Bis-quinoline-2-carboxylic acid Copper Salt as an Efficient Catalyst for Synthesis of Aryl Olefins by Heck Reaction

Article abstract of DOI:10.1007/s10562-019-02885-6

Abstract: A bis-quinoline-2-carboxylic acid copper salt as a single crystal was prepared and characterized by X-ray single crystal analysis. The crystal as a catalyst was applied to the Mizoroki–Heck coupling reaction between arylboronic acids and α-olefins. A series of diarylethenes and aryl olefins were synthesized with good to excellent yields at room temperature. The catalytic system exhibited good functional group tolerance and low pollution. Graphic Abstract: A bis-quinoline-2-carboxylic acid copper salt as a single crystal was prepared and characterized by X-ray single crystal analysis. The crystal as a catalyst was applied to the Mizoroki–Heck coupling reaction between arylboronic acids and α-olefins[InlineMediaObject not available: see fulltext.].

Full text of DOI:10.1007/s10562-019-02885-6

Catalysis Letters
https://doi.org/10.1007/s10562-019-02885-6
Bis‑quinoline‑2‑carboxylic acid Copper Salt as an Efcient Catalyst
ꢀor Synthesis oꢀ Aryl Oleꢁns by Heck Reaction
Minghui Zuo · Zhuofei Li1,2 · Wanyong Fu1,2 · Rui Guo1,2 · Chuanfu Hou1,2 · Weihao Guo1,2 · Zhizhong Sun1,2
1,2
·
Wenyi Chu1
,2
Received: 1 April 2019 / Accepted: 27 June 2019
©
Springer Science+Business Media, LLC, part of Springer Nature 2019
Abstract
A bis-quinoline-2-carboxylic acid copper salt as a single crystal was prepared and characterized by X-ray single crystal analy-
sis. The crystal as a catalyst was applied to the Mizoroki–Heck coupling reaction between arylboronic acids and α-olefns.
A series oꢀ diarylethenes and aryl olefns were synthesized with good to excellent yields at room temperature. The catalytic
system exhibited good ꢀunctional group tolerance and low pollution.
Graphic Abstract
A bis-quinoline-2-carboxylic acid copper salt as a single crystal was prepared and characterized by X-ray single crystal analy-
sis. The crystal as a catalyst was applied to the Mizoroki–Heck coupling reaction between arylboronic acids and α-olefns
.
Keywords Bis-quinoline-2-carboxylic acid copper salt · Single crystal · Mizoroki–Heck reaction · Diarylethene · Aryl
olefns
1
Introduction
Stilbenoid as important aryl oleꢀins are widely used in
important felds such as materials, medical drugs, hygiene,
and cosmetics. Diarylethene [1] and its derivatives, as the
parent structures oꢀ stilbenoid, are structural units ꢀor the
synthesis oꢀ ꢁuorescent materials [2, 3], ꢁavors [4], bio-
logically active [5] and natural product intermediates [6, 7],
especially in ꢁuorescent materials and natural products such
as piceatannol-mic-4 (anti-inꢁammatory, antibacterial) [8],
piceatannol-mic-5 (anti -biological activity) [9] and DBF
Electronic supplementary material The online version oꢀ this
article (https://doi.org/10.1007/s10562-019-02885-6) contains
supplementary material, which is available to authorized users.
*
Wenyi Chu
wenyichu@hlju.edu.cn
(
anti-tumor, hypolipidemic) [10]. In addition, Schiꢂ base
-cyano stilbene [11] and the compound BBU [12] are used
1
2
School oꢀ Chemistry and Materials Science, Heilongjiang
University, Harbin 150080, People’s Republic oꢀ China
2
in the feld oꢀ ꢁuorescent materials. The equally important
aryl olefns are α,β-unsaturated compounds and their deriva-
tives. These compounds have various physiological activi-
ties such as bactericidal, anti-allergic, anti-inꢁammatory and
Key Laboratory oꢀ Chemical Engineering Process
and Technology ꢀor High-eꢃciency Conversion,
College oꢀ Heilongjiang Province, Harbin 150080,
People’s Republic oꢀ China
Vol.:(0
1
123456789)
3

