One-Pot Synthesis of Benzene and Pyridine Derivatives via Copper-Catalyzed Coupling Reactions

Article abstract of DOI:10.1002/adsc.201700053

A highly efficient one-pot synthesis of polysubstituted pyridine has been achieved through copper-catalyzed oxidative sp³ C?H coupling of acetophenones with toluene derivatives. Besides, the polysubstituted benzene was obtained through copper-catalyzed coupling of acetophenones. Both of the reactions exhibited a good functional group tolerance to produce a 2,4,6-triphenylpyridine or 1,3,5-triarylbenzene in high yields. Compared with previous methods, these transformations allow a highly flexible and efficient preparation of substituted pyridines and benzenes. (Figure presented.).

Full text of DOI:10.1002/adsc.201700053

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DOI: 10.1002/adsc.201700053
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One-Pot Synthesis of Benzene and Pyridine Derivatives via
Copper-Catalyzed Coupling Reactions
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Jianwei Han,a Xin Guo,a Yafeng Liu,a Yajie Fu,a Rulong Yan,a and
Baohua Chena,*
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a
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Gansu
and
Key Laboratory of Nonferrous
Metal Chemistry and Resources Utilization of Gansu
Province, Lanzhou 730000, Peopleꢀs Republic of China
Fax: (+86)-931-891-2582
E-mail: chbh@lzu.edu.cn
Received: January 15, 2017; Revised: April 12, 2017; Published online: && &&, 0000
Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.201700053
pounds.[4] Due to their excellent thermal stability, they
can be used in asymmetric catalysis and coordination.
In the exploration of a 2,4,6-triphenylpyridine syn-
thesis, the most common way involves reaction of
Abstract: A highly efficient one-pot synthesis of
polysubstituted pyridine has been achieved through
copper-catalyzed oxidative sp3 CÀH coupling of
acetophenones with toluene derivatives. Besides,
acetophenones, a nitrogen source in the presence of
the polysubstituted benzene was obtained through
various catalysts.[5] Some synthesized them with 2,4,6-
copper-catalyzed coupling of acetophenones. Both
triphenylpyridine by oxime acetates.[6] Guan’s
of the reactions exhibited a good functional group
group[6c,d] reported Cu- and Fe-catalyzed synthesis of
tolerance to produce a 2,4,6-triphenylpyridine or
2,4,6-triphenylpyridine with oxime acetates in 2011
1,3,5-triarylbenzene in high yields. Compared with
and 2017 (Scheme 1, eq 1). Jiang’s group[5b] reported a
previous methods, these transformations allow a
Cu-catalyzed synthesis of 2,4,6-triphenylpyridine with
highly flexible and efficient preparation of substi-
acetophenone and benzylamine under the neat con-
tuted pyridines and benzenes.
dition in 2013 (Scheme 1, eq 2). More recently, Yi’s
group[5e] reported a HOTf-catalyzed synthesis of 2,4,6-
Keywords: polysubstituted pyridine; copper-cata-
triarylpyridine with acetophenone and benzylamine
lyzed; polysubstituted benzene; acetophenones;
under the neat condition in 2016 (Scheme 1, eq 2). In
toluene derivatives
our group,[6a] we reported the Cu-catalyzed synthesis
of 2,4,6-triphenylpyridine with oxidative sp3 CÀH
coupling of oxime acetates (Scheme 1, eq 3). Encour-
42 Pyridine is one of the most important privileged N- aged by the graceful strategies mentioned above, we
43 heterocyclic compounds in organic chemistry, that can present an economic synthetic method of 2,4,6-
44 be found in a vast array of natural products such as triphenylpyridine through copper-catalyzed oxidative
45 alkaloids.[1] The functionalized pyridines are widely sp3 CÀH coupling of acetophenones and NH4OAc
46 used in industry, and have been diversified into with toluene derivatives (Scheme 1, eq 4).
