Pd(II) complexes of novel phosphine ligands: Synthesis, characterization, and catalytic activities on Heck reaction

Article abstract of DOI:10.1080/10426507.2015.1119827

Novel phosphine oxides, (((3-methylpyridin-2-yl)amino)methyl)diphenylphosphine oxide (1) and diphenyl((pyrazin-2-ylamino)methyl)phosphine oxide (2), were synthesized and characterized. Phosphines ligands (3 and 4) were obtained by the reduction of 1 and 2 with AlH₃, monitored by³¹P NMR spectroscopy. Pd(II) complexes of 3 and 4 were synthesized and characterized (5 and 6). The catalytic activity of 5 and 6 was tested on the reaction of styrene with both activated and deactivated aryl bromides in air. The results of the catalytic experiments were discussed through DFT calculations.

Full text of DOI:10.1080/10426507.2015.1119827

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Pd(II) Complexes of Novel Phosphine Ligands:
Synthesis, Characterization and Catalytic Activities
on Heck Reaction
Orhan Altan, Osman Serindağ, Koray Sayın & Duran Karakaş
To cite this article: Orhan Altan, Osman Serindağ, Koray Sayın & Duran Karakaş (2016):
Pd(II) Complexes of Novel Phosphine Ligands: Synthesis, Characterization and Catalytic
Activities on Heck Reaction, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:
10.1080/10426507.2015.1119827
To link to this article: http://dx.doi.org/10.1080/10426507.2015.1119827
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Pd(II) Complexes of Novel Phosphine Ligands: Synthesis, Characterization and Catalytic
Activities on Heck Reaction
a
b
c
c
Orhan Altan *, Osman Serindağ , Koray Sayın , Duran Karakaş
a
Chemistry Department, Technical Sciences Vocational School, Mersin University, Mersin,
3343, TURKEY, e-mail: orhanaltan@mersin.edu.tr
3
b
Kanuni University, Science Institute, Çukurova, Adana, TURKEY
c
Department of Chemistry, Faculty of Science, Cumhuriyet University 58140 Sivas, TURKEY
Shortened title: New Pd(II) Complexes for Heck Reaction
ABSTRACT
Novel phosphine oxides, (((3-methylpyridin-2-yl)amino)methyl)diphenylphosphine oxide (1)
and diphenyl((pyrazin-2-ylamino)methyl)phosphine oxide (2), were synthesized and
characterized. Phosphines ligands (3 and 4) were obtained by the reduction of 1 and 2 with AlH3,
3
1
monitored by P NMR spectroscopy. Pd(II) complexes of 3 and 4 were synthesized and
characterized (5 and 6). The catalytic activity of 5 and 6 was tested on the reaction of styrene
with both activated and deactivated aryl bromides in air. The results of the catalytic experiments
were discussed through DFT calculations.
1
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Keywords: phosphine ligands, palladium complexes, Heck reaction, DFT calculations.
2
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INTRODUCTION
Palladium-catalyzed cross-coupling reactions leading to the formation of carbon-carbon bonds
1
,2
are among the most powerful tools in organic synthesis. Mizoroki-Heck cross-coupling
reaction is a widely used method to couple aryl halides with terminal olefins to form cinnamates
3
and stilbenes, which are of industrial importance. It is known that palladium complexes,
containing phosphine ligands, which combine both good donor strength and π-accepting
4
capacity, have a high catalytic activity in Mizoroki-Heck cross-coupling reactions.
In this study, two new phosphine oxides were synthesized and characterized. Their reduction
products were used as ligands to prepare Pd(II)-phosphine complexes. The catalytic activity of
Pd(II)-phosphine complexes was investigated on Heck Reaction of styrene with both activated
and deactivated aryl bromides in air. The results of the catalytic experiments were discussed
through DFT calculations.
