Efficient nickel(II) naringenin-oxime complex catalyzed Mizoroki-Heck cross-coupling reaction in the presence of hydrazine hydrate

Article abstract of DOI:10.1039/c7nj03148c

A novel nickel(ii) naringenin-oxime complex was designed, synthesized and characterized. Therein, the nickel(ii) naringenin oxime complex as an efficient catalyst was used in Mizoroki-Heck coupling reactions of aryl halides containing electron-rich and electron-deficient substituents with styrene, methyl acrylate and divinylbenzene (DVB), respectively. The reaction proceeded efficiently under alkaline conditions in the presence of 0.30 mol% of the Ni(ii) naringenin oxime complexand N₂H₄·H₂O as the reductant in EtOH at 80 °C, and 32 alkene products were afforded in moderate to excellent yields, containing four new olefins. The new catalytic system not only provided an inexpensive and efficient process with greener conditions, but also broadened the reaction scope.

Full text of DOI:10.1039/c7nj03148c

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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Efficient nickel(II) naringenin-oxime complex catalyzed Mizoroki-
Heck cross-coupling reaction in the presence of hydrazine hydrate
JinꢀYi Song, Yang Liu,HongꢀYan Zhao,HuaꢀTao Han,ZhuoꢀFei Li, WeiꢀHao Guo, WenꢀYi Chu* and
ZhiꢀZhong Sun*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A novel nickel(II) naringenin-oxime complex was designed, synthesized and characterized. Therein,
nickel(II) naringenin oxime complex as an efficient catalyst was used in Mizoroki-Heck coupling reactions
of aryl halides adhering electron-rich and electron-deficient substituents with styrene, methyl acrylate and
divinylbenzene (DVB), respectively. The reaction proceeded efficiently under alkaline condition in the
presence of 0.30 mol% of Ni(II) naringenin oxime complex, N2H4·H2O as reductant in EtOH at 80 oC, and 32
alkenes products were afforded in moderate to excellent yields, containing four new olfeins. The new
catalytic system not only provided an inexpensive and efficient process with greener condition, but also
broadened the reaction scope.
the review of literatures, nickel not only shows good catalytic
properties, but also more electropositive than palladium.19 And
Introduction
Alkenes constitute a series of key structural motifs presence in
numerous pharmaceuticals,1ꢀ2 natural products,3ꢀ4 and flavors.5ꢀ6
Palladiumꢀcatalyzed MizorokiꢀHeck have proven to be the most
efficient method to synthesize products containing such motifs.7ꢀ12
Traditionally, phosphine ligands/Pd(OAc)2 can catalyze the coupling
reaction in the protection of inert atmosphere, however, phosphine
ligands are accompanied with limitations such as synthetic and
handling difficulties, air and moisture sensitivity13ꢀ15 etc. Moreover,
palladium catalysts are restricted with the poor solubility and the
high cost.16ꢀ18 Therefore, it is necessary to develop a cheap and
efficient catalytic system to solve above problems. On the basis of
nickel complexes bearing N,Oꢀbased ligands as catalysts could
accelerate the crossꢀcoupling reaction as well.
In 2007, Wang et al.20 synthesized nickel complexes bearing
N,N,Oꢀchelate anionic ligands and validated the good catalytic
activity in the Heck coupling reaction of iodides with butyl acrylate.
Ojwach’s group21 prepared new nickel(II) complexes bearing N,O,Sꢀ
ligated iminoꢀpyridyl derived ligands, which were active and stable
for Heck reactions towards aryl halides with methyl acrylate. In
2012,
nickel
complexes
of
tridentate
O,N,Sꢀdonors
thiosemicarbazones catalyzed Heck coupling reactions was reported
by Bhattacharya et al.22 And the activities of nickel complexes were
found to be comparatively high than previously species. As reported
by Sridevi et al.23 in 2013, the use of nickel(II) thiosemicarbazone
complex with low loading (0.5 mol%) as an efficient catalyst for the
Heck reaction of aryl bromides with olefins. In addition,
School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, P.
