, including
two heteroarylboronic acids, progressed smoothly under the
optimized reaction conditions and afforded exclusively the
corresponding diarylmethanes in excellent yields (Table 7, entries
1−8). The chlorine atom on the aromatic ring remained intact even
when excess of boronic acid was used under the reaction
conditions. Chemoselectivity favoring benzylic chloride over aryl
chloride in the SMC reactions is quite common and is frequently
reported in the literature.[27] Interestingly, even when Cl is
replaced by Br on the aromatic ring, preference for benzylic
chloride was observed. When 4-bromobenzyl chloride (5k) was
treated with one equiv of phenylboronic acid (2a), a mixture
containing 40% of diarylmethane (with Br intact), 40% of
arylbiarylmethane (double cross-coupled product), 10% of biaryl
(with Cl intact) and 10% of 5k was obtained (from 1H NMR
spectra). However, arylbiarylmethanes were the sole products
when two equiv of arylboronic acids were used (Table 7, entries
9−12).
9[c]
88
78
87
10[c]
11[c]
12[c]
92
[a]Reaction conditions: benzyl chloride (1.00 mmol), boronic acid (1.20 mmol),
K2CO3 (2.00 mmol), water (3 mL), [Pd] (0.5 mol%), reaction time 3 h, in air.
[b]Isolated yields after column chromatography, [c]Benzyl chloride (0.50 mmol).
Table 7. Suzuki coupling reactions of chloro/bromo-benzyl chlorides[a]
A thorough literature search revealed the synthesis of heteroaryl
containing diarylmethanes had been limited only to three
examples and these routes require organic or biphasic media.[28]
Hence, the reactions of
a
few benzyl chlorides with
Entr
y
Benzyl
chloride 5
Boronic acid 2
Methylene linked
[b]Yie
ld
(%)
heteroarylboronic acids were conducted in neat water under the
optimized conditions and the results are listed in Table 8. A total
of seven heteroarylboronic acids were tested with various benzyl
chlorides as coupling partners. Initial runs using 3-
thiopheneboronic acid (2f) and eight different benzyl chlorides
containing various substituents resulted in the desired products in
excellent yields (Table 8, entries 1−6). The cross-coupling of
diaryl 6
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12[c]
65
benzyl chlorides with heteroarylboronic acids bearing
benzothiophene, benzofuran, dibenzofuran, dibenzothiophene,
thianthrene and pyridine moieties also afforded benzylated
heteroarenes in good yields (Table 8, entries 7−15). The catalyst
was also able to bring about the cross coupling reaction between
2-chloro-5-(chloromethyl)pyridine (1i) and (hetero)arylboronic
acids leading to the formation heteroaryl containing
diarylmethane derivatives including a diheteroarylmethane (Table
8, entries 16−19).
13[c]
14[c]
15[c]
78
76
51
Table 8. Synthesis of heteroaryl-containing diarylmethanes in neat water[a]
Entr
y
Benzyl
chloride 5
Boronic acid 2
Methylene linked
[b]Yie
ld
diaryl 6
(%)
1
2
3
4
95
90
89
88
16
17
87
85
18[d]
65
[a]Reaction conditions: benzyl chloride (1.00 mmol), boronic acid (1.20 mmol),
K2CO3 (2.00 mmol), water (3 mL), [Pd] (0.5 mol%), reaction time 3 h, in air.
[b]Isolated yields after column chromatography, [c]boronic acid (1.50 mmol),
[d]PPh3 (2 mol%).
5
6
86
88
The sp3(C)−sp2(C) cross coupling reactions have also been
carried out between potassium aryltrifluoroborates and benzyl
chlorides in the presence of I, which revealed that the catalyst was
also highly efficient in catalyzing these reactions. All the
substrates employed in the study produced the cross coupled
products in excellent yields within 3 h. In total, 18 combinations of
the reagents were employed and the results are listed in Table 9.
7[c]
78
Table 9. Suzuki Muyara coupling reaction of benzyl chlorides with potassium
aryltrifluoroborates[a]
8[c]
87
91
9[c]
Entr
y
Benzyl
chloride 5
Trifluoroborate
Methylene linked
[b]Yie
ld
4
diaryl 6
(%)
10[c]
71
77
1
2
95
90
11[c]
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3
91
88
18
78
4
[a]Reaction conditions: benzyl chloride (1.00 mmol), organoboron reagent (1.20
mmol), K2CO3 (2.00 mmol), water (3 mL), [Pd] (0.5 mol%), reaction time 3 h, in
air. [b]Isolated yields after column chromatography.
5
6
85
87
Further, the catalyst
I
was examined for producing
benzophenones (8) from benzoyl chlorides (7) and arylboronic
acids (2) in neat water at room temperature (Table 10). The model
coupling reactions were done between phenylboronic acid and
the acid chlorides benzoyl chloride (7a) and 4-chlorobenzoyl
chloride (7b) (Table 10, entries 1 and 2), which produced the
corresponding biaryl ketones in excellent yields. Under similar
conditions, 7b underwent coupling with several boronic acids,
including 4-dibenzofuranboronic acid (2g) (Table 10, entries 3−9).
Further, the reaction protocol was successfully applied in the
preparation of various unsymmetrical benzophenones in good to
excellent yields from their corresponding partners (Table 10,
entries 10−15). In case of 4-nitrobenzoyl chloride (7c), heating
was required due to its poor solubility in water (Table 10, entries
11 and 12). As the acid chlorides are susceptible to hydrolysis in
water they were used in slight excess (1.2 equiv).
7
8
86
88
9
78
Table 10. The cross-coupling of acid chlorides with boronic acids in neat water[a]
10
11
76
72
Entr
y
Acid
chloride 7
Boronic acid 2
Ketone 8
[b]Yie
ld
(%)
12[c]
71
88
1
2
95
13
92
14
15
86
82
3
4
5
91
93
77
16
17
85
70
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10.1002/ejoc.201701241
European Journal of Organic Chemistry
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6
84
the catalyst increased in the presence of phosphine ligands such
as PPh3 and X-Phos. The I/K2CO3/water system was also
successfully utilized in the preparation of heterocycle containing
diarylmethanes and diarylketones from the corresponding
benzyl/acid chlorides and organoboronic acids in excellent yields,
and these reactions do not require the addition of phosphines
(except in one case, where PPh3 is required). This is the first time
that a neat water mediated synthesis of biheteroaryls, heterocycle
containing diarylmethanes and diarylketones from chloro
substrates are reported. It is noteworthy that I is a unique catalyst,
which catalyzes all the three types of aforesaid reactions. Though
there are several advantages of using water as a solvent in SMC
reactions, challenge of arresting protodeboronation in
heteroboronic acids, which is reportedly enhanced by polar protic
solvents,[29] is yet to be addressed. Currently, we are working
towards developing catalyst systems, which can function at
reduced temperatures thereby decreasing protodeboronation and
homocoupling observed in some cases.
7
8
9
83
54
71
10
11
92
Experimental Section
82[c]
General considerations: All manipulations were carried out under open
atmosphere. [Pd(HL1)(PPh3)Cl2] (I) was prepared by following a method
mentioned
in
our
earlier
communication.[12]
Potassium
(hetero)aryltrifluoroborates were prepared by following the literature
procedures.[30] All commercially available chemicals including (hetero)aryl
chlorides, benzyl chlorides, benzoyl chlorides and boronic acids were used
as received. Analytical thin-layer chromatography was performed using
pre-coated silica gel 60 F254 plates and UV light at 254 nm. 1H and 13C{1H}
spectra were recorded on a Bruker 400 MHz instrument and, 19F spectra
were recorded on a Bruker 500 MHzinstrument. HR-MS were recorded on
an Agilent 6540 UHD Q-TOF mass spectrometer. IR spectra were
recorded on a Jasco 4100 FT-IR spectrometer.
12
13
78[c]
88
General procedure for Suzuki–Miyaura cross-coupling reactions: To
a 13 X 90 mm test tube with a stir bar were added boronic acid (0.75 - 1.2
mmol), K2CO3 (1 - 2 mmol), Pd catalyst (0.5 mol%), [preparation of
heterocycle-containing biaryls required the addition of 2 mol% of PPh3 or
X-Phos], and aryl/benzyl/benzoyl chloride (0.5 - 1.2 mmol) in water (2 - 3
mL) and the resulting mixture was stirred in an oil bath at 100 °C under
open atmosphere. The progress of the reaction was monitored by TLC and
with 1H NMR Spectroscopy. When there was no more significant
conversion of aryl halide noticed, the reaction mixture was cooled to room
temperature, mixed with water (5 mL) and extracted with diethyl ether (3 X
10 mL). The organic phase was dried with Na2SO4 and the solvent was
removed using a rotary evaporator. The crude product was purified by
column chromatography using a mixture of hexane/ethyl acetate as eluent
on silica gel (230 - 400 mesh). The identity of the reported products was
confirmed by comparing the NMR (1H NMR) data with the reported in the
14
15
82
91
[a]Reaction conditions: acid chloride (1.20 mmol), boronic acid (1.10 mmol),
K2CO3 (2.00 mmol), water (3 mL), [Pd] (0.5 mol%), reaction time 3 h, in air.
[b]Isolated yields after column chromatography, [c]at 80 °C.
literature and the new compounds were characterized by the NMR (1H, 13
19F NMR) spectroscopy, IR and the ESI-MS.
C
&
Analytical data for heterobiaryls:
Conclusions
2-Phenylpyridine (3aa) (entry 1 of table 1)[31]: Yield: 92% (0.141 g); Rf =
0.33 (ethyl acetate/hexane 1:49); 1H NMR (400 MHz, CDCl3): δ 8.70 (d,
1H), 8.00 – 7.98 (m, 2H), 7.70 (m, 2H), 7.50 – 7.40 (m, 3H), 7.21 – 7.17
(m, 1H) ppm.
In summary, the zwitterionic Pd(II) complex I was found to be
highly active in bringing about the cross coupling reactions
between i) heteroaryl chlorides and arylboronic acids ii) 4-
chloroacetophenone and heteroarylboronic acids and iii)
heteroaryl chlorides and heteroarylboronic acids/trifluoroborates
in neat water leading to the synthesis of heterocycle containing
biaryls. Except in few cases, the desired products were obtained
in good to excellent yields. It was observed that the efficiency of
3-Phenylpyridine (3ba) (entry 2 of table 1)[31]: Yield: 88% (0.135 g); Rf =
0.32 (ethyl acetate/hexane 1:49); 1H NMR (400 MHz, CDCl3): δ 8.87 (s,
1H), 8.61 (s, 1H), 7.98 (d, 1H), 7.58 (d, 2H), 7.48 (m, 2H), 7.42 – 7.38 (m,
2H) ppm.
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2-Methyl-6-phenylpyridine (3ca) (entry 3 of table 1)[31]: Yield: 92% (0.154
1-(5-Phenylthiophene-2-yl)ethanone (3ia) (entry 14 of table 1)[37]: Yield:
95% (0.190 g); Rf = 0.48 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz,
CDCl3): δ 7.66 – 7.64 (m, 3H), 7.43 – 7.31 (m, 4H), 2.56 (s, 3H) ppm.
g); Rf
=
0.33 (ethyl acetate/hexane 1:49); 1H NMR (400 MHz,
CDCl3): δ 7.99 (dd, 2H), 7.64 – 7.60 (m, 1H), 7.52 – 7.40 (m, 4H), 7.10 (d,
1H), 2.64 (s, 3H) ppm.