RESULTS AND DISCUSSION
Synthesis
The Mannich condensation is a powerful tool to prepare aminomethylphosphines by the reaction
of hydroxymethylphosphines with aliphatic or aromatic amines. This procedure provides a
5
-7
standard route to linear, branched and cyclic aminophosphines . In contrast to aliphatic and
8
aromatic amines, aminopyridines react sluggishly and long reaction times are required . This
may be due to either reducing the nucleophilicity of the amino group by the pyridine ring or
tautomerism phenomena on the aminopyridine. In the literature, although some
8
,9
aminopyridinemethylphosphines can be isolated in moderate yields , in our hands, 3-
3
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methylpyridin-2-amine (3) and pyrazin-2-amine (4) derivatives of aminomethylphosphines non-
isolable. Several attempts were to isolate the free phosphine ligands were unsuccessful. In order
to perform characterization properly, the crude product was treated with H
2
2
O , and the oxide
forms of the desired ligands (1 and 2) were isolated in fair yields. The route of synthesis was
given in Scheme 1.
1
0
11
Reduction of phosphine oxides can be achieved by numerous ways . The method , which uses
alane (AlH ) as reducing agent, is easy to perform, is very high yielding and does not require an
aqueous workup, was applied in this work to reduce phosphine oxides. Reduction processes were
3
3
1
achieved in >95% yield based on the P NMR and 84-88% based on the product mass (Scheme
).
1
Metal complexes (5 and 6) were synthesized immediately, by the reaction of Pd(COD)Cl with
2
phosphines in 2:1 molar ratio at room temperature.
Characterization
3
1
Oxide forms of the ligands (1 and 2), and metal complexes (5 and 6) were characterized by P,
1
3
1
C, H NMR, FT-IR spectroscopies and elemental analysis.
3
1
The P NMR spectra of 1 and 2 showed single resonances at 31.0 and 30.2 ppm, respectively,
9
c
13
which were in consistent with those reported tertiary phosphine oxides . In the C NMR
spectra, doublets at 40.3 (J = 77.4 Hz) and 40.3 (J = 78.9 Hz) ppm are indicative for the N-CH -
2
1
P bound formation, for 1 and 2 respectively. Similarly, the peaks in the H NMR spectra that are
found at 4,47 (d, JPH = 5.2 Hz)(1) and 4.42 (t, JPH = 6.0 Hz) ppm (2) are also supported the N-
1
CH
2
-P bound formation. Furthermore, the peaks in the H NMR spectra at 6.59(1) and 6.56(2)
4
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8
,
ppm (NH) are confirmed the presence of only one Ph
2
PCH group maintained on the molecule
2
9
.
The IR spectrum of 1 and 2 showed characteristic weakly absorbing stretching vibrations of
-
1
-1
-1
-1
v(NH) at 3250 cm and 3258 cm and strong absorptions of ν(P=O) at 1178 cm and 1164 cm
respectively.
3
1
After the reduction process of phosphine oxides, the peaks that are observed in the P NMR
spectra at 31.0 (1) and 30.2 (2) ppm, were shifted to -16.7 ppm (3) and -17.0 (4) which are
8
, 9
characteristic for mono-substituted aminomethylphosphines .
3
1
In the P NMR spectra of 5 and 6, the peaks at 25.5 and 26.5 ppm were demonstrated the
coordination of the ligands to the Pd(II) center, free phosphines have -16.7 ppm and -17.0 ppm
8
,9
for 3 and 4, respectively . Durran et al. have shown that, by spectroscopic and single crystal
XRD measurements, analogues of 3 and 4 prefer phosphorus coordination in a cis mode, when
8
,9a,b
the ligand : metal molar ratio was 2 : 1
. The spectroscopic results obtained in our work, are
in consistent with the literature and it can be assumed that phosphines are bound to Pd(II) center
in a cis manner. The structures of the complexes are given in Scheme 1.
Conventionally, comparing the spectroscopic data of the ligand and their metal complex is more
preferred way to indicate the electronic differentiation on the structure. However, some
differences can also be detected between the phosphine oxides and the metal-phosphine
1
2
complexes, which can be connected by the back-donation phenomena of the phosphine ligands .
