A robust, moisture- and air-stable phosphine mono-ylide palladacycle precatalyst: A simple and highly efficient system for mizoroki-heck reactions

Article abstract of DOI:10.1055/s-0033-1340319

A palladacycle phosphine mono-ylide complex was identified as an efficient catalyst system for the Mizoroki-Heck cross-coupling reactions of aromatic or aliphatic olefins with a variety of aryl bromides and chlorides, including those containing electron-donating or electron-withdrawing substituents. The reactions, which proceeded in moderate to excellent yields, required relatively low loadings of palladium (10 ppm) and were performed under aerobic conditions. High catalyst activities with turnover frequencies of up to 20,000 h ^-1 were observed at 130? °C. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0033-1340319

336▌
LETTER
lAetteRr obust, Moisture- and Air-Stable Phosphine Mono-Ylide Palladacycle Pre-
catalyst: A Simple and Highly Efficient System for Mizoroki–Heck Reactions
Palladium Catalyst for Mizoroki–Heck Reactions
Seyyed Javad Sabounchei,*a Mohsen Ahmadi,a Tayebeh Azizi,b Mohammad Panahimehra
a
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, 65174, Iran
Fax +98(81)18273231; E-mail: jsabounchei@yahoo.co.uk
b
Department of Chemistry, Payame Noor University (PNU), Hamedan, Iran
Received: 17.09.2013; Accepted after revision: 31.10.2013
gives good yields at low palladium loadings under aerobic
Abstract: A palladacycle phosphine mono-ylide complex was
conditions.
identified as an efficient catalyst system for the Mizoroki–Heck
cross-coupling reactions of aromatic or aliphatic olefins with a va-
riety of aryl bromides and chlorides, including those containing
electron-donating or electron-withdrawing substituents. The reac-
tions, which proceeded in moderate to excellent yields, required rel-
atively low loadings of palladium (10 ppm) and were performed
under aerobic conditions. High catalyst activities with turnover fre-
quencies of up to 20,000 h–1 were observed at 130 °C.
The catalyst precursor 1 used for the Mizoroki–Heck
cross-coupling reaction was prepared in high yield by re-
action of 1-biphenyl-4-yl-2-[[(diphenylphosphino)-
methyl](phenyl)phosphino]ethanone with dichloro(cyclo-
octadienyl)palladium in a 1:1 molar ratio at room temper-
ature.31
The palladium-catalyzed Mizoroki–Heck reaction is
among the most important carbon–carbon bond-forming
processes for the vinylation of aryl or vinyl halides. As a
result, considerable effort has been made to develop new
and improved protocols for the Heck coupling reaction
since the pivotal discovery of the reaction by Heck and
Mizoroki in the early 1970s.32–35
Key words: olefination, catalysis, palladium, ylides, Heck reaction
The palladium-catalyzed arylation of olefins, known as
the Heck cross-coupling reaction, is one of the most ver-
satile tools for forming carbon–carbon bonds.1–6 Toler-
ance to a wide spectrum of functional groups in both
substrates makes this reaction very useful in total synthe-
ses. Historically, palladium complexes with phosphine li-
gands have been widely used to catalyze these reactions.7–10
The phosphine ligands act as stabilizers for catalytically
active palladium(0) complexes that are generated in situ.