R. China. E-mail address:wenyichu@hlju.edu.cn. TEL/FAX: +86-451-86609135.
Key Laboratory of Chemical Engineering Process & Technology for High-efficiency
Conversion, College of Heilongjiang Province, Harbin 150080, P. R. China.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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Wang/Zong24 have shown a new type of Ni catalyst in Heck crossꢀ Ni(II) ion. In the FTꢀIR spectra of ligand, the characteristic (C=N)
coupling reaction, composed of Nꢀ(4,5ꢀdihydrooxazolꢀ2ꢀyl) band appeared at 1648 cmꢀ1, after the chelation leaded to the splitting
benzamide and the coupling of alkenes with aryl iodide or aryl of the characteristic (C=N) band in 1628 cmꢀ1, and the occurrence of
bromide in DMF provided the corresponding products with red shift, as was reported in the literature.23 Upon coordination with
moderate to good yields. Despite the good yields, there is a long time metal, the absorption bands near 545 and 465 cmꢀ1 were observed
of reflux, a high boiling solvent is used, and a small methodological from the FTꢀIR spectra of the complex and ascribable to NiꢀO and
scope, only having tested bromobenzene derivatives.
NiꢀN bands. NMR spectra of the synthesized ligand and complex
1
Naringeninꢀoxime as a N,Oꢀbased ligand is broadly investigated were measured in DMSO. For the complex, H NMR peak at 10.38
in biological chemistry owing to its chelating capability.25ꢀ26 The ppm was assigned to C=NꢀOH proton, so compared to ligand (11.21
need to abandon the use of the electron rich property of naringeninꢀ ppm), a shift of 0.83 ppm was observed. The disappearance of ꢀOH
oxime, prompted us to employ it as an organic ligand in the coupling on C5 in the 1H NMR peak indicated that the ꢀOH group of the
reaction. Herein, we reported a novel protocol for the Mizorokiꢀ ligand formed coordinate bond with metal resulting in the
Heck reaction in the presence of Ni(II) naringeninꢀoxime complex, deprotonation, then the hydrogen bond between exposed oxygen
and it was the first time to use naringeninꢀoxime as ligand to atom and OH of oxime group was formed. Similar shifts of the
promote the CꢀC crossꢀcoupling reactions. The ligand was acquired aromatic protons and C atoms were observed in the 13C NMR
in excellent yields by the oximation of naringenin, and the airꢀstable spectrum of the complex, which consistent with the observations
Ni(II) complex was synthesized by refluxing anhydrous NiCl2 with made by Volkov and coꢀworkers.27
naringenin oxime in the ration of 1:2 in the ethanolꢀethyl ether
The catalytic activity of nickel(II) naringeninꢀoxime complex
(Scheme 1). The unique catalyst displays promising application in was verified by MizorokiꢀHeck crossꢀcoupling reaction. In a model
MizorokiꢀHeck crossꢀcoupling reaction with ultraꢀlow Ni loading, reaction, the coupling of bromobenzene with styrene was studied in
meanwhile, the protocol is appropriate for heterocyclic substrates.
the presence of N2H4·H2O under air. The results were summarized in
Table 1.
Comparing the Niꢀbased catalysts in the same quantity,
Ni(OAc)2 or Ni(TFA)2 with good solubility catalyzed the reaction to
give about 40% yield (Table 1, entries 1ꢀ2). When the reaction
employed insoluble NiCl2 as catalyst, only 23% yield was obtained
(Table 1, entry 3). Surprisingly, with NiCl2 and the ligand, the yield
could be up to 69% (Table 1, entry 4). When the reaction was
performed using NiCl2/8ꢀhydroxyꢀ1ꢀtetralone (L1), and the yield
obtained was lower than for the naringeninꢀoxime as ligand (Table 1,
entry 5). To improve its solubility, the reaction was carried out in the
presence of the complex in EtOH, and the highest yield could be
achieved 88% (Table 1, entry 6). Various complex quantities were
also screened. The results showed that 0.30 mol% of the complex
was sufficient to catalyze the reaction more efficiently. When
increased the amount of the complex, no marked difference in the
yield was observed (Table 1, entries 8ꢀ9). The solvent had a
Scheme 1. Synthesis of the nickel(II) complex
Results and discussion
Complex have been fully characterized by spectroscopy (NMR,
HRMS, FTꢀIR) and by elemental analysis. The elemental contents
(C, H and N) of the synthesized complex were relatively close to its
calculated based on molecular formulae proposed. Compared IR
spectra of the synthesized ligand to complex, the strong band
emerging at 3412 cmꢀ1 in the IR spectra of ligand was assigned to the
vibration of νOꢀH. Upon complexation, the νOꢀH band was increased to
3476 cmꢀ1, indicating the occurrence of coordination of oxygen to
2 | J. Name., 2012, 00, 1-3
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dramatic influence on the Heck reaction, then polar and nonꢀpolar
solvents were selected.