M. Zuo et al.
anti-oxidation [13]. It has been increasingly used in ꢀood
additives and biopharmaceuticals feld. Such as Caꢂeic
acid (anti-bacterial) [14], Sinapic acid (anti-oxidant) [15]
[16–24] Conventional methods employed various transition
metal (Pd, Co, Ni, Cu etc.) and phosphine ligands as cata-
lysts [25–29]. In 2013, Liwosz et al. [30] used Cu(OTꢀ)
2
(
Fig. 1).
and N,N ligand 1,10-phenanthroline as the catalyst to obtain
diarylethene and its derivatives through benzyl triꢁuorobo-
rate and 1,1-diphenylethylene as substrates (Scheme 1a). In
2017, Kurandina et al. [17] reported the use oꢀ ꢀerrocene
compound as catalyst ꢀor the selective synthesis oꢀ cinna-
myl-trimethylsilane and its derivatives with iodomethyl-tri-
methylsilane and styrene as substrates (Scheme 1b). In 2018,
Hamasaka et al. [31] described Pd NNC-Pincer Complex as
an eꢂective catalyst ꢀor the Mizoroki–Heck reaction to syn-
thesize butyl (2E)-3-phenyl acrylate and its derivatives with
iodobenzene and butyl acrylate as substrates (Scheme 1c).
Although these reactions are highly eꢃcient, there are still
some disadvantages such as the use oꢀ expensive transition
metal, the diꢃculty in synthesizing N, N ligand, poor solu-
bility and environmental pollution caused by substrate halide
ion. Thereꢀore, it is the current research ꢀocus to explore low
cost catalytic reaction system and to develop a ligand with
good coordination eꢂect.
In recent years, due to the wide application oꢀ diaryle-
thenes and α,β-unsaturated compounds, it has received great
attention to develop an eꢃcient synthesis method. These
compounds are mainly obtained by Heck coupling reaction.
Based on the above problems, transition metal Cu(II) is
preꢀerred as catalyst because oꢀ its stability and low cost,
and N,O ligands are preꢀerred due to their ease oꢀ prepara-
tion and good coordination ability. Arylboronic acids are
selected as the substrate because oꢀ their good stability,
atomic economy and low pollution. Herein, a novel Mizo-
roki–Heck reaction method ꢀor synthesizing diarylethenes
and α,β-unsaturated compounds was reported by using bis-
quinoline-2-carboxylic acid copper salt as catalyst, arylbo-
ronic acid and styrene as substrates (Scheme 1d).
Fig. 1 Representative compounds with aryl olefns structure skeleton
Scheme 1 The method ꢀor
(
a)
synthesis oꢀ diarylethene
(
b)
(
c)
(
d)
1
3