1-(5-(4-Ethylphenyl)thiophen-2-yl)ethanone (3ie) (entry 15 of table 1):
Obtained as a white solid; Yield: 87% (0.199 g); mp: 101 – 103 °C; Rf =
0.35 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 7.64 (d, J
= 4.0 Hz, 1H), 7.57 (d, J = 8.2 Hz, 2H), 7.26 (dd, J = 13.7, 6.1 Hz, 3H),
2.67 (q, J = 7.6 Hz, 2H), 2.55 (s, 3H), 1.26 (t, J = 7.6 Hz, 3H) ppm; 13C
NMR (100 MHz, CDCl3): δ 190.7, 153.2, 145.7, 142.7, 133.6, 130.9, 128.7,
126.4, 123.5, 28.8, 26.6, 15.5 ppm; IR (KBr): 2963, 2869, 1648, 1533,
1442, 1353, 1277, 1029, 919, 802 cm-1; HRMS (ESI): m/z calcd for
C14H15OS [M + H]+ 231.0843, found 231.0839.
5-Methyl-2-phenylpyridine (3da) (entry 4 of table 1)[31]: Yield: 88%
(0.148 g); Rf = 0.32 (ethyl acetate/hexane 1:49); 1H NMR (400 MHz,
CDCl3): δ 8.52 (s, 1H), 7.97 (m, 2H), 7.62 (d, 1H), 7.55 (dd, 1H), 7.46 (m,
2H), 7.41 – 7.37 (m, 1H), 2.36 (s, 3H) ppm.
5-Nitro-2-phenyl-pyridine (3ea) (entry 5 of table 1)[32]: Yield: 79% (0.158
g); Rf = 0.48 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ
9.49 (s, 1H), 8.52 (dd, 1H), 8.08 (m, 2H), 7.91 (d, 1H), 7.52 (m, 3H) ppm.
2-Phenylpyrazine (3fa) (entry 6 of table 1)[33]: Yield: 90% (0.139 g); Rf =
0.42 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 9.02 (d,
1H), 8.61 (s, 1H), 8.49 (d, 1H), 8.01 (d, 2H), 7.50 (m, 3H) ppm.
1-(5-(4-Fluorophenyl)thiophene-2-yl)ethanone (3ic) (entry 16 of table
1)[37]: Yield: 92% (0.201 g); Rf = 0.44 (ethyl acetate/hexane 1:19); 1H NMR
(400 MHz, CDCl3): δ 7.64 – 7.59 (m, 3H), 7.25 – 7.08 (m, 3H), 2.56 (s, 3H)
ppm.
2-Phenylquinoline (3ga) (entry 7 of table 1 and entry 1 of table 5)[32]
:
Yield: 88% (0.179 g); Rf = 0.38 (ethyl acetate/hexane 1:49); 1H NMR (400
MHz, CDCl3): δ 8.28 – 8.18 (m, 4H), 7.91 – 7.84 (m, 2H), 7.76 (m, 1H),
7.57 – 7.48 (m, 4H) ppm.
1-(5-(4-Chlorophenyl)thiophene-2-yl)ethanone (3ib) (entry 17 of table
1)[37]: Yield: 88% (0.206 g); Rf = 0.42 (ethyl acetate/hexane 1:19); 1H NMR
(400 MHz, CDCl3): δ 7.65 (d, 1H), 7.59 – 7.57 (m, 2H), 7.40 – 7.38 (m, 2H),
7.29 (d, 1H), 2.57 (s, 3H) ppm.
6-Methyl-2-(4-chlorophenyl)pyridine (3cb) (entry 8 of table 1)[34]: Yield:
92% (0.185 g); Rf = 0.45 (ethyl acetate/hexane 1:49); 1H NMR (400 MHz,
CDCl3): δ 7.94 (d, 2H), 7.64 (t, 1H), 7.48 (d, 1H), 7.42 (d, 2H), 7.10 (d, 1H),
2.62 (s, 3H) ppm.
1-(4-(Thiophen-3-yl)phenyl)ethanone (3jf) (entry 1 of table 2)[38]: Yield:
40% (0.040 g); Rf = 0.33 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz,
CDCl3): δ 7.99 (d, 2H), 7.69 (d, 2H), 7.58 (dd, 1H), 7.43 (m, 2H), 2.62 (s,
3H) ppm.
2-(4-Fluorophenyl)-5-nitropyridine (3ec) (entry 9 of table 1)[32]: Yield:
94% (0.203 g); Rf = 0.42 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz,
CDCl3): δ 9.46 (s, 1H), 8.52 (dd, 1H), 8.11 – 8.08 (m, 2H), 7.86 (d, 1H),
7.23 – 7.18 (m, 2H) ppm.
4-(4’-Acetylphenyl)dibenzofuran (3jg) (entry 2 of table 2)[4h]: Yield: 82%
(0.116 g); Rf = 0.31 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz,
CDCl3): δ 8.13 (d, 2H), 8.04 – 7.98 (m, 4H), 7.65 – 7.60 (m, 2H), 7.51 –
7.36 (m, 3H), 2.68 (s, 3H) ppm.
2-(4-Methoxyphenyl)pyrazine (3fd) (entry 10 of table 1)[35]: Yield: 93%
(0.172 g); Rf = 0.32 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz,
CDCl3): δ 8.97 (d, 1H), 8.57 (dd, 1H), 8.43 (d, 1H), 7.97 (d, 2H), 7.03 (d,
2H), 3.87 (s, 3H) ppm.
5-(4-Acetylphenyl)-1H-indole (3jh) (entry 3 of table 2)[39]: Yield: 71%
(0.083 g); Rf = 0.35 (ethyl acetate/hexane 1:4); 1H NMR (400 MHz, CDCl3):
δ 8.30 (s, 1H), 8.03 (d, 2H), 7.91 (d, 1H), 7.74 (d, 2H), 7.47 (d, 2H), 7.25
(t, 1H), 6.62 (t, 1H), 2.64 (s, 3H) ppm.
2-(4-Ethylphenyl)quinolone (3ge) (entry 11 of table 1): Obtained as a
colorless oil; Yield: 92% (0.213 g); Rf = 0.36 (ethyl acetate/hexane 1:49);
1H NMR (400 MHz, CDCl3): δ 8.19 – 8.09 (m, 4H), 7.87 – 7.70 (m, 2H),
7.73 (t, J = 7.2 Hz, 2H), 7.51 (m, 1H), 7.37 (d, 2H), 2.74 (q, J = 7.6 Hz, 2H),
1.30 (t, J = 7.6 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ 157.5, 148.4,
145.9, 137.3, 136.8, 129.8, 129.7, 128.5, 127.7, 127.6, 127.2, 126.2, 119.1,
28.8, 15.7 ppm; IR (KBr): 3059, 2958, 2924, 2867, 1594, 1493, 1428, 1315,
1051, 943, 817, 753, 676 cm-1; HRMS (ESI): m/z calcd for C17H16N [M +
H]+ 234.1282, found 234.1267.
1-(4-(Dibenzo[b,d]thiophen-4-yl)phenyl)ethan-1-one (3ji) (entry 4 of
table 2): Obtained as a white solid; Yield: 72% (0.108 g); mp: 143 – 145 °C;
Rf = 0.37 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 8.22
– 8.18 (m, 2H), 8.12 (d, J = 8.4 Hz, 2H), 7.86 (d, J = 8.5 Hz, 3H), 7.58 (t, J
= 7.6 Hz, 1H), 7.53 – 7.46 (m, 3H), 2.69 (s, 3H) ppm; 13C NMR (100 MHz,
CDCl3): δ 197.9, 145.4, 139.5, 138.5, 136.6, 135.9, 135.7, 129.1, 128.6,
127.2, 127.1, 125.3, 124.7, 122.8, 121.9, 121.3, 26.9 ppm; IR (KBr): 3044,
1676, 1597, 1438, 1357, 1257, 1106, 842, 798, 754 cm-1; HRMS (ESI):
m/z calcd for C20H15OS [M + H]+ 303.0843, found 303.0864.
1-(4-Ethylphenyl)isoquinoline (3he) (entry 12 of table 1): Obtained as a
white solid; Yield: 80% (0.186 g); mp: 59 – 61 °C; Rf = 0.32 (ethyl
acetate/hexane 1:49); H NMR (400 MHz, CDCl3): δ 8.60 (d, J = 6.0 Hz,
1H), 8.12 (d, J = 8.4 Hz, 1H), 7.87 (d, J = 8.4 Hz, 1H), 7.69 – 7.61 (m, 4H),
7.52 (t, 1H), 7.36 (d, J = 8.4 Hz, 2H), 2.76 (q, J = 7.6 Hz, 2H), 1.32 (t, J =
7.6 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ 160.9, 144.9, 142.2, 137.0,
136.9, 131.0, 130.0, 128.0, 127.9, 127.2, 127.7, 126.9, 119.9, 28.9, 15.7
ppm; IR (KBr): 3049, 2964, 2930, 2871, 1617, 1552, 1455, 1383, 1355,
975, 828, 751, 678 cm-1; HRMS (ESI): m/z calcd for C17H16N [M + H]+
234.1282, found 234.1299.
1-(4-(Thianthren-1-yl)phenyl)ethan-1-one (3jj) (entry 5 of table 2):
Obtained as a pale yellow solid; Yield: 62% (0.103 g); mp: 199 – 201 °C;
Rf = 0.30 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 8.09
– 8.05 (m, 2H), 7.57 – 7.48 (m, 4H), 7.36 (dd, J = 7.6, 1.4 Hz, 1H), 7.30 (t,
J = 7.6 Hz, 1H), 7.27 – 7.16 (m, 3H), 2.68 (s, 3H) ppm; 13C NMR (100 MHz,
CDCl3): δ 197.9, 145.0, 141.5, 136.5, 136.3, 136.1, 135.6, 135.0, 129.9,
129.1, 129.0, 128.9, 128.7, 128.4, 128.1, 127.8, 127.4, 26.9 ppm; IR (KBr):
3059, 2998, 1675, 1599, 1444, 1385, 1350, 1263, 1108, 789, 747 cm-1;
HRMS (ESI): m/z calcd for C20H15OS2 [M + H]+ 335.0564, found 335.0597.
1
2-(4-Acetyl phenyl)benzo[b]furan (3jk) (entry 6 of table 2)[4h]: Yield: 51%
(0.059 g); Rf = 0.32 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz,
CDCl3): δ 8.04 (d, 2H), 7.94 (d, 2H), 7.62 (d, 1H), 7.53 (d, 1H), 7.33 – 7.27
(m, 2H), 7.17 (s, 1H), 2.64 (s, 3H) ppm.
2-(4-Chlorophenyl)quinolone (3gb) (entry 13 of table 1)[36]: Yield: 93%
(0.221 g); Rf = 0.42 (ethyl acetate/hexane 1:49); 1H NMR (400 MHz,
CDCl3): δ 8.22 – 8.11 (m, 4H), 7.84 – 7.82 (m, 2H), 7.75 – 7.72 (m, 1H),
7.55 – 7.46 (m, 3H) ppm.