Palladium complexes with bulky and strongly electron-
donating trialkylphosphines are favored for carbon–
carbon coupling of aryl halides with styrene;11,12 however, di-
phosphine ligands, because of their chelating effects, gen-
erally shows better coordination ability in stabilizing
active palladium species in the catalytic cycle. Among the
existing catalysts for these reactions, the most effective
are homogeneous palladium–ligand systems.13–19 The ef-
ficiency of a Heck reactions is greatly dependent on the
reactivity of the palladacycle catalyst precursors. It is well
established that palladacycle complexes containing phos-
phine ligands that combine both good donor strength and
π-accepting capacity have high catalytic activities in Heck
cross-coupling reactions.20–22 Over the past ten years, we
have studied phosphorus ylides and their palladium com-
plexes,23–28 and we have used some of these complexes in
carbon–carbon coupling reactions.29–30 Here, we describe
the use of precatalyst 1 to promote the Mizoroki–Heck
coupling reaction of aryl bromides or chlorides with ole-
fins (Scheme 1). The reaction proceeds smoothly with de-
activated aryl bromides or activated aryl chlorides and it
Many palladium phosphine complexes have been used as
catalyst in these reactions,36,37 but most suffer from prob-
lems such as a need for a high palladium loading, low
yields from less-active aryl bromides, instability toward
air and moisture, and the generation of quantities of 1,1-
diphenylethene as a byproduct.38 With these precedents in
mind, and encouraged by our earlier work,29,30,37,39,40 we
decided to explore the scope and limitations of various
substrates, as well as the efficiency of our precatalyst.
First, to optimize the reaction conditions, we examined
the model reactions of 4-bromobenzaldehyde with styrene
and with ethyl acrylate (Table 1). A control experiment in-
dicated that coupling did not proceed in the absence of a
catalyst (entry 1), and a catalyst loading of 10 ppm was
found to be optimal [entry 5; R = Ph (81%), CO2Et
(85%)].
R2
R2
[Pd]
+
X
R1
R
R1
2 = CO2Et, Ph
X = Br, Cl
Ph2
P
Cl
[Pd] =
Pd
Cl
HC PPh2
1
O
SYNLETT 2014, 25, 0336–0342
Advanced online publication: 06.12.2013
DOI: 10.1055/s-0033-1340319; Art ID: ST-2013-D0888-L
© Georg Thieme Verlag Stuttgart · New York
Scheme 1 Mizoroki–Heck cross-coupling reaction using a phos-
phine mono-ylide palladacycle as the precatalyst
0
9
3
6
-
5
2
1
4
1
4
3
7
-
2
0
9
6

LETTER
Palladium Catalyst for Mizoroki–Heck Reactions
337
Next, we examined the effects of several solvents. Polar 18 and 19). Among the inorganic bases tested, potassium
solvents such as N,N-dimethylformamide, N-methylpyr- carbonate proved to be the most efficient and gave a good
rolidin-2-one, or methanol gave acceptable yields (entries isolated yield (entry 5). On successively increasing the
5, 10, and 11), whereas nonpolar solvents such as toluene temperature from 60 °C to 100, 130, and 180 °C, the reac-
and 1,4-dioxane gave low to moderate yields of 40 and tivity of the palladacycle increased, resulting in yields of
65%, respectively (entries 12 and 13). The reaction did 44, 70, 81, and 80%, respectively (entries 4–7; R = Ph).
not proceed in water; no product was observed, even when Therefore, 10 ppm of the palladacycle with N,N-dimeth-
the reaction was extended to 48 hours (entry 14). Only a ylformamide as solvent and potassium carbonate as the
trace of product was detectable under solvent-free condi- base at 130 °C (entry 5) were chosen as the optimal con-
tions with triethylamine as base (entry 20).
ditions for the reaction.
