Pd-catalyzed ligand-free Suzuki reaction of β-substituted allylic halides with arylboronic acids in water

Article abstract of DOI:10.1039/c3ra47813k

The catalyst system consisting of Pd(TFA)₂ and KOH allows for a wide range of β-substituted allylic halides to react efficiently with various arylboronic acids in neat water under ligand-free conditions, affording the allylated arenes in high yields with broad functional group tolerance and up to 7.4 × 10⁵ TON and 15416 h^-1 TOF.

Full text of DOI:10.1039/c3ra47813k

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Pd-catalyzed ligand-free Suzuki reaction of
b-substituted allylic halides with arylboronic
acids in water†
Cite this: RSC Adv., 2014, 4, 11152
Received 20th December 2013
Accepted 11th February 2014
Chaonan Dong, Lingjuan Zhang, Xiao Xue, Huanrong Li, Zhiyong Yu, Weijun Tang
*
and Lijin Xu
DOI: 10.1039/c3ra47813k
www.rsc.org/advances
The catalyst system consisting of Pd(TFA)2 and KOH allows for a wide methods, the Pd-catalyzed Suzuki reaction of allylic halides,12,13
range of b-substituted allylic halides to react efficiently with various esters14 and alcohols15 with organoboronic compounds has
arylboronic acids in neat water under ligand-free conditions, affording received increasing attention due to its simplicity, tolerance of
the allylated arenes in high yields with broad functional group toler- various functional groups and the easy availability of reagents,
ance and up to 7.4 ꢀ 105 TON and 15 416 hꢁ1 TOF.
and it is notable that this kind of transformation could benet
considerably from the use of aqueous solvents as the reaction
media.13e,h,k–n,14j,m,15c More recently, Scrivanti and Ueda disclosed
that allylic bromides could efficiently react with aryl- and
vinylboronic acids under transition-metal-free conditions to
give the corresponding products in high yields.16 Nevertheless,
despite the exciting progress, those reported examples mainly
dealt with the cross-coupling reactions of g-substituted allylic
substrates, and less attention has been paid to the reactions
involving b-substituted allylic derivatives, with only several
reports available in the literature.13k–n As part of our continuing
effort on the development of catalysis in water,17 herein, we
report a highly efficient palladium-catalyzed ligand-free Suzuki
reaction of b-substituted allylic bromides and chlorides with
aryl- and vinylboronic acids in neat water without requiring any
organic solvent, surfactant or inert gas protection, in which
excellent group compatibility and up to 7.4 ꢀ 105 TON and
15 416 hꢁ1 TOF were observed.
Preliminary screening for optimal reaction conditions was
performed with (3-bromoprop-1-en-2-yl)benzene (1a) and
4-methoxyphenylboronic acid (2a) as the model substrates.
Following the previous reports by Scrivanti and Ueda,16 we rst
tried the coupling reaction of 1a and 2a without employing any
transition-metal catalyst. However, no reaction occurred using
either Scrivanti's or Ueda's protocol (Table 1, entries 1 and 2).