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1-(5-(Dibenzo[b,d]furan-4-yl)thiophen-2-yl)ethan-1-one (3ig) (entry 1
of table 3 and entry 4 of table 5): Obtained as a yellow solid; Yield: 72%
(0.104 g); mp: 132 – 134 °C; Rf = 0.26 (ethyl acetate/hexane 1:19); 1H
NMR (400 MHz, CDCl3): δ 8.00 – 7.89 (m, 3H), 7.79 – 7.74 (m, 2H), 7.67
(d, J = 8.2 Hz, 1H), 7.51 (t, J = 7.7 Hz, 1H), 7.39 (m, 2H), 2.62 (s, 3H) ppm;
13C NMR (100 MHz, CDCl3): δ 190.9, 156.3, 152.5, 147.0, 143.4, 133.4,
127.9, 127.1, 125.5, 125.4, 123.9, 123.4, 123.4, 121.2, 121.0, 118.5, 112.1,
26.8 ppm; IR (KBr): 3062, 1645, 1583, 1438, 1350, 1273, 1182, 1095, 835,
790, 747 cm-1; HRMS (ESI): m/z calcd for C18H13O2S [M + H]+ 293.0636,
found 293.0632.
2-(Dibenzo[b,d]furan-4-yl)pyrazine (3fg) (entry 2 of table 4): Obtained
as a white solid; Yield: 75% (0.092 g); mp: 133 – 135 °C; Rf = 0.23 (ethyl
acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 9.74 (s, 1H), 8.73 (s,
1H), 8.58 (d, J = 2.1 Hz, 1H), 8.29 (d, J = 7.7 Hz, 1H), 8.02 (dd, J = 21.1,
7.5 Hz, 2H), 7.65 (d, J = 8.2 Hz, 1H), 7.50 (t, J = 7.7 Hz, 2H), 7.39 (t, J =
7.4 Hz, 1H) ppm; 13C NMR (100 MHz, CDCl3): δ 156.2, 153.6, 149.9, 145.6,
144.5, 143.2, 127.7, 127.2, 125.5, 123.8, 123.6, 123.3, 122.4, 121.1, 120.9,
112.0 ppm; IR (KBr): 3031, 2963, 1462, 1454, 1417, 1189, 1069, 1014,
877, 793, 741 cm-1; HRMS (ESI): m/z calcd for C16H11N2O [M + H]+
247.0871, found 247.0867.
1-(5-(Dibenzo[b,d]thiophen-4-yl)thiophen-2-yl)ethan-1-one (3ii) (entry
2 of table 3): Obtained as a white solid; Yield: 71% (0.108 g); mp: 100 –
102 °C; Rf = 0.29 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3):
δ 8.21 – 8.17 (m, 2H), 7.91 – 7.87 (m, 1H), 7.77 (d, J = 4.0 Hz, 1H), 7.72
(dd, J = 7.5, 1.0 Hz, 1H), 7.65 (d, J = 3.9 Hz, 1H), 7.57 – 7.48 (m, 3H), 2.62
(s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ 190.8, 150.9, 143.8, 139.4,
137.9, 137.0, 135.4, 133.2, 128.9, 127.4, 126.9, 126.5, 125.2, 124.9, 122.8,
122.1, 122.0, 26.9 ppm; IR (KBr): 3051, 1651, 1482, 1434, 1390, 1276,
1018, 791, 755 cm-1; HRMS (ESI): m/z calcd for C18H13OS2 [M + H]+
309.0407, found 309.0431.
1-(Dibenzo[b,d]furan-4-yl)isoquinoline (3hg) (entry 3 of table 4):
Obtained as a yellow solid; Yield: 55% (0.081 g); mp: 135 – 137 °C; Rf =
0.13 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 8.73 (d, J
= 5.7 Hz, 1H), 8.11 (dd, J = 7.7, 1.1 Hz, 1H), 8.03 (d, J = 7.6 Hz, 1H), 7.95
(d, J = 8.3 Hz, 1H), 7.84 (d, J = 8.5 Hz, 1H), 7.78 (d, J = 5.7 Hz, 1H), 7.74
– 7.67 (m, 2H), 7.52 (dt, J = 15.5, 7.4 Hz, 2H), 7.43 – 7.35 (m, 3H) ppm;
13C NMR (100 MHz, CDCl3): δ 156.8, 156.4, 154.0, 142.6, 136.8, 130.4,
129.1, 127.8, 127.6, 127.4, 127.1, 125.0, 124.3, 124.2, 123.1, 123.0, 121.3,
120.9, 112.1 ppm; IR (KBr): 3050, 1657, 1582, 1495, 1447, 1405, 1184,
833, 804, 752 cm-1; HRMS (ESI): m/z calcd for C21H14NO [M + H]+
296.1075, found 296.1071.
2-(5-Acetylthiophen-2-yl)benzothiophene (3il) (entry 3 of table 3)[40]
:
Yield: 51% (0.065 g); Rf = 0.36 (ethyl acetate/hexane 1:19); 1H NMR (400
MHz, CDCl3): δ 7.82 – 7.76 (m, 2H), 7.63 (d, 1H), 7.56 (s, 1H), 7.40 – 7.33
(m, 2H), 7.29 (d, 1H), 2.57 (s, 3H) ppm.
2-(Thianthren-1-yl)pyrazine (3fj) (entry 4 of table 4): Obtained as a pale
yellow solid; Yield: 60% (0.088 g); mp: 93 – 95 °C; Rf = 0.15 (ethyl
acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 8.89 (s, 1H), 8.76 (s,
1H), 8.63 (s, 1H), 7.62 (dd, J = 7.7, 1.3 Hz, 1H), 7.48 (dd, J = 7.6, 1.3 Hz,
2H), 7.39 – 7.35 (m, 2H), 7.28 – 7.17 (m, 2H) ppm; 13C NMR (100 MHz,
CDCl3): δ 153.7, 145.1, 143.7, 143.2, 137.7, 136.7, 136.6, 136.3, 135.7,
130.3, 129.1, 129.0, 128.7, 128.1, 127.8, 127.4 ppm; IR (KBr): 3048, 1553,
1472, 1445, 1405, 1376, 1143, 1012, 789, 747, 722 cm-1; HRMS (ESI):
m/z calcd for C16H11N2S2 [M + H]+ 295.0363, found 295.0383.
2-(5-Acetyl-2-thienyl)benzo[b]furan (3ik) (entry 4 of table 3)[41]: Yield:
48% (0.058 g); Rf = 0.38 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz,
CDCl3): δ 7.65 (d, 1H), 7.58 (d, 1H), 7.51 (d, 1H), 7.46 (d, 1H), 7.35 – 7.31
(m, 1H), 7.27 – 7.25 (m, 1H), 7.04 (s, 1H), 2.58 (s, 3H) ppm.
1-(5-(1H-indol-5-yl)thiophen-2-yl)ethan-1-one (3ih) (entry 5 of table 3):
Obtained as a yellow solid; Yield: 64% (0.077 g); mp: 159 – 161 °C; Rf =
0.32 (ethyl acetate/hexane 1:4); 1H NMR (400 MHz, CDCl3): δ 8.36 (s, 1H),
7.96 (s, 1H), 7.67 (d, J = 4.0 Hz, 1H), 7.51 (dd, J = 8.5, 1.6 Hz, 1H), 7.42
(d, J = 8.5 Hz, 1H), 7.30 (d, J = 4.0 Hz, 1H), 7.26 (d, J = 3.7 Hz, 1H), 6.63
– 6.58 (m, 1H), 2.57 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ 190.8,
155.4, 141.9, 136.4, 133.9, 128.5, 125.7, 122.9, 121.1, 119.0, 111.8, 103.4,
26.6 ppm; IR (KBr): 3448, 3261, 2919, 1613, 1437, 1356, 1296, 1036, 792,
764 cm-1; HRMS (ESI): m/z calcd for C14H12NOS [M + H]+ 242.0639, found
242.0625.
2-(Thianthren-1-yl)quinolone (3gj) (entry 5 of table 4): Obtained as a
pale yellow solid; Yield: 62% (0.106 g); mp: 139 – 141 °C; Rf = 0.38 (ethyl
acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 8.89 (s, 1H), 8.57 (d,
J = 5.9 Hz, 1H), 8.03 (d, J = 7.9 Hz, 1H), 7.98 – 7.84 (m, 2H), 7.76 (t, J =
7.5 Hz, 2H), 7.69 (d, J = 7.6 Hz, 1H), 7.51 (dd, J = 7.7, 1.0 Hz, 1H), 7.45
(t, J = 7.5 Hz, 1H), 7.32 (d, J = 7.4 Hz, 1H), 7.25 (d, J = 7.0 Hz, 2H), 7.19
(t, J = 7.1 Hz, 1H) ppm; 13C NMR (100 MHz, CDCl3): δ 157.9, 147.6, 141.4,
136.7, 136.6, 136.5, 136.5, 135.9, 130.0, 129.8, 129.6, 129.1, 128.9, 128.6,
127.8, 127.7, 127.6, 127.2, 127.1, 127.0, 121.8 ppm; IR (KBr): 3044, 1591,
1499, 1444, 1423, 1395, 1142, 835, 781, 753, 723 cm-1; HRMS (ESI): m/z
calcd for C21H14NS2 [M + H]+ 344.0567, found 344.0531.
1-(5-(Thianthren-1-yl)thiophen-2-yl)ethan-1-one (3ij) (entry 6 of table
3): Obtained as a yellow solid; Yield: 62% (0.105 g); mp: 163 – 165 °C; Rf
= 0.23 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 7.73 (d,
J = 3.9 Hz, 1H), 7.54 (dd, J = 7.7, 1.3 Hz, 1H), 7.51 – 7.48 (m, 1H), 7.45 –
7.42 (m, 1H), 7.39 (dd, J = 7.7, 1.4 Hz, 1H), 7.30 – 7.21 (m, 4H), 2.61 (s,
3H) ppm; 13C NMR (100 MHz, CDCl3): δ 191.0, 149.4, 144.8, 136.7, 136.2,
135.8, 135.4, 134.0, 132.5, 129.8, 129.7, 129.4, 129.1, 128.7, 128.2, 127.9,
127.4, 26.9 ppm; IR (KBr): 3075, 3049, 1650, 1466, 1426, 1387, 1276,
1030, 921, 794, 750 cm-1; HRMS (ESI): m/z calcd for C18H13OS3 [M + H]+
341.0128, found 341.0153.
5-Nitro-2-(thianthren-1-yl)pyridine (3ej) (entry 6 of table 4): Obtained as
a yellow solid; Yield: 65% (0.109 g); mp: 109 – 111 °C; Rf = 0.30 (ethyl
acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 9.62 (s, 1H), 8.64 (d,
J = 7.0 Hz, 1H), 7.82 (d, J = 7.9 Hz, 1H), 7.66 (d, J = 7.6 Hz, 1H), 7.50 (d,
J = 7.7 Hz, 2H), 7.41 – 7.31 (m, 2H), 7.30 – 7.17 (m, 3H) ppm; 13C NMR
(100 MHz, CDCl3): δ 163.2, 144.6, 143.1, 139.1, 136.7, 136.5, 135.5,
131.6, 130.7, 130.0, 129.1, 128.9, 128.8, 128.2, 127.8, 127.3, 124.3 ppm;
IR (KBr): 3055, 1593, 1571, 1512, 1442, 1346, 1249, 856, 762, 745 cm-1;
HRMS (ESI): m/z calcd for C17H11N2O2S2 [M + H]+ 339.0262, found
339.0252.