3
1
It can be noticed that in the P NMR spectra, the formation of metal complexes resulted in
increased electron density on phosphorus atoms (5, 25.5 ppm and 6, 26.5 ppm), compared to the
5
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oxide forms (1, 31.0 ppm and 2, 30.2 ppm). Similarly, the increase of the electron density on
1
3
phosphorus atoms reflected in the C NMR spectra, as the shifting the peaks of ipso-carbon of
phenyl ring (133.9 ppm, J = 94.4 Hz, 5; 132.5 ppm, J = 104.2 Hz, 6) as well as N-C-P carbon of
methyl backbone (39.9 ppm, J = 69.4 Hz, 5; 40.3 ppm, J = 65.1 Hz, 6), to the upfield region
1
and coupling constants decreased. Finally, in the H NMR spectra, N-CH
2
-P protons were
observed as singlet at 4.46 ppm (5) and 4.31 ppm (6) which were shifted to the upfield region,
compared with the oxide forms (4.47 ppm, [d, J = 5.2 Hz] 1; 4.42 [t, J = 6.0 Hz] 2)
-1
-1
-1
The IR spectra of 5 and 6 showed bands centered at 3327 cm , 3353 cm and 327- 327 cm
-1
indicative of ν(NH) and ν(Pd-Cl), respectively. P=O bound stretching frequencies at 1178 cm
-1
(
1) and 1164 cm (2) are disappeared in the IR spectra of 5 and 6, as well.
Catalytic activity
Palladium-catalyzed cross-coupling reactions have been proved extremely powerful synthetic
tools. The effectiveness of the palladium catalyst depends on the ligand coordinated to the
1
3
palladium atom . The rate of coupling, as its well known, also depends on parameters such as
solvent, base and reaction temperature. In this study, in order to optimize the reaction conditions
bromobenzene was chosen as a model substrate for styrene. Four different bases and two
different solvents were tested with a 0.4% mol catalyst ratio at 140 °C. After 3 h, the best results
were obtained in DMF at 140 °C with 1.2 eq. Na
2
CO and the 0.4% mol catalyst ratio and these
3
conditions were chosen to investigate the catalytic activity of complexes on the reaction of
styrene with seven different aryl bromides. The results of the optimization experiments are
summarized in Table 1.
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The catalytic activity of 5 and 6 was investigated in the reaction of styrene with activated and
deactivated aryl bromides. In the light of optimization experiments, minimum reaction time set at
3
hours and reactions were continued until the complete conversion. Good to excellent yields
were obtained (Table 2). In the reactions with activated aryl bromides, 5 accelerated the reaction
more than 6 (Table 2, Entry 1-3) and in the reaction with deactivated one, 2-bromo-6-
methoxynaphthalene (Entry 4), as well. On the other hand, it can be considered that 6 is more
selective than 5. In the case of 2-bromo-6-methoxynaphthalene, only the desired product was
obtained. The results are summarized in Table 2.
DFT Calculations
Structurally similar Pd(II) complexes (5 and 6) were showed different catalytic activities on
Heck reaction. In order to understand the reason of this, we focused on Heck reaction
mechanism. It is widely accepted that oxidative addition is the rate limiting step on Heck
3
,4,13
reaction. In this step zero-valent palladium species, formed during the pre-activation process
,
reacts with aryl halides. In the literature, the zero-valent palladium was usually described as di-
0
coordinated Pd complexes.
Complex 5 and 6 are not only monophosphines but also have nitrogen donors which can be
0
coordinate to the metal center. We were supposed that tetra-coordinated Pd (5b and 6b)
complexes, which are catalytically inactive, (Scheme 2) can be formed during the pre-activation
0
process. In order to investigate this suggestion, mentioned di- and tetra- coordinated Pd
complexes are optimized at B3LYP/6-31G(d)(LANL2DZ) level in gas phase and thermodynamic
parameters of relevant complexes are investigated in detail.