47 subunits such as anti-HIV drugs, anticancer drugs,
We initially investigated our reaction by employing
48 anti-oxidation materials and anti-bacterial materials in acetophenone 1a, NH4OAc and toluene 2a as model
49 medicine, pesticides and organic materials in agricul- substrates. We chose Cu(OTf)2 as the catalyst and O2
50 ture, etc.[2] In the past years, a variety of methods have as the oxidant in toluene (1.0 mL) at 1008C for 14 h
51 been reported for the synthesis of pyridine hetero- (Table 1, entry 1), and the 2,4,6-triphenylpyridine
52 cycles. Despite efficiency and importance,[3] these (3aa) was formed in a yield of 48%. We continued to
53 methods are still restricted to high temperature and optimize the reaction parameters to obtain a better
54 other harsh conditions. Hence, an efficient method for yield. Compared with O2, air, H2O2, K2S2O8, PIDA
55 easily building the pyridine motif is urgently desirable. and DTBP, TBHP proved to be the optimal oxidants,
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Pyridines with the 2,4,6-triphenylpyridine pattern affording the desired product 3aa in 89% yield
57 play a highly important role in heterocyclic com- (Table 1, entries 1–7). Screening of other solvents,
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Table 1. Optimization of the Reaction Conditions[a]
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Entry
Catalyst
Oxidant
Solvent
Yieldb
(%)
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9
10
11
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17
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20
21
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8
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(Br)2
Cu(Cl)2
O2
Air
K2S2O8
PIDA
H2O2
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
DMSO
DMF
48
nd
trace
65
58
86
89
nd
nd
66
83
26
48
78
56
66
16
14
nd
83
33
87
DTBP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
9
10
11c
12d
13e
14
15
16
17
18
19
20f
21g
22h
PhCl
PhCl
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Scheme 1. Synthetic approaches to pyridines.
Cu(OAc)2
CuBr
CuI
27 such as DMSO, DMF and chlorobenzene showed that
28 toluene is the optimal solvent (Table 1, entries 8–10).
29 With chlorobenzene as the solvent, the 3aa yield was
30 66%. When the temperature increased to 1208C, the
31 yield of 3aa was increased to 83% (Table 1, entries
32 10–11). Various inorganic nitrogen sources such as
33 NH4Cl and (NH4)2CO3 were screened to confirm NH4
34 OAc as the best choice for the reaction system
35 (Table 1, entries 12–13). Screening of other copper
36 compound catalysts, such as Cu(OAc)2, CuBr2, CuCl2,
37 CuI and CuBr, showed that Cu(OTf)2 was the optimal
38 choice (Table 1, entries 14–19). By reducing the
39 amount of TBHP, we discovered that the reaction with
40 three equivalents of TBHP afforded the optimal result
41 (Table 1, compared with entries 7 and 20). The
42 temperature was changed to 808C, resulting in the
43 product 3aa having inferior yields. And when the
44 temperature was increased to 1208C, the yield of the
45 product did not increase (Table 1, entries 21–22).
-
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
[a] Reaction conditions: 1a (0.2 mmol), catalyst (20 mol%),
oxidant (3.0 equiv.), solvent (1.0 mL), under air, 1008C,
14 h.
[b] Yields of isolated products.
[c] 1208C.
[d] NH4Cl.
[e] (NH4)2CO3.
[f] fTBHP (2.0 equiv.).
[g] 808C.
[h] 1208C.
TBHP = terbutylhydroperoxide (5.0–6.0 M in decane),
PIDA=PhI(OAc)2, DTBP=di-t-butyl peroxide, DMSO=
demethyl sulfoxide, DMF=N,N-dimethyl formamide.
46
With the optimized conditions established, the electron-donating groups (methoxy group) on the
47 generality of the reaction was explored. We initially aromatic did not afford a good yield (3ae–3ag). In
48 investigated the generality of acetophenone, and the addition, the experimental results showed that elec-
49 results were summarized in Table 2. This coupling tron-withdrawing groups on the aromatic ring ob-
50 reaction tolerated a wide range of substituents on the tained corresponding pyridines in good to excellent
51 aromatic ring of acetophenone. According to the yields (3ah–3al), and some of them seemed to increase
52 experimental results, we found that substrates with the reaction yield slightly such as trifluoromethyl at
53 weak electron-donating groups on the aromatic ring the para-position (3aj). Disappointingly, the reaction
54 that produced the corresponding pyridines could with p-nitro-substituted acetophenone did not obtain
55 provide excellent yields (3ab–3ad), such as methyl the desired product 3ap, indicating that the acetyl
56 regardless of the functional groups at the para-, meta-, group of the aromatic ring could not cause a reaction
57 or ortho-position. However, the substrates with strong because of the electron conjugation and induction of
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the nitro group. In the intermolecular effect, both para
and meta-position had good yields. The yield of the
ortho-position (3ag) was poor due to a large ortho-
blockage. In addition, 2-acetylnaphthalene, 2-acetyl-
furan and a-tetralone also afforded the corresponding
pyridines (3am–3ao) in moderate yields respectively.