2-(Dibenzo[b,d]furan-4-yl)-5-methylpyridine (3dg) (entry 1 of table 4):
Obtained as a white solid; Yield: 65% (0.084 g); mp: 93 – 95 °C; Rf = 0.41
(ethyl acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 8.62 (s, 1H),
8.30 (d, J = 8.1 Hz, 1H), 8.24 (dd, J = 7.7, 0.9 Hz, 1H), 7.99 (d, J = 7.6 Hz,
2H), 7.71 – 7.62 (m, 2H), 7.48 (t, J = 7.7 Hz, 2H), 7.38 (t, J = 7.5 Hz, 1H),
2.43 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ 156.2, 153.7, 151.2, 150.4,
137.3, 132.2, 127.3, 127.8, 125.2, 124.5, 124.2, 123.9, 123.4, 123.0, 121.0,
120.8, 111.9, 18.5 ppm; IR (KBr): 2992, 2919, 1586, 1563, 1484, 1447,
1410, 1186, 837, 751 cm-1; HRMS (ESI): m/z calcd for C18H14NO [M + H]+
260.1075, found 260.1063.
2-(Dibenzo[b,d]thiophen-4-yl)quinolone (3gi) (entry 7 of table 4):
Obtained as a white solid; Yield: 75% (0.116 g); mp: 129 – 131 °C; Rf =
0.58 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 8.43 (d, J
= 7.7 Hz, 1H), 8.33 – 8.27 (m, 2H), 8.25 – 8.22 (m, 1H), 8.19 (dd, J = 7.6,
0.9 Hz, 1H), 8.12 (d, J = 8.7 Hz, 1H), 8.00 – 7.97 (m, 1H), 7.89 – 7.85 (m,
1H), 7.81 (m, 1H), 7.65 (t, J = 7.7 Hz, 1H), 7.59 (m, 1H), 7.50 (m, 2H) ppm;
13C NMR (100 MHz, CDCl3): δ 155.8, 147.6, 142.8, 138.5, 137.6, 136.9,
134.8, 133.3, 130.0, 129.3, 127.6, 127.1, 126.9, 126.8, 125.7, 124.7, 124.2,
122.7, 122.6, 121.5, 118.7 ppm; IR (KBr): 3046, 1592, 1499, 1444, 1395,
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10.1002/ejoc.201701241
European Journal of Organic Chemistry
FULL PAPER
1307, 1105, 835, 781, 753 cm-1; HRMS (ESI): m/z calcd for C21H14NS [M
1-Benzyl-4-ethylbenzene (6ae) (entry 3 of table 6)[45]: Yield: 86% (0.168
g); Rf = 0.88 (hexane); 1H NMR (400 MHz, CDCl3): δ 7.37 (m, 2H), 7.31 –
7.24 (m, 3H), 7.21 (s, 4H), 4.04 (s, 2H), 2.71 (q, 2H), 1.32 (t, 3H) ppm.
+ H]+ 312.0846, found 312.0872.
2-(Dibenzo[b,d]thiophen-4-yl)pyrazine (3fi) (entry
8 of table 4):
Obtained as a yellow solid; Yield: 78% (0.102 g); mp: 137 – 139 °C; Rf =
0.20 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz, CDCl3): δ 9.31 (d, J
= 0.9 Hz, 1H), 8.85 (s, 1H), 8.57 (d, J = 2.4 Hz, 1H), 8.32 (d, J = 7.7 Hz,
1H), 8.26 – 8.18 (m, 1H), 8.10 (d, J = 7.5 Hz, 1H), 7.95 – 7.89 (m, 1H),
7.64 (t, J = 7.7 Hz, 1H), 7.52 – 7.44 (m, 2H) ppm; 13C NMR (100 MHz,
CDCl3): δ 152.1, 143.0, 142.9, 142.6, 141.7, 137.9, 137.7, 134.7, 130.5,
127.2, 125.1, 124.8, 124.5, 123.2, 122.6, 121.6 ppm; IR (KBr): 3047, 1515,
1465, 1436, 1370, 1283, 1155, 1017, 798, 746 cm-1; HRMS (ESI): m/z
calcd for C16H11N2S [M + H]+ 263.0643, found 263.0659.
1-Ethyl-4-(4-methylbenzyl)benzene (6ce) (entry 4 of table 6)[46]: Yield:
88% (0.185 g); Rf = 0.87 (hexane); 1H NMR (400 MHz, CDCl3): δ 7.13 (m,
8H), 3.94 (s, 2H), 2.63 (q, 2H), 2.34 (s, 3H), 1.24 (t, 3H) ppm.
1-Ethyl-4-(4-fluorobenzyl)benzene (6de) (entry 5 of table 6): Obtained
as a colorless oil; Yield: 75% (0.160 g); Rf = 0.88 (hexane); 1H NMR (400
MHz, CDCl3): δ 7.16 – 7.07 (m, 6H), 6.99 – 6.93 (m, 2H), 3.92 (s, 2H), 2.62
(q, J = 7.6 Hz, 2H), 1.22 (t, J = 7.6 Hz, 3H) ppm; 13C NMR (100 MHz,
CDCl3): δ 161.5 (d, JC-F = 242 Hz), 142.3, 138.3, 137.2 (d, JC-F = 4 Hz),
130.4 (d, JC-F = 8 Hz), 128.9, 128.1, 115.3 (d, JC-F = 21 Hz), 40.8, 28.6,
15.7 ppm; 19F NMR (470 MHz, CDCl3): δ -117.6 ppm; IR (KBr): 3019, 2965,
2929, 2871, 1603, 1508, 1456, 1224, 1157, 849, 815 cm-1; HRMS data
could not be obtained.
2-(Dibenzo[b,d]thiophen-4-yl)pyridine (3ai) (entry 9 of table 4)[42]: Yield:
72% (0.094 g); Rf = 0.54 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz,
CDCl3): δ 8.88 (d, 1H), 8.26 (dd, 1H), 8.21 (m, 1H), 8.02 – 7.97 (m, 2H),
7.92 (m, 1H), 7.86 – 7.81 (m, 1H), 7.60 (t, 1H), 7.50 – 7.45 (m, 2H), 7.31
(m, 1H) ppm.
1-(4-Ethylbenzyl)-2-methoxybenzene (6ee) (entry 6 of table 6): Obtained
as a colorless oil; Yield: 77% (0.174 g); Rf = 0.31 (hexane); 1H NMR (400
MHz, CDCl3): δ 7.15 – 7.23 (m, 1H), 7.11 (d, 4H), 6.80 – 6.73 (m, 3H), 3.92
(s, 2H), 3.77 (s, 3H), 2.61 (q, J = 7.6 Hz, 2H), 1.21 (t, J = 7.6 Hz, 3H) ppm;
13C NMR (100 MHz, CDCl3): δ 159.8, 143.1, 142.1, 138.2, 129.5, 129.0,
128.1, 121.5, 114.9, 111.4, 55.3, 41.7, 28.6, 15.7 ppm; IR (KBr): 3004,
2963, 2931, 2835, 1600, 1488, 1457, 1259, 1153, 1047, 779, 692 cm-1;
HRMS data could not be obtained.
3-(4-Ethylphenyl)pyridine (3be) (entry 2 of table 5)[43]: Yield: 92% (0.084
g); Rf = 0.35 (ethyl acetate/hexane 1:49); 1H NMR (400 MHz, CDCl3): δ
8.86 (d, 1H), 8.58 (d, 1H), 7.98 (m, 1H), 7.52 – 7.49 (d, 2H), 7.47 – 7.43
(m, 1H), 7.33 – 7.30 (d, 2H), 2.74 – 2.68 (q, 2H), 1.30 – 1.26 (t, 3H) ppm.
2-(4-Fluorophenyl)pyrazine (3fc) (entry 3 of table 5)[33]: Yield: 93%
(0.080 g); Rf = 0.41 (ethyl acetate/hexane 1:19); 1H NMR (400 MHz,
CDCl3): δ 9.02 (s, 1H), 8.68 (d, 1H), 8.52 (d, 1H), 8.03 (m, 2H), 7.21 (m,
2H) ppm.
1-(4-Ethylbenzyl)naphthalene (6be) (entry 7 of table 6 and entry 15 of
table 9): Obtained as a colorless oil; Yield: 86% (0.211 g); Rf = 0.68
(hexane); 1H NMR (400 MHz, CDCl3): δ 8.09 – 8.02 (m, 1H), 7.92 – 7.86
(m, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.52 – 7.42 (m, 3H), 7.33 (d, J = 7.0 Hz,
1H), 7.15 (d, J = 1.6 Hz, 4H), 4.46 (s, 2H), 2.64 (q, J = 7.5 Hz, 2H), 1.25 (t,
J = 7.6 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ 142.1, 137.9, 137.0,
134.1, 132.3, 128.8, 128.8, 128.1, 127.4, 127.2, 126.1, 125.7, 125.7, 124.5,
38.8, 28.6, 15.7 ppm; IR (KBr): 3046, 2963, 2928, 2870, 1595, 1511, 1453,
1395, 1260, 1115, 778 cm-1; HRMS data could not be obtained.
2-(Dibenzo[b,d]furan-4-yl)-6-methylpyridine (3cg) (entry 5 of table 5):
Obtained as a white solid; Yield: 62% (0.080 g); mp: 70 – 72 °C; Rf = 0.51
1
(ethyl acetate/hexane 1:19); H NMR (400 MHz, CDCl3): δ 8.30 (dd, J =
7.7, 1.1 Hz, 1H), 8.21 (d, J = 7.8 Hz, 1H), 8.00 (dd, J = 7.6, 1.2 Hz, 2H),
7.76 (t, J = 7.8 Hz, 1H), 7.64 (d, J = 8.2 Hz, 1H), 7.51 – 7.46 (m, 2H), 7.38
(m, 1H), 7.17 (d, J = 7.7 Hz, 1H), 2.69 (s, 3H) ppm; 13C NMR (100 MHz,
CDCl3): δ 158.6, 156.2, 153.8, 153.1, 136.9, 127.5, 127.3, 125.1, 124.7,
124.2, 123.4, 123.0, 122.2, 121.4, 121.1, 120.8, 111.9, 25.0 ppm; IR (KBr):
3048, 2918, 1575, 1490, 1444, 1388, 1260, 1187, 1106, 835, 781, 750 cm-
1; HRMS (ESI): m/z calcd for C18H14NO [M + H]+ 260.1075, found 260.1093.
2-(4-Ethylbenzyl)naphthalene (6fe) (entry 8 of table 6 and entry 16 of
table 9): Obtained as a colorless oil; Yield: 88% (0.216 g); Rf = 0.69
(hexane); 1H NMR (400 MHz, CDCl3): δ 7.85 – 7.77 (m, 3H), 7.68 (s, 1H),
7.51 – 7.42 (m, 2H), 7.36 (dd, J = 8.4, 1.7 Hz, 1H), 7.21 – 7.15 (m, 4H),
4.15 (s, 2H), 2.66 (q, J = 7.6 Hz, 2H), 1.27 (t, J = 7.6 Hz, 3H) ppm; 13C
NMR (100 MHz, CDCl3): δ 142.2, 139.0, 138.3, 133.8, 132.2, 129.1, 128.2,
128.1, 127.8, 127.8, 127.7, 127.2, 126.1, 125.4, 41.9, 28.6, 15.7 ppm; IR
(KBr): 3051, 2964, 2927, 2869, 1603, 1510, 1435, 1367, 1178, 1118, 813,
723, 540 cm-1; HRMS data could not be obtained.