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Optimized structures of complexes are represented in Figures S 15-S 18 (Supplemental
Materials) and structural parameters are given in Table S 1. The most stable complexes for each
equilibrium are determined by using total energy (ETotal), enthalpy (H) and Gibbs free energy
(
G). Additionally, equilibrium constants (K) for each transformation are predicted (Table S 2).
Catalytic activity rankings of these complexes are investigated by using some quantum chemical
parameters which are energy of HOMO (EHOMO), energy gap between LUMO and HOMO
(EGAP), global hardness (η), global softness (σ), electronegativity (χ), electrophilicity index (ω),
nucleophilicity index (N) and dipole moment (µ) (Table S 3).
According to the DFT calculations, 5b and 6b are probable species. However complex 5a and 6a
are more stable complexes. Equilibrium constants of 5a ⇌ 5b and complex 6a ⇌ 6b are
calculated as 0.984 and 0.857, respectively. These equilibrium constants were not indicated
significant correlation between equilibrium constants and catalytic activities.
E
HOMO and nucleophilicity are the quantum chemical descriptors that usually associated with
electron donating ability. High value of EHOMO and nucleophilicity shows the tendency of
1
4,15
electron transfer to appropriate molecule
. If EHOMO and nucleophilicity are decisive for the
catalytic reactivity in the oxidative addition step, 5a should be a more active catalyst than 6a,
which is in agreement with the experimental results.
CONCLUSIONS
phosphines can be isolated in moderate yields but those pyridine/pyrazine containing phosphine
ligands (3) and (4) were non-isolable. Fortunately, the oxide forms of the ligands 1 and 2 were
properly isolated and characterized. Their palladium complexes (5 and 6) were synthesized by
the reaction of phosphines (3 and 4), obtained by the reduction processes, with CODPdCl
2
at
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room temperature in good yields. The catalytic activity of the complexes was tested on the Heck
reaction. Good to excellent yields were obtained on the reaction of styrene with both activated
and deactivated aryl bromides in air.
EXPERIMENTAL
All reactions were performed under argon, all chemicals and solvents were purchased from
Aldrich and used directly without further purification unless otherwise stated. EtOH and de-
ionized H
molecular sieve. THF and Et
argon. Bis(hydroxymethyl)diphenylphosphonium chloride , AlH
were prepared according to literature procedures. IR spectra were recorded by using a Perkin
2
O were degassed prior to use. CH
2
Cl was distilled under argon and stored 4 Å
2
2
O were dried over sodium-benzophenonekethyl and distilled under
1
6
13
17
3
-THF and PdCl (COD)
2
1
13
31
Elmer FT-IR/FIR/NIR Spectrometer Frontier Spectrometer. H-NMR, C-NMR and P-NMR
spectra were recorded on Bruker 400 MHz NMR Spectrometer with chemical shifts (δ) in ppm to
high frequency of SiMe
4
and H
3
PO , respectively. Elemental analysis were performed on LECO
4
CHNS-932 with TCD detector. GC analyses were performed on a PerkinElmer Clarus 500 gas
chromatograph equipped with a flame-ionization detector (FID) and a 30 m capillary column
1
13
31
containing dimethylpolysiloxane stationary phase. H, C and P NMR spectra of synthesized
compounds are presented in Supplemental Materials (Figures S 1-S 14).