In water medium (even under reflux conditon), the yield of the
reaction was very low (20%), owing to the poor solubility of the
substrates (Table 1, entry 10). Nonꢀpolar solvent was adverse to the
reaction, which only gave almost 34% yield (Table 1, entry 11).
However, when chosen polar solvents like DMF, DMSO, MeOH
and PrOH, approximately 70% yields of the products were isolated
(Table 1, entries 12ꢀ15). A slight increase in yields was observed
when different ration of EtOH/H2O (1:1, 1:3, 3:1) were used as
solvents (Table 1, entries 16ꢀ18). Results indicated that adding the
polar protic solvent EtOH into the reaction, the yield was substantial
increased to 88% (Table 1, entry 6).
Table 1 Effects of catalysts, solvents, bases and temperatures in the
Heck crossꢀcoupling reactionsa of bromobenzene with styrene
Catal.
Base
Temp.
(oC)
80
Yieldb
(%)
38
Entry
Solvent
Reductant
(mol%)
(equiv.)
1
2
3
Ni(OAc)2 (0.30)
Ni(TFA)2 (0.30)
NiCl2 (0.30)
EtOH
EtOH
EtOH
Na2CO3 (2.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
N2H4·H2O
N2H4·H2O
N2H4·H2O
80
40
80
23
NiCl2 (0.30) + L
(0.60)
4
5
EtOH
EtOH
Na2CO3 (2.0)
Na2CO3 (2.0)
80
80
N2H4·H2O
N2H4·H2O
69
63
The base also exerted a strong role in the reaction. With organic
bases like Et3N, ethylenediamine (EDA) and pyridine, transꢀstilbene
was obtained lower than 35% yield (Table 1, entries 20ꢀ22). Among
the various inorganic bases used for the MizorokiꢀHeck coupling
reation (Table 1, entries 6, 24ꢀ27), Na2CO3 (2.0 equiv.) was the
found to be the most suitable (88%, Table 1, entry 6). When
experiments were carried out in the presence of N2H4·H2O as a
reductant, the yield was significantly increased to 88%. When
N2H4·H2O was present as base (even increase the amount to 2.5
equiv.), the yield only reached 83% (Table 1, entries 6 and 20). It
indicated adding a little amount of reductant under alkali conditon
maybe activate the reducing ability of hydrazine so that promote the
coupling process.28ꢀ30 Different temperatures in the range rtꢀ120 oC
showed that 80 oC was the optimal for the reaction, even raise to
higher temperature, the yield had no significant change (Table 1,
entries 30ꢀ31).
NiCl2 (0.30) +
L1 (0.60)
6
Complex (0.30)
Complex (0.10)
Complex (0.50)
Complex (1.0)
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
EtOH
EtOH
Na2CO3 (2.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
80
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
88
51
85
85
20
34
75
65
66
61
7
80
8
EtOH
80
9
EtOH
80
10
11
12
13
14
15
H2O
reflux
reflux
reflux
reflux
reflux
reflux
Toluene
DMF
DMSO
MeOH
PrOH
EtOH:H2O
=1:1
16
17
18
19
20
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
Na2CO3 (2.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
reflux
reflux
reflux
80
N2H4·H2O
N2H4·H2O
N2H4·H2O
ꢀꢀ
75
73
78
82
83
EtOH:H2O
=1:3
EtOH:H2O
=3:1
N2H4·H2O
(2.0)
EtOH
EtOH
N2H4·H2O
(2.5)
80
ꢀꢀ
21
22
23
24
25
26
27
28
29
30
31
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
Complex (0.30)
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
Et3N (2.0)
80
80
80
80
80
80
80
rt
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
N2H4·H2O
25
33
EDA (2.0)
Pyridine (2.0)
NaOH (2.0)
Na2CO3 (2.5)
Na2CO3 (1.5)
Na2CO3 (1.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
Na2CO3 (2.0)
From the experimental data, we determined the optimized
conditions: the complex (0.30 mol%), Na2CO3 (2.0 equiv.),
N2H4·H2O (0.5 equiv.) in EtOH (4 mL) at 80 oC under air. With the
optimum reaction system, the MizorokiꢀHeck coupling reations of
various aryl halides with alkenes were examined to explore the
scope. The results were summarized in Table 2. As shown in Table
2, the MizorokiꢀHeck reaction of bromobenzene with styrene gave a
88% yield within 7.5 h (Table 2, entry 1). The properties and
positions of the substituents of aryl bromides were in association
with the yields.