Having selecting N,N-dimethylformamide as the optimal Next, we studied the application of these conditions to re-
solvent, we investigated the effects of various bases on the actions of styrene with various aryl bromides and chlo-
reaction. It was clear that inorganic bases (Table 1 entries rides, and the results are summarized in Table 2. In most
5 and 15–17) were much better than organic ones (entries cases, products were obtained in very good to excellent
Table 1 Mizoroki–Heck Coupling: Optimization of the Reaction Conditions
H
R
O
H
O
+
R
Br
Entrya
Catalyst (ppm)
Solvent
Base
Temp (°C)
Yieldb (%)
R = Ph
R = CO2Et
1
2
–
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
NMP
MeOH
toluene
1,4-dioxane
H2O
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Na2CO3
Cs2CO3
NaF
130
130
130
180
130
100
60
–
–
1000
100
10
10
10
10
50
5
83
80
83
81
70
44
81
56
72
62
40
48
–
85
84
86
85
80
56
85
63
75
65
43
52
–
3
4
5
6
7
8
130
130
130
60
9
10
11
12
13
14c
15
16
17
18
19
20
21
10
10
10
10
10
10
10
10
10
10
10
10
100
80
100
130
130
130
130
130
90
DMF
DMF
DMF
DMF
DMF
–
72
73
68
70
47
trace
trace
76
79
65
70
48
trace
trace
NaOAc
Et3N
Et3N
DMF
–
130
a Reaction conditions: 4-BrC6H4CHO (1 mmol), olefin (2 mmol), base (1.5 mmol), solvent (3 mL), palladacycle catalyst (5–1000 ppm), 24 h,
under air.
b Isolated yield.
c Reaction extended to 48 h.
© Georg Thieme Verlag Stuttgart · New York
Synlett 2014, 25, 336–342

338
S. J. Sabounchei et al.
LETTER
yields and >99% trans selectivity. Under the optimized
reaction conditions, both electron-deficient and electron-
rich aryl bromides coupled cleanly in good to excellent
yields (entries 2–5). Coupling of activated aryl bromides
with styrene proceeded in excellent yields (entries 3–5),
and even bromobenzene, an electronically neutral sub-
strate, coupled in excellent yield (entry 1). A nonactivated
aryl bromide bearing a methyl group coupled with styrene
in good yield (entry 2), and good reactivities were also ob-
served for coupling reactions of styrene with 1-bromo-
naphthalene and with 2-bromothiophene (Table 2, entries
6 and 7).
Table 2 Mizoroki–Heck Cross-Coupling Reactions of Aryl Halides
with Styrene
catalyst (10 ppm)
+
ArX
Ar
1a–7a
Entrya
X
Ar
Yieldb
(%)
TONc
TOFd
(h–1)
1
2
3
4
5
6
7
8
Br
Br
Br
Br
Br
Br
Br
Cl
Ph
76.5
70.2
80.0
48.1
79.2
69.3
75.4
76500
70200
80000
48100
79200
69300
75400
3180
2920
3330
2000
3300
2880
3140
4-Tol
Various aryl chlorides were also found to couple with sty-
rene under similar conditions, although their reactivities
were lower than those of their bromo counterparts. An
electronically neutral aryl chloride gave a moderate yield
(entry 8). The efficiency of the robust palladacycle cata-
lysts for coupling of aryl chlorides with olefins in Mizoro-
ki–Heck reactions commonly increases when the reaction
temperature is above 180 °C, as occurred in entries 8–10,
but this is frequently associated with oxidation of the
phosphorus ligand.41,42 With the electron-rich 4-chlorotol-
uene, the yield was moderate (entry 9), and the electron-
deficient substrate 4-chloroacetophenone coupled simi-
larly (entry 10). These observations are in keeping with
the fact that oxidative addition reactions of aryl chlorides
occur less readily than do those of aryl bro-
mides.12,21,37,39,40
4-MeCOC6H4
4-HCOC6H4
4-O2NC6H4
2-thienyl
1-naphthyl
Ph
62.0
62000
(70100)
2580
(2920)
(70.1)f
9
Cl
Cl
4-Tol
51.1
51100
(62000)
2120
(2580)
(62.0)f
10
4-MeCOC6H4
60.0
60000
(73200)
2500
(3050)
(73.2)f
a Reaction conditions: aryl halide (1 mmol), styrene (2 mmol), K2CO3
(1.5 mmol), DMF (3 mL), catalyst (10 ppm), 24 h, 130 °C.
b Isolated yield.