Synthesis
3
-CH
3
-py-2-NHCH
2
P(O)Ph
2
(1): To a solution of bis(hydroxymethyl)diphenylphosphonium
O (2:1, 15 mL) NEt (1.0 mL) was added followed by
chloride (0.7630 g, 2.7 mmol) in EtOH:H
2
3
the appearance of cloudy solution. Then, 3-methylpyridin-2-amine (0.2808 g, 2.6 mmol) was
9
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added and the mixture was refluxed for 36 h. After cooling to room temperature the mixture was
extracted with CH
removed under reduced pressure and remaining oily residue was dissolved THF (5 mL). H
30%, 1 mL) was added to this solution and stirred for 24 h. White solid was obtained by adding
2
Cl
2
(3 × 10 mL). Organic layer was separated and dried on MgSO , volatiles
4
2
O
2
(
-1
-1
1
n-hexane. Yield: 0.5424 g (64.7%) (1). IR : 3250 cm (νNH), 1178 cm (νP=O). H NMR (400
3
12-21
1
MHz, ) δ 8.05 (d, J = 4.8 Hz, 1H ), 7.48 – 7.27 (m, 10H
), 7.17 (d, J = 6.9 Hz, 1H ), 6.59 (s,
7
2
8
22 13
1
H ), 6.53 (dd, J = 6.9, 5.2 Hz, 1H ), 4.47 (d, J = 5.2 Hz, 2H ), 2.04 (s, 3H ). C NMR (101
5
3
1
10,
MHz, CDCl
3
): δ 156.6 (d, J = 4.3 Hz, C ), 145.4 (C ), 136.8 (C ), 135.9 (d, J = 141.74 Hz, C
1
1
14, 19
12, 16, 17, 21
13, 15,
), 133.0 (d, J = 17.7 Hz, C
), 129.0 (d, J = 6.7 Hz, C
), 128.65 (d, J = 6.5 Hz, C
1
8, 20
6
2
8
22 31
)
, 116.9 (C ), 113.0 (C ), 40.3 (d, J = 77.4 Hz, C ), 16.6 (C ). P NMR (162 MHz, ): δ 31.0
(
s). Anal. Calcd for C19
H
19
2
N OP: C, 70.80; H, 5.94; N, 8.69; Found: C, 70.94; H, 5.96 N, 9.00
pyz-2-NHCH
2
P(O)Ph
2
(2): This compound was prepared by the same procedure described
-1
above for 1 and obtained as light yellow solid (0.5931 g). Yield : 64.0%. IR : 3258 cm (νNH),
-1
1
3
1
164 cm (νP=O). H NMR (400 MHz, CDCl ) δ 8.07 (d, J = 1.2 Hz, 1H ), 7.89 (dd, J = 2.6, 1.4
3
2
12, 16, 17, 21
6
13, 14, 15, 18, 19,
Hz, 1H ), 7.83 – 7.75 (m, 4H
), 7.73 (d, J = 2.8 Hz, 1H ), 7.59 – 7.35 (m, 6H
2
0
7
8
13
)
, 6.56 (s, 1H ), 4.42 (t, J = 6.0 Hz, 2H ). C NMR (101 MHz, CDCl
3
) δ 154.2 (d, J = 5.9 Hz,
5
3
10, 11
14, 19
6
C ), 141.1 (C ), 133.7 (d, J = 154.6 Hz, C
), 132.3 (d, J = 2.8 Hz, C
), 131.4 (C ), 131.1
1
2, 16, 17, 21
2
13, 15, 18, 20
(
d, J = 9.8 Hz, C
), 130.4 (C ), 128.8 (d, J = 11.8 Hz, C
C ). P NMR (162 MHz, CDCl ) δ 30.2 (s). Anal. Calcd for C17
3.59. Found: C, 65.81; H, 5.19; N, 13.64
-CH -py-2-NHCH PPh (3): AlH -THF (1.48 mL, 0.55 M) was added slowly to stirred
), 40.3 (d, J = 78.9 Hz,
8
31
3
H
16
3
N OP: C, 66.01; H, 5.21; N,
1
3
3
2
2
3
solution of 1 (0.250 g, 0.78 mmol) in dry-THF (5 mL). The mixture was refluxed for 1 h and
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3
1
reaction was monitored by P-NMR spectroscopy. After the reduction was complete, the
mixture was cooled to room temperature and methanol (95 μL, 2.33 mmol) was added. The
slurry was filtered over celite and washed with hot dry-THF (3 × 5 mL). The volatiles in filtrate
were removed under reduced pressure, and the oily product was obtained (0.200 g). Yield:
3
1
(
84%). 3. P NMR (162 MHz, CDCl
pyz-2-NHCH PPh (4): This compound was prepared by the same procedure for 3 given above
and obtained as colorless oil (0.225 g). Yield: 88%. P NMR (162 MHz, CDCl
3
) δ -16.7 (s).