3-(Dibenzo[b,d]furan-4-yl)pyridine (3bg) (entry 6 of table 5): Obtained
as a colorless oil; Yield: 61% (0.074 g); Rf = 0.38 (ethyl acetate/hexane
1:19); 1H NMR (400 MHz, CDCl3): δ 9.16 (d, J = 1.7 Hz, 1H), 8.66 (dd, J =
4.8, 1.6 Hz, 1H), 8.25 – 8.22 (m, 1H), 8.00 – 7.94 (m, 2H), 7.60 (dd, J =
7.7, 1.1 Hz, 2H), 7.50 – 7.43 (m, 3H), 7.37 (m, 1H) ppm; 13C NMR (100
MHz, CDCl3): δ 156.2, 153.4, 149.6, 148.8, 136.1, 132.3, 127.6, 126.6,
125.2, 124.0, 123.6, 123.5, 123.1, 122.3, 120.9, 120.7, 111.9 ppm; IR
(KBr): 3053, 2955, 1567, 1450, 1426, 1395, 1189, 1128, 1009, 752, 710
cm-1; HRMS (ESI): m/z calcd for C17H12NO [M + H]+ 246.0918, found
246.0902.
1-Methyl-2-(4-methylbenzyl)benzene (6gm) (entry 9 of table 6)[46]: Yield:
1
78% (0.153 g); Rf = 0.89 (hexane); H NMR (400 MHz, CDCl3): δ 7.15 –
7.14 (m, 3H), 7.10 – 7.07 (m, 3H), 7.01 (d, J = 7.0 Hz, 2H), 3.95 (s, 2H),
2.31 (s, 3H), 2.25 (s, 3H) ppm.
Analytical data for (hetero)diarylmethanes:
4-(2-Methylbenzyl)benzaldehyde (6gn) (entry 10 of table 6): Obtained as
a white solid; Yield: 87% (0.182 g); mp: 129 – 131 ºC; Rf = 0.33 (ethyl
acetate/hexane 1:49); H NMR (400 MHz, CDCl3): δ 9.97 (s, 1H), 7.81 –
7.77 (m, 2H), 7.28 (d, J = 8.0 Hz, 2H), 7.18 (dd, J = 6.4, 3.3 Hz, 3H), 7.13
– 7.08 (m, 1H), 4.07 (s, 2H), 2.22 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3):
δ 192.1, 148.1, 137.8, 136.8, 134.8, 130.7, 130.2, 130.1, 129.5, 127.1,
126.4, 39.9, 19.8 ppm; IR (KBr): 3015, 2960, 2907, 1684, 1604, 1423,
1287, 1179, 926, 741cm-1; HRMS (ESI): m/z calcd for C15H15O [M + H]+
211.1123, found 211.1135.
1
Diphenylmethane (6aa) (entry 1 of table 6 and entry 1 of table 9)[44]: Yield:
1
95% (0.159 g); Rf = 0.89 (hexane); H NMR (400 MHz, CDCl3): δ 7.24 –
7.22 (m, 4H), 7.17 – 7.14 (m, 6H), 3.94 (s, 2H) ppm.
1-Benzylnaphthalene (6ba) (entry 2 of table 6 and entry 2 of table 9)[10]
:
Yield: 92% (0.200 g); Rf = 0.82 (hexane); 1H NMR (400 MHz, CDCl3): δ
8.00 – 7.98 (m, 1H), 7.86 – 7.84 (m, 1H), 7.75 (d, 1H), 7.46 – 7.39 (m, 3H),
7.29 – 7.24 (m, 3H), 7.20 – 7.18 (m, 3H), 4.46 (s, 2H) ppm.
1-(4-Methoxybenzyl)-2-methylbenzene (6gd) (entry 11 of table 6)[47]
:
1
Yield: 92% (0.195 g); Rf = 0.32 (hexane); H NMR (400 MHz, CDCl3): δ
7.17 – 7.10 (m, 4H), 7.05 (d, 2H), 6.83 (d, 2H), 3.93 (s, 2H), 3.79 (s, 3H),
2.25 (s, 3H) ppm.
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10.1002/ejoc.201701241
European Journal of Organic Chemistry
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1-(2-Methylbenzyl)naphthalene (6go) (entry 12 of table 6): Obtained as
a colorless oil; Yield: 85% (0.197 g); Rf = 0.85 (hexane); 1H NMR (400 MHz,
CDCl3): δ 8.00 (dd, J = 6.2, 3.5 Hz, 1H), 7.90 (dd, J = 6.0, 3.5 Hz, 1H),
7.77 (d, J = 8.2 Hz, 1H), 7.50 (dd, J = 6.3, 3.3 Hz, 2H), 7.41 – 7.36 (m, 1H),
7.25 (d, J = 6.1 Hz, 1H), 7.19 (t, J = 7.2 Hz, 1H), 7.13 – 7.04 (m, 2H), 6.93
(d, J = 7.5 Hz, 1H), 4.42 (s, 2H), 2.34 (s, 3H) ppm; 13C NMR (100 MHz,
CDCl3): δ 138.5, 136.8, 136.2, 133.9, 132.4, 130.2, 129.8, 128.9, 127.0,
126.5, 126.5, 126.2, 126.1, 125.8, 125.7, 124.0, 36.3, 19.8 ppm; IR (KBr):
3048, 2916, 1597, 1490, 1457, 1394, 1258, 1160, 1105, 1016, 781, 741
cm-1; HRMS data could not be obtained.
13C NMR (100 MHz, CDCl3): δ 142.3, 140.0, 137.9, 131.9, 130.4, 128.9,
128.7, 128.2, 41.0, 28.6, 15.7 ppm; IR (KBr): 3028, 2965, 2927, 1595,
1489, 1436, 1180, 1092, 1015, 802, 724 cm-1; HRMS data could not be
obtained.
1-(4-(4-Chlorobenzyl)phenyl)ethan-1-one (6ip) (entry 2 of table 7)[51]
:
Yield: 92% (0.225 g); Rf = 0.32 (ethyl acetate/hexane 1:49); 1H NMR (400
MHz, CDCl3): δ 7.88 (d, 2H), 7.28 – 7.22 (m, 4H), 7.10 (d, 2H), 3.99 (s,
2H), 2.57 (s, 3H) ppm.
3-(4-Chlorobenzyl)thiophene (6if) (entry 3 of table 7)[52]: Yield: 93%
(0.194 g); Rf = 0.86 (hexane); H NMR (400 MHz, CDCl3): δ 7.28 – 7.23
(m, 3H), 7.12 (d, 2H), 6.92 – 6.89 (m, 1H), 6.87 (dd, 1H), 3.94 (s, 2H) ppm.
2-(4-Fluorobenzyl)naphthalene (6fc) (entry 13 of table 6)[48]: Yield: 83%
(0.196 g); Rf = 0.82 (hexane); H NMR (400 MHz, CDCl3): δ 7.85 – 7.71
1
1
(m, 3H), 7.60 (s, 1H), 7.52 – 7.42 (m, 2H), 7.29 (m, 1H), 7.21 – 7.17 (m,
2H), 7.01 – 6.97 (m, 2H), 4.12 (s, 2H) ppm.
4-(4-Chlorobenzyl)dibenzo[b,d]furan (6ig) (entry 4 of table 7): Obtained
as a white solid; Yield: 72% (0.210 g); mp: 76 – 78 °C; Rf = 0.68 (hexane);
1H NMR (400 MHz, CDCl3): δ 7.97 – 7.93 (m, 1H), 7.83 (dd, J = 7.6, 1.2
Hz, 1H), 7.59 (d, J = 8.2 Hz, 1H), 7.49 – 7.44 (m, 1H), 7.35 (td, J = 7.6, 0.9
Hz, 1H), 7.30 – 7.24 (m, 5H), 7.22 – 7.18 (m, 1H), 4.31 (s, 2H) ppm; 13C
NMR (100 MHz, CDCl3):δ 156.2, 154.6, 138.6, 132.1, 130.4, 128.7, 127.7,
127.2, 124.7, 124.6, 124.3, 123.1, 122.9, 120.9, 119.0, 111.9, 35.2 ppm;
IR (KBr): 3045, 3019, 2916, 1583, 1489, 1446, 1181, 1088, 825, 799, 744
cm-1; HRMS data could not be obtained.
4-(Naphthalen-1-ylmethyl)benzaldehyde (6fn) (entry 14 of table 6):
Obtained as a colorless oil; Yield: 82% (0.201 g); Rf = 0.16 (ethyl
1
acetate/hexane 1:49); H NMR (400 MHz, CDCl3): δ 9.96 (s, 1H), 7.92 –
7.87 (m, 2H), 7.82 – 7.77 (m, 3H), 7.49 (m, 3H), 7.37 – 7.32 (m, 3H), 4.53
(s, 2H) ppm; 13C NMR (100MHz, CDCl3): δ 192.0, 148.2, 135.4, 134.8,
134.1, 132.1, 130.1, 129.4, 128.9, 127.8, 127.7, 126.3, 125.9, 125.7, 124.1,
39.4 ppm; IR (KBr): 3049, 2827, 2733, 1697, 1602, 1509, 1426, 1392,
1306, 1212, 1167, 841, 783 cm-1; HRMS (ESI): m/z calcd for C18H15O [M
+ H]+ 247.1123, found 247.1094.
1-Chloro-3-(4-ethylbenzyl)benzene (6je) (entry 5 of table 7 and entry 14
of table 9): Obtained as a colorless oil; Yield: 90% (0.207 g); Rf = 0.86
(hexane); 1H NMR (400 MHz, CDCl3): δ 7.21 – 7.07 (m, 8H), 3.93 (s, 2H),
2.64 (q, J = 7.6 Hz, 2H), 1.24 (t, J = 7.6 Hz, 3H) ppm; 13C NMR (100 MHz,
CDCl3): δ 143.6, 142.4, 137.5, 134.3, 129.8, 129.1, 129.0, 128.2, 127.2,
126.4, 41.3, 28.6, 15.7 ppm; IR (KBr): 3053, 2965, 2928, 2870, 1594, 1511,
1433, 1195, 1117, 779, 688 cm-1; HRMS data could not be obtained.
Di(naphthalen-1-yl)methane (6bo) (entry 15 of table 6)[49]: Yield: 92%
(0.246 g); Rf = 0.83 (hexane); 1H NMR (400 MHz, CDCl3): δ 8.09 – 8.04 (d,
2H), 7.93 (d, 2H), 7.79 (d, 2H), 7.55 – 7.48 (m, 4H), 7.36 (t, 2H), 7.10 (d,
2H), 4.91 (s, 2H) ppm.
1-(4-(2,4,6-Trimethylbenzyl)phenyl)ethan-1-one (6hp) (entry 16 of table
6 and entry 17 of table 9): Obtained as a white solid; Yield: 81% (0.204 g);
mp: 79 – 81 °C; Rf = 0.30 (ethyl acetate/hexane 1:49); 1H NMR (400 MHz,
CDCl3): δ 7.86 – 7.81 (m, 2H), 7.11 (d, J = 8.4 Hz, 2H), 6.91 (s, 2H), 4.07
(s, 2H), 2.56 (s, 3H), 2.31 (s, 3H), 2.19 (s, 6H) ppm; 13C NMR (100 MHz,
CDCl3): δ 198.0, 146.3, 137.1, 136.2, 135.2, 133.0, 129.1, 128.7, 128.1,
35.0, 26.6, 21.0, 20.2 ppm; IR (KBr): 2937, 2913, 2857, 1671, 1599, 1412,
1356, 1267, 960, 785 cm-1; HRMS (ESI): m/z calcd for C18H21O [M + H]+
253.1592, found 253.1609.