To extend the scope of this catalytic system, we examined
the coupling reactions of various aryl bromides and chlo-
rides with ethyl acrylate under the same optimized condi-
tions, and the results are presented in Table 3. In general,
all the aryl halides gave the corresponding products (1b–
7b) in moderate to good yields of 51% to 88% in the pres-
ence of 10 ppm of the palladium catalyst.
c TON = (moles of product)/(moles of catalyst).
d TOF = TON/time (h).
f The reaction was carried out under reflux at 180 °C.
Table 3 Mizoroki–Heck Cross-Coupling Reactions of Aryl Halides with Ethyl Acrylate (Abschnitt 1 von 2)
Entrya
ArX
Product
Time (h)
24
Yield (%)b
TON
TOF (h–1)
3600
O
OEt
1
PhBr
86
86400
1b
O
OEt
2
3
4-TolBr
29
68
81
67800
81000
2330
H3C
2b
O
OEt
O
4-MeCOC6H4Br
4
20250
CH3
3b
Synlett 2014, 25, 336–342
© Georg Thieme Verlag Stuttgart · New York

LETTER
Palladium Catalyst for Mizoroki–Heck Reactions
339
Table 3 Mizoroki–Heck Cross-Coupling Reactions of Aryl Halides with Ethyl Acrylate (Abschnitt 2 von 2) (continued)
Entrya
ArX
Product
Time (h)
Yield (%)b
TON
TOF (h–1)
O
OEt
O
4
4-HCOC6H4Br
4
76
75700
18920
H
4b
O
OEt
5
6
7
4-O2NC6H4Br
4
24
17
72
82
88
72000
81600
88400
18000
3400
5200
O2N
5b
O
Br
OEt
S
S
6b
OEt
O
Br
7b
1b
O
OEt
63100
(74200)
2620
(3090)
8
9
PhCl
24
24
63 (74)c
51 (63)c
O
OEt
51000
(63000)
2125
(2625)
4-TolCl
H3C
2b
O
OEt
69000
(79000)
2870
(3290)
O
10
4-MeCOC6H4Cl
24
69 (79)c
CH3
3b
a Reaction conditions: aryl halide (1 mmol), ethyl acrylate (2 mmol), K2CO3 (1.5 mmol), DMF (3 mL), catalyst (10 ppm), 130 °C.
b Isolated yield.
c The reaction was carried out under reflux at 180 °C.
Although several catalytic systems have been reported to pling of styrene and ethyl acrylate with aryl halides were
support Mizoroki–Heck cross-coupling reactions, phos- achieved with conventional palladium catalysts such as
phine mono-ylide palladacycles of the type exemplified di-(η3-allyl)dichlorodipalladium,44 palladium(II) ace-
by 1 are novel with respect to the P and CH phosphorus tate,45 and palladium(II) acetate with 6 mol% of Dave-Phos6
ylide environment. The electronic and steric nature of the (entries 1–3 and 6), as well as with N-heterocyclic carbene
ligand and the coordination number of palladium signifi- palladium complex46 (entries 4 and 5), a phosphane
cantly affect the oxidative addition and reductive elimina- palladacycle47 (entry 7), palladacycles modified with C,N
tion steps.43
and C,S chelate ligands48,52 (entries 8 and 12), P,C and P,P
chelate palladacycles39 (entries 13 and 14), cyclopalladated
ferrocenylimines49 (entries 9 and 11), and a supported pal-
ladium catalyst50 (entry 10). Table 4 shows that palladacy-
A comparison of phosphine mono-ylide palladacycle 1
with other catalytic systems in Mizoroki–Heck reactions
is presented in Table 4. Satisfactory results for the cou-
© Georg Thieme Verlag Stuttgart · New York
Synlett 2014, 25, 336–342

340
S. J. Sabounchei et al.
LETTER
cle catalyst 1 (entries 15 and 16) gives superior yields with In conclusion, we have developed an efficient and new
lower catalyst loadings under aerobic conditions in com- catalyst precursor for the Mizoroki–Heck cross-coupling
parison with similar catalytic systems (entries 4–7, 10, reaction. In the presence of complex 1 as precatalyst, var-
and 12). Finally, we compared catalyst 1 with our previ- ious aryl bromides, including those with electron-donat-
ous catalysts (entries 13 and 14) to examine the relation- ing or electron-withdrawing substituents, coupled
ships between the reaction rates and the structures of the effectively to give the corresponding products in moder-
palladacycles and the presence bulky phosphine ligands. ate to excellent yield as trans-isomers. Further studies on
As can be seen in Table 4, the steric hindrance and coor- the applicability of this system to other organic transfor-
dination number in palladacycle 1 affects the oxidative mations are currently under way.