2
2
31
3
) δ -17.0 (s).
(
3-CH
3
-py-2-NHCH
2
PPh
2
)
2
PdCl
2
(5): Pd(COD)Cl
2
(0.043 g, 0.15 mmol) in CH
2
Cl
2
(5 mL)
was added to a solution of 3 (0.094 g, 0.31 mmol) in CH
2
Cl (20 mL) and then stirred at room
2
temperature for 30 min. After completion of the reaction, the reaction mixture was concentrated
under reduced pressure, and diethyl ether was added to precipitate the product. The resulting
-
1
light yellow solid was filtered and then dried. Yield: 0.102 g (86%). IR : 3327 cm (νNH), 327
-
1
1
and 285 cm (νPd-Cl) . H NMR (400 MHz, ) δ 8.04 (s, 2H), 7.53 – 7.29 (m, 20H), 7.17 (s, 2H),
1
3
6
.54 (s, 2H), 5.69 (s, 2H), 4.46 (s, 4H), 1.90 (s, 6H). C NMR (101 MHz, ) δ 156.6 (d, J = 3.6
Hz), 145.4 (s), 136.8 (s), 133.9 (d, J = 94.4 Hz), 133.0 (d, J = 18.3 Hz), 129.0 (d, J = 6.6 Hz),
3
1
1
28.7 (d, J = 6.6 Hz), 116.9 (s), 113.03 (s), 39.9 (d, J = 69.4 Hz), 16.6 (s). P NMR (162 MHz,
CDCl ) δ 25.5 (s). Anal. Calcd for C38 Pd: C, 57.77; H, 4.85; Cl, 8.98; N, 7.09; P,
.84; Pd, 13.47. Found: C, 58.06 H, 4.87; N, 7.12.
Pyz-2-NHCH PPh PdCl (6): This compound was prepared by the same procedure for 5
given above and obtained as light yellow solid. Yield : 0.082 g (63%). IR : 3353 cm (νNH), 319
3
H
38Cl
2
N P
4 2
7
(
2
2
)
2
2
-1
-1
1
and 284 cm (νPd-Cl). H NMR (400 MHz, ) δ 8.07 (s, 2H), 7.90 (d, J = 0.8 Hz, 2H), 7.83 –
1
3
7
.75 (m, 4H), 7.73 (d, J = 2.7 Hz, 2H), 7.56 – 7.40 (m, 6H), 5.22 (s, 2H), 4.31 (s, 4H). C NMR
11
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(
101 MHz, ) δ 154.2 (d, J = 5.8 Hz), 141.1 (s), 132.5 (d, J = 104.2 Hz), 132.3 (d, J = 1.9 Hz),
3
1
1
31.4 (s), 131.1 (d, J = 9.5 Hz), 130.4 (s), 128.8 (d, J = 11.7 Hz), 40.3 (d, J = 65.1 Hz). P NMR
) δ 26.5 (s). Anal. Calcd for C34 Pd: C, 53.46; H, 4.22; Cl, 9.28; N,
1.00; P, 8.11; Pd, 13.93. Found: C, 53.25; H, 4.24; N, 10.96.