30
78
87
80
66
trace
54
60
100
120
86
85
a Reaction conditions: bromobenzene (1.0 mmol, 1.0 equiv.), styrene
(1.3 equiv.), base, N2H4·H2O (0.5 equiv.), solvent (4 mL), under air,
7.5 h. b Yield of isolated product.
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Table 2 Heck crossꢀcoupling reactionsa of aryl halides with alkenes It was observed that 4ꢀsubstituted aryl bromides with electronꢀ
catalyzed by using the complex
withdrawing substituents such as nitro, formyl, cyano and bromo
groups (Table 2, entries 2ꢀ5) led to high yields of the corresponding
products. 4ꢀSubstituted aryl bromides with electronꢀdonating groups
like methyl and methoxy groups (Table 2, entries 6ꢀ7) underwent
the reaction smoothly to give moderate yields of products. The scope
of the reaction was investigated further by synthesizing naphthyl
olefin and ethylꢀ2ꢀmethylꢀ4ꢀstyrylbenzoate in good yields (85% and
83%, Table 2, entries 8ꢀ9). Furthermore, steric hindrance due to the
orthoꢀsubstituents on the aryl bromides affected the reaction
progress. orthoꢀNitrobromobenzene needed longer reaction time and
gave lower yield (73%) than paraꢀnitrobromobenzene (Table 2,
entries 2 and 10).
Time Yieldb
Entry
X
R1
R2
(h)
7.5
(%)
88
90
82
85
82
80
78
85
83
73
70
93
96
94
95
88
82
78
71
1
Br
Br
Br
Br
Br
Br
Br
Br
H
4ꢀNO2
4ꢀCHO
4ꢀCN
Ph
2
Ph
7.5
3
Ph
8.0
4
Ph
7.5
5
4ꢀBr
Ph
9.0
6
4ꢀMe
Ph
11.0
12.5
10.5
10.0
16.0
14.5
7.0
7
4ꢀOMe
1ꢀNaphthyl
Ph
Ph
8
9
Br 3ꢀMe,4ꢀCOOEt
Ph
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Cl
Cl
Cl
Cl
2ꢀNO2
3ꢀPyridyl
H
Ph
Then the reactions of aryl bromides with methyl acrylate were
tolerated in order to show the originality of the complex. The
coupling of bromobenzene with methyl acrylate afforded the methyl
cinnamate in 93% yield (Table 2, entry 12). Similar to the reaction
with styrene, the reactivity of aryl bromides adhering electronꢀ
withdrawing groups was found to be higher than those with electronꢀ
donating groups (Table 2, entries 13ꢀ17). Sterically hindered orthoꢀ
nitrobromobenzene could also react effectively with methyl acrylate
in a moderate yield (Table 2, entry 18). We further investigated the
MizorokiꢀHeck reaction of heterocyclic bromide like 3ꢀpyridyl
bromide with styrene and methyl acrylate (Table 2, entries 11, 19),
both of them gave the olefins products in medium yields, though the
yields were lower compared to bromobenzene with electronꢀ
donating and electronꢀwithdrawing substituent groups. Mizorokiꢀ
Heck crossꢀcoupling reactions were also employed for the synthesis
of pꢀphenylene vinylene. The results illustrated that both nonꢀ
substituted and 4ꢀsubstituted bromobenzene provided moderate
yields with divinylbenzene during the reaction, and the mainly
products were monoꢀcoupling olefins (Table 2, entries 20ꢀ26). When
increased the quantity of aryl bromides, the bisꢀcoupling olefins
products were also isolated in good yields (Table 2, entry 20).