1-(4-(3-Chlorobenzyl)phenyl)ethan-1-one (6jp) (entry 6 of table 7):
Obtained as a colorless oil; Yield: 88% (0.215 g); Rf = 0.31 (ethyl
acetate/hexane 1:49); H NMR (400 MHz, CDCl3): δ 7.93 (d, J = 8.3 Hz,
2H), 7.30 (d, J = 8.5 Hz, 2H), 7.23 (m, 2H), 7.19 (t, J = 1.8 Hz, 1H), 7.09
(m, 1H), 4.03 (s, 2H), 2.61 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ
197.9, 145.9, 142.2, 135.6, 134.5, 130.0, 129.2, 129.1, 128.9, 127.2, 126.8,
41.6, 26.7 ppm; IR (KBr): 3055, 2920, 1681, 1601, 1415, 1357, 1267, 779,
692 cm-1; HRMS (ESI): m/z calcd for C15H14ClO [M + H]+ 245.0733, found
245.0703.
1
4-(2,4,6-Trimethylbenzyl)benzaldehyde (6hn) (entry 17 of table 6)[50]
:
Yield: 78% (0.185 g); Rf = 0.31 (ethyl acetate/hexane 1:49); 1H NMR (400
MHz, CDCl3): δ 9.95 (s, 1H), 7.76 (d, 2H), 7.17 (d, 2H), 6.92 (s, 2H), 4.09
(s, 2H), 2.30 (s, 3H), 2.19 (s, 6H) ppm.
1-Chloro-3-(4-fluorobenzyl)benzene (6jc) (entry 7 of table 7): Obtained
as a colorless oil; Yield: 85% (0.187 g); Rf = 0.85 (hexane); 1H NMR (400
MHz, CDCl3): δ 7.25 – 7.20 (m, 2H), 7.16 – 7.12 (m, 3H), 7.07 – 7.04 (m,
1H), 7.01 – 6.97 (m, 2H), 3.93 (s, 2H) ppm; 13C NMR (100 MHz, CDCl3): δ
161.7 (d, JC-F = 243 Hz), 143.1, 136.0 (d, JC-F = 3 Hz), 134.5, 130.5 (d, JC-
1-(2,4,6-Trimethylbenzyl)naphthalene (6ho) (entry 18 of table 6):
Obtained as a white solid; Yield: 88% (0.229 g); mp: 96 – 98 °C; Rf = 0.81
(hexane); 1H NMR (400 MHz, CDCl3): δ 8.25 (d, J = 8.3 Hz, 1H), 7.89 (d,
J = 7.9 Hz, 1H), 7.68 (d, J = 8.2 Hz, 1H), 7.62 – 7.49 (m, 2H), 7.24 (dd, J
= 10.7, 4.5 Hz, 1H), 6.95 (s, 2H), 6.69 – 6.63 (m, 1H), 4.40 (s, 2H), 2.34 (s,
3H), 2.16 (s, 6H) ppm; 13C NMR (100 MHz, CDCl3): δ 137.6, 136.0, 135.5,
133.8, 133.2, 132.4, 129.0, 129.0, 126.6, 126.0, 125.9, 125.7, 123.7, 123.3,
31.5, 21.1, 20.0 ppm; IR (KBr): 3045, 2913, 2856, 1591, 1481, 1445, 1393,
1375, 1253, 1159, 1025, 851, 789, 766 cm-1; HRMS data could not be
obtained.
= 8 Hz), 129.9, 129.1, 127.1, 126.6, 115.5 (d, JC-F = 21 Hz), 40.8 ppm;
F
19F NMR (470 MHz, CDCl3): δ -117.6 ppm; IR (KBr): 3043, 2919, 1600,
1508, 1432, 1224, 1158, 1091, 822, 785 cm-1; HRMS data could not be
obtained.
3-(3-Chlorobenzyl)thiophene (6jf) (entry 8 of table 7): Obtained as a
colorless oil; Yield: 86% (0.179 g); Rf = 0.87 (hexane); 1H NMR (400 MHz,
CDCl3): δ 7.32 – 7.26 (m, 2H), 7.24 – 7.22 (m, 2H), 7.14 – 7.11 (m, 1H),
6.98 (m, 1H), 6.93 (d, J = 4.9Hz, 1H), 3.99 (s, 2H) ppm; 13C NMR (100
MHz, CDCl3): δ 142.8, 140.6, 134.4, 129.8, 129.0, 128.4, 127.1, 126.5,
126.0, 121.7, 36.3 ppm; IR (KBr): 3058, 2913, 1594, 1476, 1432, 1179,
1119, 1079, 772, 717, 688 cm-1; HRMS data could not be obtained.
1,3,5-Trimethyl-2-(4-methylbenzyl)benzene (6hm) (entry 19 of table 6
1
and entry 18 of table 9)[44]: Yield: 86% (0.192 g); Rf = 0.85 (hexane); H
NMR (400 MHz, CDCl3): δ 7.12 (d, 2H), 7.03 – 6.93 (m, 4H), 4.06 (s, 2H),
4-Benzyl-1,1'-biphenyl (6ka) (entry 9 of table 7)[10]: Yield: 88% (0.107 g);
Rf = 0.61 (hexane); 1H NMR (400 MHz, CDCl3): δ 7.59 – 7.54 (m, 2H), 7.51
(d, 2H), 7.41 (t, 2H), 7.27 (m, 8H), 4.02 (s, 2H) ppm.
2.38 (s, 6H), 2.29 (s, 6H) ppm.
1-Chloro-4-(4-ethylbenzyl)benzene (6ib) (entry 1 of table 7 and entry 13
of table 9): Obtained as a colorless oil; Yield: 95% (0.219 g); Rf = 0.84
(hexane); 1H NMR (400 MHz, CDCl3): δ 7.23 (d, J = 8.2 Hz, 2H), 7.09 (m,
6H), 3.89 (s, 2H), 2.61 (q, J = 7.6 Hz, 2H), 1.21 (t, J = 7.6 Hz, 3H) ppm;
4-Ethyl-4'-(4-ethylbenzyl)-1,1'-biphenyl (6ke) (entry 10 of table 7):
Obtained as a white solid; Yield: 78% (0.117 g); mp: 66 – 68 °C; Rf = 0.6
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10.1002/ejoc.201701241
European Journal of Organic Chemistry
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(hexane); 1H NMR (400 MHz, CDCl3): δ 7.49 (dd, J = 8.2, 1.8 Hz, 4H), 7.27
– 7.22 (m, 4H), 7.14 (s, 4H), 3.98 (s, 2H), 2.65 (dq, J = 23.1, 7.6 Hz, 4H),
1.24 (dt, J = 17.8, 7.6 Hz, 6H) ppm; 13C NMR (100 MHz, CDCl3): δ 143.3,
142.2, 140.3, 139.1, 138.6, 138.4, 129.4, 129.0, 128.4, 128.1, 127.2, 127.1,
41.3, 28.6, 28.6, 15.8, 15.7 ppm; IR (KBr): 3086, 3023, 2959, 2924, 2866,
1494, 1439, 1396, 1111, 1049, 836, 807, 778 cm-1; HRMS data could not
be obtained.
CDCl3): δ 8.03 (m, 1H), 7.36 (m,1H), 7.32 – 7.27 (m, 2H), 7.22– 7.15 (m,
3H), 6.67 (m, 1H), 3.92 (s, 3H), 3.90 (s, 2H) ppm.
4-(Naphthalen-2-ylmethyl)dibenzo[b,d]thiophene (6fi) (entry 10 of
table 8): Obtained as a white solid; Yield: 71% (0.230 g); mp: 129 – 131 °C;
Rf = 0.54 (hexane); 1H NMR (400 MHz, CDCl3): δ 7.97 (d, J = 7.9 Hz, 1H),
7.88 (d, J = 7.5 Hz, 1H), 7.77 (d, J = 8.2 Hz, 1H), 7.55 – 7.38 (m, 6H), 7.30
– 7.22 (m, 2H), 7.10 (dd, J = 17.9, 7.4 Hz, 2H), 6.89 (d, J = 7.5 Hz, 1H),
4.68 (s, 2H) ppm; 13C NMR (100 MHz, CDCl3): δ 140.0, 136.6, 135.9, 135.6,
134.0, 132.2, 129.2, 129.0, 128.9, 128.8, 128.0, 127.8, 127.5, 127.4, 127.3,
127.1, 126.3, 125.8, 125.8, 124.2, 37.5 ppm; IR (KBr): 3050, 2920, 1553,
1441, 1400, 1163, 1109, 1021, 777, 752 cm-1; HRMS data could not be
obtained.
3-(4-(Thiophen-3-yl)benzyl)thiophene (6kf) (entry 11 of table 7):
Obtained as a white solid; Yield: 87% (0.111 g); mp: 82 – 83 °C; Rf = 0.56
(hexane); 1H NMR (400 MHz, CDCl3): δ 7.53 (d, J = 8.1 Hz, 2H), 7.41 (t, J
= 2.1 Hz, 1H), 7.37 (d, J= 2.1 Hz, 2H), 7.27 – 7.21 (m, 3H), 6.96 – 6.91 (m,
2H), 4.00 (s, 2H) ppm; 13C NMR (100 MHz, CDCl3): δ 142.3, 141.5, 139.7,
134.0, 129.3, 128.6, 126.7, 126.4, 126.3, 125.8, 121.4, 120.1, 36.3 ppm;
IR (KBr): 3094, 2879, 1499, 1426, 1206, 1083, 1015, 861, 829, 771, 701
cm-1; HRMS (ESI): m/z calcd for C15H13S2 [M + H]+ 257.0458, found
257.0471.
2-(3-Methylbenzyl)benzofuran (6mk) (entry 11 of table 8)[55]: Yield: 77%
1
(0.171 g); Rf = 0.71 (hexane); H NMR (400 MHz, CDCl3): δ 7.45 – 7.37
(m, 2H), 7.21 – 7.12 (m, 3H), 7.08 – 7.03 (m, 3H), 6.34 (s, 1H), 4.03 (s,
2H), 2.30 (s, 3H) ppm.
2–Benzylbiphenyl (6la) (entry 12 of table 7)[10]: Yield: 92% (0.112 g); Rf =
0.61 (hexane); H NMR (400 MHz, CDCl3): δ 7.38 – 7.11 (m, 12H), 6.97
1
2-(3-Methylbenzyl)thianthrene (6mj) (entry 12 of table 8): Obtained as a
colorless oil; Yield: 65% (0.209 g); Rf = 0.51 (hexane); 1H NMR (400 MHz,
CDCl3): δ 7.51 – 7.48 (m, 2H), 7.40 (d, J = 7.6 Hz, 1H), 7.25 – 7.22 (m,
2H), 7.18 – 7.10 (m, 3H), 7.04 – 7.00 (m, 3H), 4.22 (s, 2H), 2.31 (s, 3H)
ppm; 13C NMR (100 MHz, CDCl3): δ 140.7, 139.8, 138.2, 136.6, 136.0,
135.8, 135.7, 129.8, 129.3, 129.1, 128.7, 128.5, 127.9, 127.7, 127.5, 127.3,
127.1, 126.1, 40.4, 21.6 ppm; IR (KBr): 3052, 2919, 2856, 1606, 1559,
1445, 1408, 1251, 1113, 1034, 746 cm-1; HRMS (ESI): m/z calcd for
C20H17S2 [M + H]+ 321.0771, found 321.0773.