(
162 MHz, CDCl
3
H
32Cl
2
N P
6 2
1
General procedure for Heck cross-coupling reaction
Heck coupling reactions were carried out in air. In a typical experiment, an oven-dried, sealed
tube equipped with a magnetic stir bar was charged with aryl bromide (0.1 mmol), styrene (0.12
mmol) and a base (0.12 mmol). The catalyst solution (0.0004 mmol catalyst in 2.0 ml solvent)
was then added. The reaction mixture was placed in a silicon oil bath at 140 °C and stirred. After
the required reaction time, the mixture was allowed to cool to room temperature, diluted with
CH
2
Cl
2
, and washed with HCl aqueous solution and brine. The organic phase was separated and
SO , and the solvent was evaporated. The residue was chromatographed on silica
dried over Na
2
4
gel using an ethyl acetate/hexane (1:5) mixture as eluent. Conversion percentages were
determined from the solution by GC analysis, and isolated yields, which were characterized by
1
13
H and C NMR, determined by GC based on ArBr.
Computational Method
Numerical calculations were achieved by using GaussView 5.0.8 and Gaussian 09 AM64L-
1
8
1
9
20,21
G09RevD.01 . Becke,3-parameter,Lee-Yang-Parr (B3LYP) method
was selected as
computational method for studied complexes. LANL2DZ and 6-31G(d) basis sets were used in
complex calculations for metal atoms and rest atoms in complex, respectively. All calculations
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were made in gas phase. Imaginary frequency was not obtained in whole calculations. According
to Koopmans theorem, the HOMO and LUMO energies were associated with Eqs. (1) and (2):
I  EHOMO
A  ELUMO
(1)
(2)
Some quantum chemical parameters which are EGAP, η, σ, χ, ω and N were calculated by using
1
9,22-25
Eqs. (3)-(8)
EGAP  ELUMO  EHOMO
I  A
(3)
(4)


2
1


(5)
(6)
(7)

I  A



2
2

2

1
N 
(8)

ACKNOWLEDGMENTS
This work was supported by Çukurova University Scientific Research Projects (FEF2009D7).
The authors thank to Dr. Mustafa Kemal YILMAZ for GC analysis and Tuncay INCE for NMR
spectra recording. The numerical calculations reported in this paper are performed at TUBITAK
ULAKBIM, High Performance and Grid Computing Center (TRUBA Resources).
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a, b
Table 1. The results of optimization experiments of Heck reaction.
Entry
Base
Solvent
T (°C) Conversion (%)
1
2
3
4
5
6
7
8
Na
2
CO
CO
NaOAc
NEt
Na CO
CO
3
DMF
DMF
140
140
140
140
140
140
140
140
92
38
K
2
3
DMF
77
3
DMF
18
2
3
1,4-Dioxane
1,4-Dioxane
< 5
< 5
13
K
2
3
NaOAc 1,4-Dioxane
NEt 1,4-Dioxane
3
< 5
a
Conditions : Bromobenzene (0.1 mmol), stryrene (0.12 mmol), Base (0.12 mmol), catalyst
0,0004 mmol), solvent (2.0 mL)
(
b
Percentage conversions were determined by GC based on bromobenzene after 3 h.
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a
Table 2. Results of Heck cross-coupling reaction of styrene with aryl bromides.
b
c
Entry
ArBr
Cat.
Time (h)
Conversion
%)
Yield
(%)
(
1
5
6
5
6
5
6
5
6
5
6
5
6
5
6
3
8
3
8
3
8
3
8
8
8
8
8
8
8
100
100
100
100
100
100
96
82
85
91
93
93
92
87
78
78
81
73
75
86
78
2
3
4
5
6
78
85
88
78
81
7
94
89
a
Conditions : ArBr (0.1 mmol), stryrene (0.12 mmol), Na
2
CO (0.12 mmol), catalyst (0.0004
3
mmol), DMF (2.0 mL)
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b
Percentage conversions were determined by GC based on ArBr.
c
1
13
Isolated yields, which were characterized by H and C NMR, determined by GC based on
ArBr
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Scheme 1. Synthetic route of ligands and metal complexes
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Scheme 2. Supposed structures occurred after the pre-activation step.
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