Bromobenzene with double substituents involved in the reaction,
medium yields could be obtained as well. Especially, 3,4ꢀ
dibenzyloxybromobenzene as substrate coupled with divinylbenzene
Ph
CO2Me
4ꢀNO2
4ꢀCHO
4ꢀCN
CO2Me
7.0
CO2Me
7.5
CO2Me
7.0
4ꢀMe
CO2Me
8.0
4ꢀOMe
2ꢀNO2
3ꢀPyridyl
H
CO2Me
9.0
CO2Me
15.5
13.0
CO2Me
4ꢀCH2=CHꢀC6H4ꢀ
4ꢀCH2=CHꢀC6H4ꢀ
4ꢀCH2=CHꢀC6H4ꢀ
4ꢀCH2=CHꢀC6H4ꢀ
4ꢀCH2=CHꢀC6H4ꢀ
4ꢀCH2=CHꢀC6H4ꢀ
4ꢀCH2=CHꢀC6H4ꢀ
4ꢀCH2=CHꢀC6H4ꢀ
4ꢀCH2=CHꢀC6H4ꢀ
Ph
10.5 88,85c
4ꢀNO2
4ꢀCHO
4ꢀCN
11.5
12.0
12.0
13.5
13.5
13.0
14.5
15.0
9.5
89
86
88
80
78
76
78
74
66
68
61
56
4ꢀMe
4ꢀOMe
4ꢀCH2CN
3,4ꢀ(OBn)2
3,5ꢀ(CF3)2
H
4ꢀCHO
4ꢀMe
Ph
10.5
13.0
20.0
Ph
2ꢀNO2
Ph
a Reaction conditions: aryl halides (1.0 mmol, 1.0 equiv.), alkenes
(1.3 equiv.), Na2CO3 (2.0 equiv.), N2H4·H2O (0.5 equiv.), complex
o
b
(0.30 mol%), EtOH (4 mL), 80 C, under air. Yield of isolated
product. c bromobenzene (1.5 mmol), alkenes (1.3 equiv.), Na2CO3
(3.0 equiv.), N2H4·H2O (0.5 equiv.), complex (0.30 mol%), EtOH (4
mL), 80 oC, t=11.5 h, under air.
4 | J. Name., 2012, 00, 1-3
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in 75%
ARTICLE
yield,
which
is
superior
to
3,5ꢀ
Conclusions
ditrifluoromethylbromobenzene (Table 2, entries 27ꢀ28). Likewise,
the reaction of aryl chlorides with styrene could also occurred in the
optimal condition with midꢀlow yields (Table 2, entries 29ꢀ32).
Therein, four new olefins products were produced under the catalytic
system (Table 2, entries 9, 26ꢀ28). pꢀPhenylene vinylene and its
derivatives were the important units in the fields of the synthesis of
lightꢀemitting materials as well as studied on fieldꢀeffect transistor
and amphiphilic materials.31ꢀ32 Among the new isolated olefins, the
product of (E)ꢀ1,3ꢀbis(trifluoromethyl)ꢀ5ꢀ(4ꢀvinylstyryl)benzene
displays the better fluorescence (Table 2, entry 28).
In conclucion, a novel nickel(II) naringenin oxime complex as the
catalyst was successfully synthesized and applied in the Mizorokiꢀ
Heck crossꢀcoupling reactions, where electronꢀrich and electronꢀ
poor functionalized aryl halides with alkenes were catalyzed to
afford the corresponding products in moderate to high yields,
including four new olefins. The methodology not only provided a
simple and green reaction condition, but also enhanced good group
tolerance to obtain abundant alkenes products.
Experimental section
Based on the above results, and also in accordance with
previous literature reports,19, 33 a plausible mechanism as shown in
Scheme 2 is hypothesized.
General procedure for Heck cross-coupling reaction
In 10 mL reaction flask was charged with complex (0.30 mol %) and
N2H4·H2O (0.5 equiv.), then added aryl halides (1.0 mmol, 1.0
equiv.), olefin (1.3 equiv.), Na2CO3 (2.0 equiv.) and EtOH (4 mL).
Initially, LNi(0) catalyst (A) is formed by the activation of the
nickel(II) naringenin oxime complex in the presence of hydrazine
hydrate, and then the oxidative addition of bromobenzene to LNi(0)
catalyst produces the intermediate(B), which undergoes the
coordinationꢀinsertion of styrene into the bond of PhꢀNi to afford the
intermediates (C). Then, βꢀhydrogen elimination provides the target
compound transꢀstilbene and the intermediate (D). Reductive
elimination provides the regeneration of the LNi(0) catalyst in the
alkaline condition.
o
The reaction mixture was stirred at 80 C and the progress was
monitored by TLC analysis. After completion of the reaction, the
reaction mixture was poured into water and the aqueous layer was
extracted with ethyl acetate 3 times (3 × 10 mL), and the combined
organic layer was dried over anhydrous sodium sulfate. After
filtration and removal of the solvent, the residue was purified by
column chromatography (petroleum ether/ethyl acetate = 10:1 as
eluent) to afford the pure product. The characterizations of the
synthesized products are all matched with the authentic samples (see
the Supporting information).
Acknowledgements
We are grateful for the financial support of Fund of Natural Science
Foundation with grant (No. B201207 and B201208) of Heilongjiang
Province of China.
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