addition and reductive elimination steps43 and, as expect-
ed, the reaction is significantly slower.
Table 4 Comparison of Catalytic Activities of Various Palladium Complexes that Promote the Mizoroki–Heck Coupling of Olefins with Aryl
Halides
R1
R2
+
R1
R2
X
Entry
ArX
Catalysta
[Pd] (ppm) Base
Solvent
Temp (°C) Time (h) Yield (%)
R2 = Ph
R2 = CO2Et
c
1b
2
PhBr
PhI
[Pd1]44
[Pd2]45
–
Na2CO3
DMA
ILd
120
100
100
140
140
80
24
4
87
86
–
10
Et3N
94e
48
–
3
4-O2NC6H4Br [Pd2]45
10
Et3N
IL
24
3
–
4
PhBr
PhBr
[Pd3]46
[Pd3]46
12,000
12,000
20,000
10,000
0.5
NaOAc
NaOAc
DMF
100
100
92
5
H2O
24
24
8
–
6
4-HCOC6H4Cl [Pd4]6
Bu4NAc
K3PO4
K2CO3
Et3N
1,4-dioxane
DMF–H2O
NMP
89
94
90
98.7h
96i
99k
–
7
PhCl
PhBr
PhI
[Pd5]47
[Pd6]48
[Pd7]49
[Pd8]50
[Pd9]51
[Pd10]52
[Pd11]39
[Pd12]39
[Pd13]m
[Pd13]m
85
82f
8
150
100
100
140
120
130
130
130
130
34
8
86.6g
9
3.27
2000
100
5000
10
1,4-dioxane
DMA
DMF
38.2
64
10
11j
12
13
14
15
16
PhI
Bu3N
24
24
15
4
PhBr
PhBr
PhBr
4-TolCl
PhBr
PhCl
K3PO4
Et3N
91
DMA
NMP
86
Cs2CO3
K2CO3
K2CO3
K2CO3
74l
73
46
86.4
71.1
10
DMF
4
45
10
DMF
24
24
76.5
62.0
10
DMF
a [Pd1]: [Pd(η3-All)Cl]2; [Pd2]: Pd(OAc)2; [Pd3]: N-heterocyclic carbene Pd complex; [Pd4]: Pd(OAc)2 + (6 mol% of Dave-Phos); [Pd5]:
β-diketiminatophosphane Pd complex; [Pd6]: di-3-chlorobis(dimethylbenzylamine-6-C,N)dipalladium(II); [Pd7]: Cyclopalladated ferrocenyl-
imines; [Pd8]: Palladium catalyst supported on a commercial synthetic adsorbent, DIAION HP20; [Pd9]: [PdCl{[(η5-C5H5)]Fe[(η5-
C5H3)C(CH3)=]NC12H25]}]2 (cyclopalladated ferrocenylimines); [Pd10]: Furancarbothioamide-based palladacycle; [Pd11]:
[(P^P)Pd(P^C)](OTf)2; [Pd12]: [Pd(dppe)(OTf)2]; [Pd13]: 1 (this work).
b Using 0.75 mmol of TBAB.
c [ArX]/[Pd] = 10000.
d Ionic Liquid [(HQ-PEG1000-DIL)(BF4)].
e Reaction time 2 h.
f Reaction time 10 h with C4H3SCl as starting material.
g Reaction time 29 h.
h Reaction time 2.5 h.
i Reaction time 4 h.
j TBAB co-catalyst.
k Reaction time 12 h.
l K2CO3 and DMF.
m This work.