Obviously, in this case the use of transition-metal catalyst is
required. Considering a number of attractive advantages of
using water as a solvent for organic reactions,2,3 we therefore
chose water as the reaction medium for subsequent study. In
the presence of catalytic amount of Pd(OAc)2 (0.01 mol%), we
carried out the coupling reaction with NEt3 as the base in pure
water, and a 18% yield of the expected product 3aa was achieved
(Table 1, entry 3). However, employing Pd2(dba)3, PdCl2 or Pd/C
led to lower yields (Table 1, entries 4–6). Pd(PPh3)4 afforded a
As one of the most powerful protocols for the construction of C–
C bonds in organic synthesis, the Pd-catalyzed Suzuki reaction
has been extensively studied with great success during the last
several decades.1 Recently there has been much research
interest in developing catalyst systems capable of allowing this
cross coupling reaction to be performed in water. The attrac-
tiveness of water lies in the fact that it is cheap, clean, non-toxic,
non-ammable, non-explosive and non-carcinogenic, and its
high heat capacity can help prevent exothermic reactions from
overheating on a large scale. Obviously, carrying out organic
reactions in water would lead to substantial environmental,
economical and safety gains.2 As a result, a number of catalytic
Suzuki reactions have proved to be feasible in water,3 and
strategies developed to overcome the major concern about
water solubility of catalysts and substrates include the use
of water-soluble ligands,4 phase-transfer catalysis,5 organic
co-solvents,6 microwave or ultrasound.7 Of particular note is
that recent developments have enabled the aqueous Suzuki
reactions to proceed smoothly in neat water under ligand-free
conditions without calling for any phase-transfer catalyst, co-
solvent or degassing.8
Allylated arenes are valuable reagents for the construction of
useful molecules,9 and they are also important structural motifs
present in many biologically active natural products.10 There-
fore, a signicant amount of effort has been focused on the
efficient preparation of these compounds, and many methods
are now available in the literature.11 Among these known
Department of Chemistry, Renmin University of China, Beijing, 100872, China. E-mail:
xulj@chem.ruc.edu.cn
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c3ra47813k
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Table 1 Screening conditions for Pd-catalyzed Suzuki reaction of 1a and 2aa
Entry
Solvent
[Pd]
Base
Time (h)
Yieldb (%)
1
Toluene
CH2Cl2–H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
None
None
Pd(OAc)2
Pd2(dba)3
PdCl2
K2CO3
Cs2CO3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
HNEt2
HNiPr2
Cy2NMe
NaOAc
NaOH
K2CO3
KF
Cs2CO3
Na2CO3
K3PO4
KOH
KOH
KOH
KOH
KOH
K2CO3
K2CO3
HNiPr2
KOH
3
18
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
nd
nd
18
8
16
11
40
68
16
85
9
28
55
37
51
26
34
58
95
nd
73
60
75
nd
nd
92
86
74
2c
3
4
5
6
7
8
9
Pd/C
Pd(PPh3)4
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
None
10
11
12
13
14
15
16
17
18
19
20
21d
22e
23f
24g
25h
26i
27j
28k
Pd(TFA)2
Pd(TFA)2
Pd(TFA)2
Pd/C
PdCl2
H2O
H2O
H2O
Pd(OAc)2
Pd(TFA)2
Pd(TFA)2
3
12
48
KOH
a
Reaction conditions: 1a (1.0 mmol), 2a (1.2 mmol), catalyst (0.01 mol%), base (1.2 mmol), solvent (3.0 mL), 90 ꢂC. nd: not detected. b Isolated yield.
1.5 eq. of Cs2CO3 were added. d 0.1 eq. of TEMPO was added. e 0.1 eq. of HQ was added. f Reaction temperature 60 ꢂC. g 1a (1.0 mmol), 2a (1.0
c
mmol), Pd/C (0.3 mol%), base (3.0 mmol), H2O (10.0 mL), 25 ꢂC. h 1a (0.50 mmol), 2a (0.55 mmol), PdCl2 (2 mol%), base (1.5 mmol), Na2SO4 (8 mol
%), H2O (4.0 mL), 25 ꢂC. i 1a (0.50 mmol), 2a (0.75 mmol), Pd(OAc)2 (0.25 mol%), base (1.0 mmol), H2O (1.0 mL), 100 ꢂC. j S/C ¼ 100 000. k S/C ¼
1 000 000.
40% yield (Table 1, entry 7), and the best yield of 68% was be highly effective for the Suzuki reaction of aryl halides in neat
obtained in the case of Pd(TFA)2 (Table 1, entry 8). In order to water, were also examined (Table 1, entries 24–26). Only Liu's
improve the reaction efficiency, we then explored the perfor- protocol proved equally effective (Table 1, entry 26), but the high
mance of other bases. Clearly, the reaction was sensitive to the catalyst loading made it less attractive. Remarkably, the catalyst
choice of base (Table 1, entries 9–19). It is notable that HNiPr2, loading could be decreased to 0.001 mol% without compro-
reported to be highly effective in Pd-catalyzed Suzuki reaction of mising catalytic activity (Table 1, entry 27). It is worth noting
aryl halides with aryl boronic acids in neat water,8a gave a good that at an even lower loading of 0.0001 mol% (S/C ¼ 1 000 000)
yield of 85% (Table 1, entry 10), and KOH resulted in the best of the catalyst, a good yield of 74% was still obtained albeit over
reactivity with a nearly quantitative yield (Table 1, entry 19). As a longer reaction time of 48 h (Table 1, entry 28), corresponding
expected, a control experiment indicated that no reaction took to 7.4 ꢀ 105 TON and 15 416 hꢁ1 TOF. It should be pointed out
place in the absence of palladium catalyst (Table 1, entry 20). that the homocoupling reaction of 2a and isomerization of the
Recent studies disclosed that TEMPO (2,2,6,6-tetramethyl-1- product were not detected in all cases. Under the same reaction
piperidinyloxy) and HQ (hydroquinone) could greatly facilitate conditions, the reaction of 2a with 2-phenylprop-2-en-1-ol or
the Pd-catalyzed cross coupling reactions,18 but only reduced 2-phenylallyl acetate was attempted, but we did not observe any
reactivity was observed in our case (Table 1, entries 21 and 22). product. Noteworthy is that all the reactions were performed
Lower temperature disfavored the reaction as the yield of 3aa smoothly in air without an inert atmosphere.