(d, 2H), 3.95 (s, 2H) ppm.
3-Benzylthiophene (6af) (entry 1 of table 8)[11]: Yield: 95% (0.165 g); Rf =
0.89 (hexane); 1H NMR (400 MHz, CDCl3): δ 7.31 – 7.19 (m, 6H), 6.91 –
6.90 (m, 2H), 3.97 (s, 2H) ppm.
3-(4-Methylbenzyl)thiophene (6cf) (entry 2 of table 8)[11]: Yield: 90%
(0.169 g); Rf = 0.88 (hexane); 1H NMR (400 MHz, CDCl3): δ 7.23 (dd, 1H),
7.09 (s, 4H), 6.90 (dd, 2H), 3.93 (s, 2H), 2.32 (s, 3H) ppm.
4-(2-Methylbenzyl)dibenzo[b,d]thiophene (6gi) (entry 13 of table 8):
Obtained as a white solid; Yield: 78% (0.224 g); mp: 74 – 76 °C; Rf = 0.62
(hexane); 1H NMR (400 MHz, CDCl3): δ 8.20 – 8.15 (m, 1H), 8.05 (d, J =
7.8 Hz, 1H), 7.89 – 7.85 (m, 1H), 7.50 – 7.44 (m, 2H), 7.39 (t, J = 7.6 Hz,
1H), 7.25 – 7.20 (m, 2H), 7.19 – 7.13 (m, 2H), 7.04 (dd, J = 7.3, 0.7 Hz,
1H), 4.23 (s, 2H), 2.29 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ 139.4,
139.3, 137.2, 137.1, 136.2, 135.8, 134.9, 130.5, 130.1, 127.0, 126.8, 126.6,
126.2, 125.0, 124.5, 123.0, 121.9, 119.7, 38.5, 19.8 ppm; IR (KBr): 3057,
3014, 2915, 2877, 1576, 1439, 1396, 1305, 1250, 1043, 790, 749 cm-1;
HRMS (ESI): m/z calcd for C20H17S [M + H]+ 289.1051, found 289.1023.
3-(3-Methylbenzyl)thiophene (6mf) (entry 3 of table 8)[11]: Yield: 89%
(0.167 g); Rf = 0.88 (hexane); H NMR (400 MHz, CDCl3): δ 7.25 – 7.22
(m, 1H), 7.20 – 7.16 (m, 1H), 7.03 – 6.99 (m, 3H), 6.91 (m, 2H), 3.94 (s,
2H), 2.32 (s, 3H) ppm.
1
3-(2-Methylbenzyl)thiophene (6gf) (entry 4 of table 8)[11]: Yield: 88%
1
(0.165 g); Rf = 0.86 (hexane); H NMR (400 MHz, CDCl3): δ 7.25 – 7.23
(m, 1H), 7.17 – 7.12 (m, 4H), 6.89 (dd, 1H), 6.82 – 6.79 (m, 1H), 3.97 (s,
2H), 2.27 (s, 3H) ppm.
4-(2,4,6-Trimethylbenzyl)dibenzo[b,d]furan (6hg) (entry 14 of table 8):
Obtained as a white solid; Yield: 76% (0.228 g); mp: 80 – 85 °C; Rf = 0.65
(hexane); 1H NMR (400 MHz, CDCl3): δ 8.01 – 7.95 (m, 1H), 7.79 (d, J =
7.7 Hz, 1H), 7.66 (d, J = 8.2 Hz, 1H), 7.52 – 7.46 (m, 1H), 7.37 (m, 1H),
7.16 (t, J = 7.6 Hz, 1H), 6.95 (s, 2H), 6.74 (dd, J = 7.5, 0.8 Hz, 1H), 4.38
(s, 2H), 2.34 (s, 3H), 2.25 (s, 6H) ppm; 13C NMR (100 MHz, CDCl3): δ
156.2, 154.8, 137.5, 136.0, 132.6, 129.1, 127.1, 125.6, 124.8, 124.3, 123.6,
123.0, 122.8, 120.9, 118.3, 111.9, 28.3, 21.1, 20.2 ppm; IR (KBr): 3059,
3027, 2911, 1587, 1494, 1450, 1422, 1325, 1185, 1078, 844, 753, 698 cm-
1; HRMS (ESI): m/z calcd for C22H20ONa [M + Na]+ 323.1411, found
323.1431.
3-(Naphthalen-2-ylmethyl)thiophene (6ff) (entry 5 of table 8): Obtained
as a Colorless oil; Yield: 86% (0.192 g); Rf = 0.67 (hexane); 1H NMR (400
MHz, CDCl3):δ 7.82 – 7.73 (m, 3H), 7.63 (d, J = 0.5 Hz, 1H), 7.47 – 7.39
(m, 2H), 7.33 (dd, J = 8.4, 1.7 Hz, 1H), 7.27 – 7.21 (m, 1H), 6.97 – 6.91
(m, 2H), 4.13 (s, 2H) ppm; 13C NMR (100 MHz, CDCl3): δ 141.5, 138.2,
133.7, 132.2, 128.6, 128.2, 127.8, 127.7, 127.6, 127.0, 126.1, 125.8, 125.5,
121.5, 36.8 ppm; IR (KBr): 3046, 2913, 2854, 1595, 1509, 1435, 1397,
1259, 1078, 829, 731 cm-1; HRMS data could not be obtained.
3-(2,4,6-Trimethylbenzyl)thiophene (6hf) (entry 6 of table 8)[11]: Yield:
88% (0.190 g); Rf = 0.78 (hexane); 1H NMR (400 MHz, CDCl3): δ 7.22 (m,
1H), 6.88 – 6.86 (m, 3H), 6.63 (s, 1H), 3.95 (s, 2H), 2.28 (s, 3H), 2.24 (s,
6H) ppm.
2-(2,4,6-Trimethylbenzyl)benzofuran (6hk) (entry 15 of table 8):
1
Obtained as a colorless oil; Yield: 51% (0.127 g); Rf = 0.68 (hexane); H
NMR (400 MHz, CDCl3): δ 7.41 (dd, J = 11.6, 4.6 Hz, 2H), 7.19 (m, 2H),
6.92 (s, 2H), 6.08 (d, J = 0.9 Hz, 1H), 4.10 (s, 2H), 2.34 (s, 6H), 2.31 (s,
3H) ppm; 13C NMR (100 MHz, CDCl3): δ 157.6, 155.0, 137.1, 136.4, 130.8,
129.1, 129.0, 123.3, 122.5, 120.3, 110.9, 102.6, 28.8, 21.1, 20.0 ppm; IR
(KBr): 3006, 2919, 2861, 1588, 1451, 1253, 1163, 1136, 952, 853, 746 cm-
1; HRMS (ESI): m/z calcd for C18H19O [M + H]+ 251.1436, found 251.1408.
2-Benzylbenzo[b]thiophene (6al) (entry 7 of table 8)[53]: Yield: 78%
(0.174 g); Rf = 0.71 (hexane); 1H NMR (400 MHz, CDCl3): δ 7.66 – 7.63 (d,
1H), 7.57 (d, 1H), 7.35 – 7.15 (m, 7H), 6.92 (s, 1H), 4.14 (s, 2H) ppm.
4-Benzyldibenzo[b,d]furan (6ag) (entry 8 of table 8)[11]: Yield: 87%
1
(0.224 g); Rf = 0.68 (hexane); H NMR (400 MHz, CDCl3): δ 7.94 – 7.90
(m, 1H), 7.79 (dd, 1H), 7.57 (m, 1H), 7.46 – 7.40 (m, 1H), 7.35 – 7.14 (m,
8H), 4.33 (s, 2H) ppm.
5-Benzyl-2-chloropyridine (6na) (entry 16 of table 8)[11]: Yield: 87%
(0.177 g); Rf = 0.56 (hexane); 1H NMR (400 MHz, CDCl3): δ 8.26 (s, 1H),
7.41 (dd, 1H), 7.33 – 7.26 (m, 2H), 7.23 (dd, 2H), 7.14 (dd, 2H), 3.94 (s,
2H) ppm.
5-Benzyl-2-methoxypyridine (6aq) (entry 9 of table 8)[54]: Yield: 91%
(0.181 g); Rf = 0.51 (ethyl acetate/hexane 1:49); 1H NMR (400 MHz,
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10.1002/ejoc.201701241
European Journal of Organic Chemistry
FULL PAPER
2-Chloro-5-(naphthalen-1-ylmethyl)pyridine (6no) (entry 17 of table 8):
Obtained as a yellow oil; Yield: 85% (0.215 g); Rf = 0.32 (hexane); 1H NMR
(400 MHz, CDCl3): δ 8.33 (d, J = 2.2 Hz, 1H), 7.90 – 7.84 (m, 2H), 7.79 (d,
J = 8.3 Hz, 1H), 7.45 (m, 3H), 7.35 (dd, J = 8.2, 2.3 Hz, 1H), 7.27 (d, J =
7.0 Hz, 1H), 7.16 (d, J = 8.2 Hz, 1H), 4.39 (s, 2H) ppm. 13C NMR (100 MHz,
CDCl3): δ 149.8, 149.4, 139.1, 135.2, 134.8, 134.1, 131.8, 129.0, 128.0,
127.5, 126.5, 126.0, 125.7, 124.2, 123.8, 35.6 ppm. IR (KBr): 3046, 2917,
1584, 1563, 1509, 1459, 1382, 1288, 1200, 1104, 1022, 814, 794 cm-1;
HRMS (ESI): m/z calcd for C16H13ClN [M + H]+ 254.0736, found 254.0757.
Analytical data for ketones:
Benzophenone (8aa) (entry 1 of table 10)[58]: Yield: 95% (0.172 g); Rf =
0.68 (ethyl acetate/hexane 1:99); 1H NMR (400 MHz, CDCl3): δ 7.82 – 7.80
(m, 4H), 7.61 – 7.47 (m, 6H) ppm.
(4-Chlorophenyl)(phenyl)methanone (8ba) (entry 2 of table 10)[15d]
Yield: 92% (0.199 g); Rf = 0.71 (ethyl acetate/hexane 1:99); 1H NMR (400
MHz, CDCl3): δ 7.78 – 7.74 (m, 4H), 7.59 (m, 1H), 7.51 – 7.45 (m, 4H) ppm.
:
2-Chloro-5-(thiophen-3-ylmethyl)pyridine (6nf) (entry 18 of table 8)[11]
:
(4-Chlorophenyl)(4-ethylphenyl)methanone (8be) (entry 3 of table 10):
Obtained as a white solid; Yield: 91% (0.222 g); mp: 87 – 89 °C; Rf = 0.61
(ethyl acetate/hexane 1:99); 1H NMR (400 MHz, CDCl3): δ 7.75 – 7.70 (m,
4H), 7.45 (d, 2H), 7.31 (d, 2H), 2.74 (q, 2H), 1.28 (t, 3H) ppm; 13C NMR
(100 MHz, CDCl3): δ 195.4, 149.9, 138.7, 136.4, 134.9, 131.5, 130.4,
128.7, 128.1, 29.1, 15.4 ppm; IR (KBr): 2970, 2928, 2859, 1645, 1608,
1403, 1280, 1144, 1086, 852, 753, 675 cm-1; HRMS (ESI): m/z calcd for
C15H14ClO [M + H]+ 245.0733, found 245.0757.