Bis‑quinoline‑2‑carboxylic acid Copper Salt as an Efcient Catalyst ꢀor Synthesis oꢀ Aryl…
2
Results and Discussion
substrates (Table 1, entry 8). MeOH/H2O (1:1) was used as
the solvent to give a moderate yield oꢀ 79% (Table 1, entry
9). EtOH as the solvent also gave a yield oꢀ 85% (Table 1,
entry 10). When the non-polar solvent toluene was used, the
reaction was unꢀavorable, and the yield was 60% (Table 1,
entry 11). However, polar aprotic solvents such as DMF and
DMSO were selected and gave the product yields in 80% and
78%, respectively (Table 1, entries 12 and 13). Thereꢀore,
MeOH was an appropriate solvent and could give 95% yield
(Table 1, entry 5).
The synthesized copper complex was characterized by
X-ray single crystal analysis. The ORTEP oꢀ the molecu-
lar structure oꢀ the Cu(C H NO ) (H O) complex is
1
0
10
2 2
2
shown in Fig. 2, and the crystal data is listed in the sup-
port inꢀormation. X-ray diꢂraction analysis indicated that
the Cu(C H NO ) (H O) complex crystallized in the
1
0
10
2 2
2
monoclinic system and the space group P 2 /c. The molecu-
1
lar structure oꢀ the complex contains a Cu atom and two
quinoline-2-carboxylic acid (Ligand) units, and the copper
atom consists oꢀ two quinoline nitrogen (N1, and N2) atoms
and two ketone oxygens (O2, O3,) atoms. This paper is to
determine the novel copper complex as a catalyst ꢀor the
Mizoroki–Heck cross-coupling reaction. (CCDC 1892561).
In order to evaluate the catalytic activity oꢀ the bis-quin-
oline-2-carboxylic acid copper salt ꢀor the Mizoroki–Heck
cross-coupling reaction, phenylboronic acid and styrene
were used as the substrates to screen reaction conditions,
and the results were summarized in Table 1.
The bases as another important ꢀactor were also inves-
tigated including organic and inorganic bases. The organic
n
bases such as Et3N, pyridine and Bu3N were employed to
give the yields in 95%, 88% and 85%, respectively (Table 1,
entries 5, 14–15). For inorganic bases such as K2CO3,
Na2CO3 and NaOH, the reactions gave moderate yields in
82%, 83% and 76%, respectively (Table 1, entries 16–18).
Thereꢀore, triethylamine was appropriate ꢀor this reaction,
and the yields decreased with the increase or decrease oꢀ its
equivalent number (Table 1, entry 5). In addition, when the
reaction was heated at 50 °C and 66 °C, the yield decreased
to 60% and 40% (Table 1, entries 19–20). Thereꢀore, based
on experimental results and previous reports [32, 33], room
temperature is best temperature in the reaction work.
Base on above experimental results, it was determined
that the optimal reaction system was arylboronic acid
(1.0 mmol, 1.0 eq.) and α-olefn (1.5 eq.) as the reaction
substrates, bis-quinoline-2-carboxylic acid copper salt
(0.50 mol%) as catalyst, MeOH (10 ml) as solvent, Et3N
(2.0 eq.) as base, at room temperature ꢀor 4 h.
Firstly, catalysts as critical ꢀactors ꢀor the reaction were
screened, compared with some Cu(II) catalysts, Cu(OTꢀ)
2
as the catalyst gave a yield oꢀ 65% (Table 1, entry 1), while
CuSO only gave a low yield oꢀ 35% (Table 1, entry 2).
4
When quinaldic acid as a ligand was added into the reaction
systems oꢀ Cu(OTꢀ) and CuSO , the yields were increased
2
4
to 75% and 40%, respectively (Table 1, entries 3–4). While
synthesized Cu complex was used as the catalyst gave a high
yield in 95% (Table 1, entry 5). In addition, the ratios oꢀ
the complex did not aꢂect the reaction very much (Table 1,
entries 5–7).
Aꢀter determining the optimal reaction system, we ꢀurther
explored the substrate range oꢀ arylboronic acid and olefns,
and the results were summarized in Table 2.
Next, reaction solvents as important ꢀactors ꢀor the Heck
reaction were screened. In an aqueous medium, the reaction
yield was a little low (45%) due to poor solubility oꢀ the
First, using the substrate aryl chloride and phenylboronic
acid to react with styrene, the reaction yield oꢀ aryl chlo-
ride is very low, only 35%, compared to the best yield oꢀ
boric acid, so the fnal use oꢀ substrate aryl Table 2, entries
1
–2). 4-Substituted arylboronic acid with electron with-
drawing group such as –NO , –CHO, –Br and –CN gave
2
high yields oꢀ the corresponding product in 90%, 88%, 86%
and 85%, respectively (Table 2, entries 3–6). Similarly,
the electron-donating such as –CH and –OCH also gave
3
3
the corresponding product in high yields (Table 2, entries
7
–8). 2-Substituted arylboronic acid with electron-donating
or electron withdrawing group, such as –CH and –NO ,
3
2
gave similar yields in 78% and 79%, respectively, but less
than that oꢀ 4-substituted arylboronic acid because oꢀ the
steric hindrance eꢂect (Table 2, entries 9–10). In addition,
naphthyl substituent was ꢀurther studied to obtain the target
product in good yield oꢀ 83% (Table 2, entry 11).
When the olefn was changed to methyl acrylate, phe-
nylboronic acid gave the corresponding product with excel-
lent yield (Table 2, entry 12). 4-Substituted arylboronic
Fig. 2 The molecular structure oꢀ Cu(C H NO ) (H O) complex
1
0
10
2 2
2
and H-atoms are omitted ꢀor clarity
1
3