Besides, the 3-acetylpyridine was also investigated,
but the desired product 3aq was not found.
Table 2. Synthesis of pyridines from different acetopheno-
ne[a,b]
In order to acquire a variety of polyfunctional
10 pyridines, we next investigated the scope of various
11 methylarenes (Table 3). Toluene was not suitable as a
12 solvent for this reaction. It has been found that
13 chlorobenzene is a relatively better solvent for this
14 purpose (Table 1, entry 11). The optimal temperature
15 for the reaction was determined to be 1208C and this
16 method was further expanded by the utilization of a
17 wide range of substituted toluenes. The experimental
18 results showed that both the electron-donating groups
19 and the electron-withdrawing groups on the aromatic
20 ring proceeded successfully to come up with the
21 desired products in good yields (3ba–3bk). Disap-
22 pointingly, the reaction with 2-nitrotoluene did not
23 obtain the desired product 3bl indicating that the 2-
24 nitrotoluene cannot cause the reaction because of the
25 electron conjugation and induction of the nitro group.
26 In the intermolecular effect, the corresponding pyr-
27 idines were obtained in good yields, regardless of the
28 functional groups at the para-, meta-, or ortho-
29 position.
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To widen the diversity of substrates for polysub-
31 stituted pyridines, we tried to use propiophenones and
32 methyl heterocycles as substrates for this transforma-
33 tion (Scheme 2). Propiophenones and 2-methylfuran
34 afforded the corresponding pyridines (4aa and 5aa) in
35 moderate yields respectively. Disappointingly, the
36 reaction with 2- methylpyridine and 2-methylquinoline
37 did not obtain the desired product (5ab and 5ac).
38
Considering the wide substrate selectivity by the
39 Cu(OTf)2 catalysis, a series of experiments were
40 carried out to explore the mechanisms of reaction. As
41 shown in Scheme 3, we conducted a controlled trial.
42 First, we found no reaction occurring when the
43 catalyst was absent. To our surprise, the trisubstituted
44 benzene (6a) scaffold was obtained in a 83% yield,
45 when only adding in acetophenone 1a and the catalyst
46 with the toluene as solvent (Scheme 3a). At the same
47 time, other corresponding acetophenones successfully
48 obtained the desired products in good yields (6b–e).
49 The results showed that the epimerization of the enol
50 form of the protonated ketone might be a key
51 intermediate in the catalytic cycle. In addition, it
52 opened up a new method for an efficient way to
[a] Reaction conditions: 1 (0.2 mmol), Cu(OTf)2 (20 mol%),
NH4OAc (0.6 mmol) and TBHP (0.6 mmol) in Toluene
(1.0 mL) at 1008C for 14 h.
[b] Isolated yields.
53 synthesize benzene. The reaction was not carried out benzaldehyde (Scheme 3b) or the benzyl alcohol
54 when acetophenone 1a, the catalyst and ammonium (Scheme 3c) were added with toluene as the solvent,
55 acetate were added to the reaction system with the 2,4,6-triphenylpyridine was obtained in a good
56 toluene as the solvent. And when the acetophenone yield. This indicated that the reaction may be toluene
57 1a, the catalyst, the ammonium acetate and the
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Table 3. Synthesis of pyridines from diverse arylmethane[a,b]
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Scheme 2. Synthesis of pyridines from 4a, 5a, 5b and 5c.
to benzaldehyde C by the TBHP.[8] Next, nucleophilic
addition of B to C would afford imine intermediate
D.[9] The intermediate E would be formed by con-
densation reaction of intermediate D with another
molecule of acetophenone 1a. Then intermediate E
through beta-elimination and oxidation would afford
intermediate F.[10] Cu(OTf)2 would be formed by
getting rid of copper ions and HOTf, which completed
the catalytic cycle. Next, isomerization of F would
produce complex G and electrocyclization of inter-
mediate G, assisted by Cu(OTf)2 forms intermediate
H. Finally, the intermediate H would undergo dehy-
dration step to furnish the desired product 3aa.
[a] Reaction conditions: 1a (0.2 mmol), 2 (0.6 mmol),
Cu(OTf)2 (20 mol%), NH4OAc (0.6 mmol) and TBHP
(0.6 mmol) in PhCl (1.0 mL) at 1208C for 14 h.