Yield: 65% (0.136 g); Rf = 0.36 (hexane); 1H NMR (400 MHz, CDCl3): δ
8.27 (d, 1H), 7.46 (dd, 1H), 7.28 (m, 1H), 7.24 (s, 1H), 6.97 – 6.91 (m, 1H),
6.87 (dd, 1H), 3.96 (s, 2H) ppm.
1-Benzyl-4-methylbenzene (6ca) (entry 2 of table 9)[10]: Yield: 90%
1
(0.164 g); Rf = 0.89 (hexane); H NMR (400 MHz, CDCl3): δ 7.33 – 7.29
(m, 2H), 7.24 – 7.20 (m, 3H), 7.12 (m, 4H), 3.98 (s, 2H), 2.35 (s, 3H) ppm.
1-Benzyl-3-methylbenzene (6ma) (entry 3 of table 9)[10]: Yield: 91%
(0.165 g); Rf = 0.88 (hexane); H NMR (400 MHz, CDCl3): δ 7.35 – 7.27
(m, 2H), 7.21 – 7.15 (m, 4H), 7.01 – 6.98 (m, 3H), 3.94 (s, 2H), 2.31 (s,
3H) ppm.
(4-Chlorophenyl)(4-methoxyphenyl)methanone (8bd) (entry 4 of table
10)[59]: Yield: 93% (0.229 g); Rf = 0.38 (ethyl acetate/hexane 1:99); 1H NMR
(400 MHz, CDCl3): δ 7.80 (d, 2H), 7.71 (d, 2H), 7.45 (d, 2H), 6.97 (m, 2H),
3.90 (s, 3H) ppm.
1
1-Benzyl-2-methylbenzene (6ga) (entry 4 of table 9)[10]: Yield: 88%
(0.160 g); Rf = 0.88 (hexane); H NMR (400 MHz, CDCl3): δ 7.28 – 7.09
(m, 9H), 3.98 (s, 2H), 2.24 (s, 3H) ppm.
(4-(tert-Butyl)phenyl)(4-chlorophenyl)methanone (8br) (entry 5 of table
10)[15c]: Yield: 77% (0.210 g); Rf = 0.68 (ethyl acetate/hexane 1:99); 1H
NMR (400 MHz, CDCl3): δ 7.74 (dd, 4H), 7.50 (dd, 2H), 7.45 (d, 2H), 1.37
(s, 9H) ppm.
1
1-Benzyl-4-fluorobenzene (6da) (entry 5 of table 9)[10]: Yield: 85% (0.158
g); Rf = 0.89 (hexane); 1H NMR (400 MHz, CDCl3): δ 7.23 – 7.20 (m, 2H),
7.17 – 7.11 (m, 5H), 6.86 (t, 2H), 3.95 (s, 2H) ppm.
Bis(4-chlorophenyl)methanone (8bb) (entry 6 of table 10)[60]: Yield: 84%
(0.210 g); Rf = 0.65 (ethyl acetate/hexane 1:99); 1H NMR (400 MHz,
CDCl3): δ 7.72 (d, 4H), 7.46 (m, 4H) ppm.
1-Benzylnaphthalene (6ba) (entry 6 of table 9)[56]: Yield: 87% (0.189 g);
Rf = 0.82 (hexane); 1H NMR (400 MHz, CDCl3): δ 8.01 – 7.98 (m, 1H), 7.88
– 7.86 (m, 1H), 7.78 (d, 1H), 7.49 – 7.41 (m, 3H), 7.31 – 7.26 (m, 3H), 7.22
– 7.20 (m, 3H), 4.47 (s, 2H) ppm.
(4-Chlorophenyl)(4-fluorophenyl)methanone (8bc) (entry 7 of table
10)[61]: Yield: 83% (0.194 g); Rf = 0.63 (ethyl acetate/hexane 1:99); 1H NMR
(400 MHz, CDCl3): δ 7.82 – 7.78 (m, 2H), 7.72 – 7.69 (m, 2H), 7.46 – 7.42
(m, 2H), 7.17 – 7.12 (m, 2H) ppm.
2-Benzylnaphthalene (6fa) (entry 7 of table 9)[48]: Yield: 86% (0.187 g);
Rf = 0.8 (hexane); 1H NMR (400 MHz, CDCl3): δ 7.78 – 7.71 (m, 3H), 7.61
(s, 1H), 7.43 – 7.37 (m, 2H), 7.30 – 7.25 (m, 3H), 7.21 – 7.16 (m, 3H), 4.11
(s, 2H) ppm.
1-(4-(4-Chlorobenzoyl)phenyl)ethanone (8bp) (entry 8 of table 10)[62]
:
Yield: 54% (0.139 g); Rf = 0.58 (ethyl acetate/hexane 1:99); 1H NMR (400
MHz, CDCl3): δ 8.14 (d, 2H), 8.06 (d, 2H), 7.51 (d, 2H), 7.33 (m, 2H), 2.63
(s, 3H) ppm.
2-Benzyl-1,3,5-trimethylbenzene (6ha) (entry 8 of table 9)[44]: Yield: 88%
1
(0.185 g); Rf = 0.84 (hexane); H NMR (400 MHz, CDCl3): δ 7.23 – 7.15
(4-Chlorophenyl)(dibenzo[b,d]furan-4-yl)methanone (8bg) (entry 9 of
table 10): Obtained as a white solid; Yield: 71% (0.217 g); mp: 123 –
125 °C; Rf = 0.38 (ethyl acetate/hexane 1:99); 1H NMR (400 MHz, CDCl3):
δ 8.17 (dd, J = 7.7, 1.0 Hz, 1H), 8.00 (d, J = 7.5 Hz, 1H), 7.85 (d, J = 8.5
Hz, 2H), 7.71 (dd, J = 7.6, 0.9 Hz, 1H), 7.57 – 7.52 (m, 1H), 7.51 – 7.43
(m, 4H), 7.39 (dd, J = 11.4, 4.3 Hz, 1H) ppm; 13C NMR (100 MHz, CDCl3):
δ 192.8, 156.5, 153.8, 139.7, 136.2, 131.7, 128.9, 128.7, 128.0, 125.8,
124.6, 123.4, 123.3, 122.9, 122.8, 120.8, 112.3 ppm; IR (KBr): 3041, 1657,
1587, 1485, 1412, 1289, 1187, 1089, 948, 848, 747 cm-1; HRMS (ESI):
m/z calcd for C19H12ClO2 [M + H]+ 307.0525, found 307.0551.
(m, 3H), 7.00 (d, 2H), 6.88 (s, 2H), 4.01 (s, 2H), 2.28 (s, 3H), 2.20 (s, 6H)
ppm.
1-(4-Fluorobenzyl)-3-methylbenzene (6mc) (entry 9 of table 9)[10]: Yield:
1
78% (0.156 g); Rf = 0.86 (hexane); H NMR (400 MHz, CDCl3): δ 7.18 –
7.12 (m, 3H), 7.05 – 6.96 (m, 5H), 3.92 (s, 2H), 2.33 (s, 3H) ppm.
1-(4-Fluorobenzyl)-2-methylbenzene (6gc) (entry 10 of table 9)[47]: Yield:
1
76% (0.152 g); Rf = 0.87 (hexane); H NMR (400 MHz, CDCl3): δ 7.16 –
7.14 (m, 3H), 7.08 – 7.04 (m, 3H), 6.94 (t, 2H), 3.96 (s, 2H), 2.23 (s, 3H)
ppm.
(4-Methoxyphenyl)(phenyl)methanone (8ad) (entry 10 of table 10)[63]
:
Yield: 92% (0.195 g); Rf = 0.28 (ethyl acetate/hexane 1:99); 1H NMR (400
MHz, CDCl3): δ 7.84 – 7.82 (d, 2H), 7.75 (dd, 2H), 7.55 (m, 1H), 7.49 –
7.45 (m, 2H), 6.98 – 6.95 (d, 2H), 3.89 (s, 3H) ppm.
1-(4-(3-Methylbenzyl)phenyl)ethan-1-one (6mp) (entry 11 of table 9)[51]
:
Yield: 72% (0.161 g); Rf = 0.25 (ethyl acetate/hexane 1:49); 1H NMR (400
MHz, CDCl3): δ 7.89 (d, 2H), 7.29 (d, 2H), 7.20 (t, 1H), 7.07 – 6.96 (m, 3H),
4.00 (s, 2H), 2.58 (s, 3H), 2.33 (s, 3H) ppm.
(4-Ethylphenyl)(4-nitrophenyl)methanone (8ce) (entry 11 of table 10):
Obtained as a white solid; Yield: 82% (0.209 g); mp: 79 – 81 °C; Rf = 0.38
(ethyl acetate/hexane 1:99); 1H NMR (400 MHz, CDCl3): δ 7.93 – 7.92 (d,
2H), 7.91 – 7.90 (d, 2H), 7.75 – 7.72 (d, 2H), 7.35 – 7.33 (d, 2H), 2.78 –
2.72 (q, 2H), 1.33 – 1.25 (t, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ 194.7,
150.9, 149.8, 143.5, 134.0, 130.7, 130.6, 128.4, 123.6, 29.2, 15.3 ppm; IR
1-(4-(4-Fluorobenzyl)phenyl)ethan-1-one (6dp) (entry 12 of table 9)[57]
:
Yield: 71% (0.162 g); Rf = 0.28 (ethyl acetate/hexane 1:49); 1H NMR (400
MHz, CDCl3): δ 7.88 (d, 2H), 7.25 (d, 2H), 7.12 (dd, 2H), 6.98 (t, 2H), 4.00
(s, 2H), 2.57 (s, 3H) ppm.
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10.1002/ejoc.201701241
European Journal of Organic Chemistry
FULL PAPER
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Acknowledgements
We gratefully acknowledge the Department of Science and
Technology (DST), New Delhi for financial support. We thank the
Central Instrumentation Facility, Pondicherry University for NMR
spectra. VR also thanks UGC, India for a senior research
fellowship.
Keywords: Heterobiaryl • Palladium • Suzuki-Miyaura coupling •
Water • Zwitterionic
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European Journal of Organic Chemistry
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European Journal of Organic Chemistry
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Cross coupling reactions*
V. Ramakrishna,[a] M. Jhansi Rani,[a] and N. Dastagiri Reddy*[a]
Page No. – Page No.
A Zwitterionic Palladium(II) Complex as a Precatalyst for Neat
Water Mediated Cross-Coupling Reactions of Heteroaryl,
Benzyl and Aryl Acid Chlorides with Organoboron Reagents
A zwitterionic palladium(II) complex was found to be an efficient catalyst for catalyzing Suzuki-Miyaura cross coupling reactions
of aryl and heteroaryl organoboron reagents with various heteroaryl chlorides, aryl- and heteroaryl-methyl chlorides, and aryl
acid chlorides in neat water.
[a]
Prof. Dr. N. Dastagiri Reddy, V. Ramakrishna, M. Jhansi Rani
Department of Chemistry
Pondicherry University (A Central University)
This article is protected by copyright. All rights reserved.