Synlett 2014, 25, 336–342
© Georg Thieme Verlag Stuttgart · New York

LETTER
Palladium Catalyst for Mizoroki–Heck Reactions
341
1-Biphenyl-4-yl-2-[[(diphenylphosphino)methyl](phenyl)phos-
phino]ethanone
(16) Christmann, U.; Vilar, R. Angew. Chem. Int. Ed. 2005, 44,
366.
(Ph2P)2CH2 (0.50 g, 1.30 mmol) was dissolved in CHCl3 (8 mL),
and a solution of 1-(3-bromobiphenyl-4-yl)ethanone (0.36 g, 1.30
mmol) in CHCl3 (4 mL) was added dropwise. The mixture was
stirred for 15 h at r.t. then concentrated to about 2 mL under reduced
pressure. Et2O (2 × 10 mL) was added and the phosphonium salt
was collected by filtration and dried under reduced pressure. The
salt (0.33 g, 0.50 mmol) was treated with a solution of Et3N (0.50
mL) in toluene (15 mL), and the Et3N·HBr was filtered off. Concen-
tration of the toluene layer to about 1 mL and subsequent addition
of Et3N (25 mL) precipitated a white solid; yield: 0.21 g (71%); mp
(17) Fleckenstein, C. A.; Plenio, H. Chem. Eur. J. 2007, 13, 2701.
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2011, 696, 940.
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Salehzadeh, S.; Gholiee, Y.; Karamian, R.; Asadbegy, M.;
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J. Coord. Chem. 2010, 63, 1165.
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1
144–146 °C. IR (KBr): 1565 cm–1 (νC=O). H NMR (89.60 MHz,
CDCl3): δ = 3.70 (d, 2J PH = 14.22, 2 H, CH2), 4.36 (br s, 1 H, CH),
7.27–8.02 (m, 29 H, Ph). 31P NMR (36.26 MHz, CDCl3): δ = –29.78
2
2
(d, J PP = 63.67, PPh2), 11.32 (d, J PP = 63.24, PCH). 13C NMR
(100.62 MHz, CDCl3): δ = 24.52 (dd, 1JPC = 57.64, 32.28, PCH2P),
49.94 (d, J PC = 114.46, CH), 124.89–141.84 (m, Ph), 184.60 (s,
1
CO). Anal. Calcd. for C39H32OP2: C, 80.95; H, 5.57. Found: C,
80.86; H, 5.56.
Mizoroki–Heck Reaction of Aryl Halides with Olefins; General
Procedure
A mixture of the aryl halide (1 mmol), olefin (2 mmol), palladacycle
catalyst 1 (10 ppm), K2CO3 (1.5 mmol), and DMF (3 mL) was heat-
ed to 130 °C. The mixture was then cooled to r.t. and the solvent
was removed under reduced pressure. The mixture was diluted with
hexane (15 mL), and H2O (15 mL) was added. The organic layer
was separated, washed with brine (15 mL), dried (CaCl2), and con-
centrated under reduced pressure. Liquid products were purified by
column chromatography [silica gel, hexane–EtOAc (80:20)],
whereas solids were purified by crystallization (EtOH–H2O) or by
slow evaporation of a solution in hexane. Products were identified
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2013, 66, 411.
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114.
(31) Phosphine Mono-ylide Palladacycle 1
A solution of 4-PhC6H4C(O)CH=PPh2CH2PPh2 (0.289 g,
0.5 mmol) in CH2Cl2 (5 mL) was added dropwise to a soln
of [PdCl2(COD)] (0.142 g, 0.5 mmol) in CH2Cl2 (5 mL). The
mixture was stirred at r.t. for 2 h and then concentrated to ~2
mL and treated with hexane (~25 mL) to give a yellow solid.
(32) Heck, R. F.; Nolley, J. P. J. Org. Chem. 1972, 37, 2320.
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