[b] Isolated yields.
On the other hand, the interaction of Cu (OTf)2
and intermediate A would afford an intermediate of
I.[11] Next, the intermediate J would be formed by a
condensation reaction of intermediate I with a second
molecule of acetophenone 1a. Subsequently, the
48 oxidation to benzaldehyde and benzaldehyde should condensation of intermediate J with a third molecule
49 have been another key intermediate of the reaction. of acetophenone 1a would form intermediate K, which
Based on previous studies and reported litera- would lead to the production of intermediate L upon
50
51 ture,[7–11] a plausible reaction mechanism has been releasing copper ions. Cu(OTf)2 would be formed by
52 proposed to explain the formation of product 3aa and getting rid of copper ions and HOTf, which completed
53 6a (Scheme 4). First, acetophenone 1a would be the catalytic cycle. Then the intermediate L would
54 isomerized to intermediate A and intermediate B undergo electrocyclization promoted by Cu(OTf)2 to
55 would be formed by intermediate A, Cu(OTf)2 and furnish intermediate M. Finally, the intermediate M
56 NH4OAc, with H2O, HOTf and HOAc being re- through dehydration step would afford the desired
57 leased.[7] While toluene 2a would be easily converted product 6a.
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Scheme 3. Mechanistic studies.
Scheme 4. Possible mechanism.
In summary, we have developed a new, mild and
36 highly efficient Cu(OTf)2 catalyst for the one-pot
37 synthesis of polysubstituted pyridines and benzene.
38 These processes afforded some new approaches to
39 polysubstituted pyridines and benzenes with advan-
40 tages such as ready availability of the starting materi-
41 als (acetophenone and toluene), tolerance to a wide
42 range of functional groups, cheap catalysts and mild
43 conditions. Based on the above study, further research
44 on the details of the mechanism and the synthetic
45 applications of this transformation are currently on-
46 going in our laboratories.
anhydrous Na2SO4 and evaporation. The residue was purified
by column chromatography on silica gel (petroleum ether/
EtOAc=40:1) to yield the isolated product 3aa.
Synthesis of 4-(4-methylphenyl)-2,6-diphenylpyridine (3ba):
A test tube was charged with acetophenone (0.2 mmol),
para-xylene (0.6 mmol), Cu(OTf)2 (20 mol%), NH4OAc
(0.6 mmol) and TBHP (0.6 mmol) in PhCl (1.0 mL). The
mixture was stirred at 1208C for 14 h under air. When the
reaction was completed (detected by TLC), the mixture was
cooled to room temperature. The mixture was diluted with
water and extracted with EtOAc (33 20 mL). The combined
organic layers were dried over anhydrous Na2SO4 and
evaporation. The residue was purified by column chromatog-
raphy on silica gel (petroleum ether/EtOAc=40:1) to yield
the isolated product 3ba.
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Experimental Section
Synthesis of 2,4,6-triphenyl-pyridine (3aa): A test tube was
charged with acetophenone (0.2 mmol), Cu(OTf)2
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Synthesis of 5’-phenyl-1,1’:3’,1’’-terphenyl (6a): A test tube
was charged with acetophenone (0.6 mmol) and Cu(OTf)2
(20 mol%) in toluene (1.0 mL). The mixture was stirred at
1008C for 14 h under air. When the reaction was completed
(detected by TLC), the mixture was cooled to room temper-
ature. The mixture was diluted with water and extracted with
EtOAc (33 20 mL). The combined organic layers were dried
(20 mol%), NH4OAc (0.6 mmol) and TBHP (0.6 mmol) in
toluene (1.0 mL). The mixture was stirred at 1008C for 14 h
under air. When the reaction was completed (detected by
TLC), the mixture was cooled to room temperature. The
mixture was diluted with water and extracted with EtOAc
(33 20 mL). The combined organic layers were dried over
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over anhydrous Na2SO4 and evaporation. The residue was
purified by column chromatography on silica gel (petroleum
ether/EtOAc=50:1) to yield the isolated product 6a.
1H NMR and 13C NMR spectra were determined on
300 MHz and 75 MHz in CDCl3. unknown products were
further characterized by HRMS (TOF-ESI), the melting
points of solid products were determined on a microscopic
apparatus.
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Acknowledgements
We are grateful for financial support from the National
Science Foundation of P. R. of China (No. 21372102,
21672086).
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