dropped to 75% at 70 ꢂC (Table 1, entry 23). The protocols
developed respectively by Liu,8a Bora8b and Hirao,8c reported to then investigated the reaction of 1a with other organoboronic
Having established the optimized reaction conditions, we
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Table 2 Pd-catalyzed Suzuki reaction of 1a with organoboronic acids Table 2 (Contd.)
in watera
Entry
24
Organoboron
Yieldb (%) (product)
92 (3ay)
Entry
Organoboron
Yieldb (%) (product)
2y
2z
1
2
3
4
2b
2c
2d
2e
90 (3ab)
92 (3ac)
87 (3ad)
84 (3ae)
25
93 (3az)
a
Conditions: 1a (1.0 mmol), 2 (1.2 mmol), Pd(TFA)2 (0.01 mol%), KOH
b
(1.2 mmol), H2O (3.0 mL), 90 ꢂC, 3 h. Isolated yield.
5
6
7
8
2f
81 (3af)
90 (3ag)
88 (3ah)
91 (3ai)
acids. As can be seen from Table 2, a range of arylboronic acids
reacted smoothly with 1a in neat water in the presence of 0.01
mol% Pd(TFA)2 to produce the expected 2,3-diarypropenes in
good to excellent yields in 3 h (Table 2, entries 1–20). It was
found that the reaction was highly tolerant of various functional
groups with different electronic and steric properties. Notably,
the sensitive halogen substituent (Br and Cl) in the aromatic
ring of arylboronic acids could well survive under the current
conditions, affording the corresponding products in high yields
(Table 2, entries 8–11). Interestingly, the presence of a hydroxyl
group on the aryl ring of arylboronic acid did not affect the
reaction, and the expected product 3am could be obtained in
90% yield (Table 2, entry 12). Steric hindrance seems to have
little inuence on the reaction efficiency as evidenced by the
fact that arylboronic acids bearing substituents at the 2-position
showed good reactivity (Table 2, entries 4, 5, 9, 11, 19). The
reactions involving heteroarylboronic and alkenylboronic acids
were also highly efficient, delivering the corresponding prod-
ucts in 83–93% yields (Table 2, entries 21–25). To showcase the
practicability of this process, we tried the cross coupling of 5 g
of 1a with 2a (30.61 mmol) in the presence of 0.01 mol%
Pd(TFA)2 in water. The reaction afforded the desired product
3aa in 91% isolated yield in 8 h.
2g
2h
2i
9
2j
90 (3aj)
89 (3ak)
90 (3al)
10
11
2k
2l
12
13
14
15
2m
2n
2o
90 (3am)
87 (3an)
81 (3ao)
88 (3ap)
2p
16
17
18
19
2q
2r
2s
2t
87 (3aq)
84 (3ar)
88 (3as)
83 (3at)
The reaction of 1a with other organoboronic derivatives
under the optimized reaction conditions was subsequently
investigated. The arylboronic ester, 4,4,5,5-tetramethyl-2-
phenyl-1,3,2-dioxaborolane, underwent smooth allylation in
water, affording the expected product 3ab in 78% yield (Scheme
1, (1)). A better yield of 88% was achieved with potassium
phenyl triuoroborate as the coupling partner (Scheme 1, (2)).