M. Zuo et al.
Table 1 Optimization oꢀ the reaction conditions oꢀ phenylboronic acid with styrene
a
Entry
Catal. (mol%)
Solvent
Base(equiv.)
Temp.(°C)
Yield (%)
1
2
3
4
5
6
7
8
9
Cu(OTꢀ) (0.5)
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
Et N
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
50
65
35
75
40
2
3
CuSO (0.5)
Et N
4
3
Cu(OTꢀ) (0.5)+L
Et N
2
3
CuSO (0.5)+L
Et N
4
3
b
c
Complex(0.5)
Complex(0.3)
Complex(0.7)
Complex(0.5)
Complex(0.5)
Complex(0.5)
Complex(0.5)
Complex(0.5)
Complex(0.5)
Complex(0.5)
Complex(0.5)
Complex(0.5)
Complex(0.5)
Complex(0.5)
Complex(0.5)
Complex(0.5)
Et N
92 ,95,94
3
Et N
92
95
45
79
85
60
80
78
88
85
82
83
76
60
40
3
Et N
3
H O
Et N
2
3
MeOH:H O(1:1)
EtOH
Toluene
DMF
DMSO
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
Et N
2
3
10
11
12
13
14
15
16
17
18
19
20
Et N
3
Et N
3
Et N
3
Et N
3
Pyridine
n
Bu N
3
K CO
2
3
Na CO
2
3
NaOH
Et N
3
Et N
66
3
Reaction conditions: phenylboronic acid (1.0 mmol, 1.0 eq.), styrene (1.5 eq.), base (2.0 eq.), solvent (10 mL), 4 h
a
Yield oꢀ isolated product
Base (1.5 eq.)
Base (2.5 eq.)
b
c
acid with electron withdrawing group such as –NO , –CN
In order to insight into the reaction process, control
experiments (shown in Scheme 2) were conducted. Firstly,
radical inhibition experiment was conducted using TEMPO
as blocker (Scheme 2a), phenyl radical [35] was isolated in
26% yield (spectroscopic data are in the Supporting Inꢀorma-
tion), and the desired diarylethene product was not detected,
it indicates that the reaction is a radical reaction mechanism.
When the reaction was under pure oxygen environment,
signifcant change in yield was not observed (Scheme 2b).
However, when the reaction was under nitrogen protection,
diarylethene product was pretty low (Scheme 2c), this sug-
gests that oxygen in the air is an important ꢀactor in the
reaction.
2
and –CHO gave good yields oꢀ 94–95% (Table 2, entries
1
3–15), while 4-substituted arylboronic acid with electron-
donating groups such as –OMe and –Me gave yields oꢀ 82%
and 83% (Table 2, entries 16–17). 2-Nitro phenylboronic
acid gave a moderate yield oꢀ 78% because oꢀ the steric hin-
drance eꢂect (Table 2, entry 18). In addition, the substrate
oꢀ 4-substituted diolefns were also extended, the yields oꢀ
electron-withdrawing group –NO , –CHO, –CN and elec-
2
tron-donating group –CH , –OCH were similar in medium
3
3
and upper yield (Table 2, entries 19–24). Both monoolefns
and diolefns gave high to excellent yields. Based on this
research, non-terminal olefns were studied and synthesized,
and the yield only reached 39% (Table 2, entry 25). There-
Based on these experimental results and previous liter-
atures [30, 34, 35], a plausible mechanism is assumed as
shown in Scheme 3.
ꢀ
ore, non-terminal olefns also can be applied to this system,
but the yield is lower. Finally, when the reaction substrate
was detected to be benzylboronic acid, the yield oꢀ the prod-
uct was 75% (Table 2, entry 26). In summary, this reaction
showed good ꢀunctional group tolerance.
II
Under the action oꢀ Cu complex, phenylboronic acid
is oxidized by C–B bond split to produce intermediate A.
Next, phenyl radical as intermediate B is generated, Cu(II)
1
3

Bis‑quinoline‑2‑carboxylic acid Copper Salt as an Efcient Catalyst ꢀor Synthesis oꢀ Aryl…
Table 2 Substrates scope oꢀ cross-coupling reactions catalyzed by the complex
a
Entry
X
R1
R2
Yield (%)
1
2
3
4
5
6
7
8
9
H
H
–Ph
–Ph
Ph
96
35
90
88
86
85
85
85
78
79
83
95
94
93
95
82
83
78
85
84
88
86
85
85
39
75
Cl
4-NO2
4-CHO
4-Br
4-CN
4-Me
4-OMe
2-Me
2-NO2
1-Naphthyl
H
4-NO2
4-CN
4-CHO
4-Me
4-OMe
2-NO2
H
4-NO2
4-CN
4-CHO
4-CH3
4-OCH3
H
–Ph
–Ph
–Ph
–Ph
–Ph
–Ph
–Ph
–Ph
–CO Me
–CO Me
–CO Me
–CO Me
–CO Me
–CO Me
–CO Me
4-CH =CH–C H –
4-CH =CH–C H –
2 6 4
4-CH =CH–C H –
4-CH =CH–C H –
4-CH =CH–C H –
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
2
2
2
2
2
2
2
2
6
4
2
6
4
2
6
4
2
6
4
4-CH =CH–C H –
–C(Me)=CH–Ph
Ph
2
6
4
b
c
Ph–CH2–
Reaction conditions: phenylboronic acid 1.0 mmol (1.0 eq.), alkenes (1.5 eq.), Et N (2.0 eq.), complex (0.50 mol%), MeOH 10 mL, RT ꢀor 4 h
3
a
Yield oꢀ isolated product
Substrates are Ph–B(OH) and Ph–CH =CH–CH
b
2
2
3
c
Substrates are Ph–CH –B(OH) and Ph–CH=CH
2
2
2
Scheme 2 Experiments ꢀor
mechanism research
(a)
(b)
(c)
1
3

M. Zuo et al.
4.2 Synthesis of Complex
The quinaldine acid ligand and copper nitrate were added
to a round bottom ꢁask with anhydrous ethanol and diethyl
ether as mixed solvent. The mixture was stirred at room tem-
perature ꢀor 2 h, fltered and dried to give a pale pink solid.
Acknowledgements This work was supported by Fund oꢀ Natural Sci-
ence Foundation oꢀ Heilongjiang Province oꢀ China (No. B2018012).
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