20
21
22
2u
2v
79 (3au)
83 (3av)
85 (3aw)
2w
23
2x
88 (3ax)
Scheme 1 Allylation of other organoboronic derivatives.
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Table 3 Pd-catalyzed Suzuki reaction of b-arylated allylic halides with organoboronic acids in watera
Entry
Allylic halide
Organoboron
Yieldb (%) (product)
1
2
1b
1b
2a
2b
82 (3ba)
79 (3bb)
3
4
5
6
7
8
9
1b
1b
1b
1b
1c
1c
1d
2k
2o
2s
2u
2c
2q
2b
80 (3bk)
78 (3bo)
84 (3bs)
88 (3bu)
75 (3cc)
78 (3cq)
76 (3db)
10
11
1d
1d
2c
79 (3dc)
77 (3dq)
2q
12
13
14
15
16
17
1e
1e
1e
1e
1f
2r
2x
2y
2z
2x
2k
82 (3er)
89 (3ex)
81 (3ey)
88 (3ez)
85 (3fx)
80 (3gk)
1g
18
19
20
21
1g
1h
1i
2x
2b
2a
2b
90 (3gx)
83 (3hb)
85 (3ia)
95 (3ib)
1i
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Table 3 (Contd.)
Entry
22
Allylic halide
Organoboron
Yieldb (%) (product)
80 (3iu)
1i
1j
1j
1j
2u
2a
2b
2u
23
88 (3ja)
24
85 (3jb)
25
83 (3ju)
26
27
28
29
1k
1k
1l
2a
2q
2b
2c
91 (3aa)
89 (3aq)
83 (3lb)
80 (3lc)
1l
30
1l
1l
2q
2x
75 (3lq)
79 (3lx)
31
a
Conditions: allylic halide 1 (1.0 mmol), organoboronic acid 2 (1.2 mmol), Pd(TFA)2 (0.01 mol%), KOH (1.2 mmol), water (3.0 mL), 90 ꢂC, 3 h.
Isolated yield.
b
We then turned our attention to the coupling reactions of with organoboronic acids were studied. However no reaction
other b-arylated allylic halides with organoboronic acids, and was observed in the coupling reaction of 1m with organo-
the results are summarized in Table 3. Under the same boronic acids under the same reaction conditions. This
conditions as described above, it was found that various problem could be resolved simply by increasing the S/C ratio to
allylic bromides with different substituents on the aryl ring 1000, which allowed the smooth allylation of 2b, 2q and 2x to
could undergo successful coupling reaction with a range of give good results (Scheme 2).
organoboronic acids, and the presence of functional groups
We also explored the reaction of the di-bromo-substituted
in both coupling partners did not affect the transformation substrate 1n with arylboronic acids (Scheme 3). It was found
(Table 3, entries 1–25). For example, the allylic bromide 1g that the double arylated products 3ba and 3nq were isolated in
bearing a sensitive bromine substituent on the aryl ring good yields, and the vinyl bromide could not be tolerated.
could be efficiently transformed into the target products with Similar observation has been reported by Ikegami and co-
high yields, leaving the sp2 C–Br bond intact (Table 3, entries workers in the aqueous Suzuki reaction catalyzed by assembled
17 and 18). The effectiveness of the current catalyst system Pd complex.13l
was further demonstrated in the arylation of allylic chloride.
When (3-chloroprop-1-en-2-yl)benzene (1k) was employed,
the coupling reaction proceeded effectively, affording the
target compound 3aa and 3aq in 91% and 89% yield,
respectively (Table 3, entries 26 and 27). The b-alkylated
allylic halide 1l also cross-coupled with aryl and vinyl boronic
acids to give the expected products in good yields (Table 3,
entries 28–31).
To expand the scope of our catalyst system further, the
coupling reactions of other types of b-substituted allylic halide Scheme 2 The reactions of substrate 1m with organoboronic acids.
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In summary, we have demonstrated that in the presence of
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A mixture of allylic halide 1 (1.0 mmol), arylboronic acid 2
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temperature. Water (5.0 mL) was added, and the mixture was
extracted with CH2Cl2 (3 ꢀ 5.0 mL). The combined organic
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Acknowledgements
Financial support from the National Natural Science Founda-
tion of China (21072225, 21172258, 21372258 and 91127039) is
greatly acknowledged.
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