Nickel-Catalyzed Direct Coupling of Allylic Alcohols with Organoboron Reagents

Article abstract of DOI:10.1002/cjoc.201800237

The direct coupling of allylic alcohols with arylboronic acids or their derivatives catalyzed by Ni(cod)₂ in the presence of a catalytic amount of base has been developed. A wide variety of allylic substrates or arylboronic acids turned out to be applicable to this catalytic system. The present method does not require the use of ligands for stabilizing the nickel catalyst in most cases or additional activators for activation of allylic alcohols.

Full text of DOI:10.1002/cjoc.201800237

Nickel-Catalyzed Direct Coupling of Allylic Alcohols with Organoboron Reagents†
Gaonan Wang, Yi Gan and Yuanhong Liu*
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular
Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of
Sciences, Chinese Academy of Sciences, 345 Lingling Lu,
Shanghai 200032, People’s Republic of China.
† Dedicated to Professor Xiyan Lu on the occasion of his 90th birthday.
R1
cat. Ni(cod)2, cat. K2CO3
R1
Ar
OH
Ar-BR
+
2
MeCN, 50 oC
ligand and activator-free 37 examples
Ar-BR2 = ArB(OH)2, ArB(pin), ArB(nep), (ArBO)3, Ar3B
simple system high efficiency wide FG group tolerance
Abstract: The direct coupling of allylic alcohols with arylboronic acids or their derivatives
catalyzed by Ni(cod)2 in the presence of a catalytic amount of base has been developed. A
wide variety of allylic substrates or arylboronic acids turned out to be applicable to this
catalytic system. The present method does not require the use of ligands for stabilizing the
nickel catalyst in most cases or additional activators for activation of allylic alcohols.
Keywords: nickel catalysis, cross-coupling, allylic alcohols, arylboronic acids
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been through the copyediting, typesetting, pagination and proofreading process, which
may lead to differences between this version and the Version of Record. Please cite this
article as doi: 10.1002/cjoc.201800237
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Introduction
Transition-metal-catalyzed allylic substitution reactions (ASRs) represents a powerful
method for producing useful synthetic intermediates which have been widely applied in
organic synthesis and natural product synthesis.[1] Among these reactions, metal-catalyzed
coupling reactions of allylic alcohol derivatives with organometallic reagents such as
Grignard reagents,[2] organozinc reagents[3] or aryl boron reagents[4] provides an unique
and efficient protocol for the synthesis of functionalized olefinic products. Due to the poor
leaving ability of the hydroxy group, most of these studies focused on the metal-catalyzed
allylation reactions using allylic carboxylates, carbonates, phosphates, halides and related
compounds as the substrates. However, there have been only limited reports using
unprotected allylic alcohols as the substrates directly. From an economical and an
environmental point of view, direct reaction of unprotected allylic alcohols with these
organometallic reagents is highly desirable. Since organoboron reagents are generally
stable, non-toxic, easily available and compatible with various functional groups, in recent
years, significant improvements have been achieved for the direct coupling of allylic
alcohols with arylboronic acids or esters using Pd[5], Ir[6] or Rh[7] as the catalysts (Scheme
1). Although these approaches have been proved to be highly useful, there is a need to
develop a cost-effective and more active metal catalyst. In this context, Ni-based catalysts[8]
are highly attractive for these transformations than noble metals because of their low cost
and wide availability. However, such reactions are quite rare. In 2011, Kobayashi and
co-workers developed a nickel-catalyzed allyl–allyl cross-couplings between alcohols and
allyl boronates.[9] However, no allyl–aryl cross-coupling via reactions with arylboron
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reagents were described in this paper. In addition, Ni(cod)2 was ineffective for this reaction.
Before 2017, only Ni-catalyzed coupling reaction of 2-cyclohexen-1-ol derivatives with
PhB(OH)2 have been reported (two-examples).[4a,c] During our work going-on, recently,
Michaelis[10] reported a first general nickel-catalyzed Suzuki cross-coupling of allylic
o
alcohols with arylboronic esters at 100 C. In this reaction, the pre-synthesized
nickel-catalyst [(TMEDA)Ni(o-tolyl)Cl] and the bidentate NHC/phosphine ligands were
required for enhancing the stability of the nickel catalyst and improving the reaction
efficiency. Nevertheless, the development of more simple and efficient catalyst system that
allows the facile assembly of 3-arylated alkene products under mild reaction conditions
would greatly enhance the utility of this reaction. During our work on nickel-catalyzed
coupling reactions,[11] we found a new nickel-catalyzed direct coupling of allylic alcohols
with arylboronic acids. Compared to known methods,[5-7, 9-10] this reaction has some
advantages such as avoiding the use of any ligands or activators,[12] and milder reaction
o
conditions (50 C in most cases). The method was also successfully extended to
arylboronic esters, boroxines or triarylborons. Herein, we reported the details of this
reaction.
Scheme 1. Metal-Catalyzed Cross-Coupling of Allylic Alcohols with Organoboron
Reagents
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Previous work:
R1
R1
cat. Pd, Ir, Rh
cat. Ni(PPh3)4
ArB(OH)2 or
ArB(OR)2
OH
Ar
+
Kobayashi et al:
R1
OH
+
Bpin
toluene or MeCN
25-40 oC
R1
Michaelis et al:
R1
R1
cat. Ni/ligand
OH
Ar
+ ArB(OR)2
KOtBu, K3PO4
MeCN, 100 oC
+ Cl-
Ar
N
N
Ni = [(TMEDA)Ni(o-tolyl)Cl]
PPh2 ligand
This work:
R1
cat. Ni(cod)2
cat. base
R1
ArB(OH)2 or
ArB(OR)2
Ar
OH
+
MeCN, 50 oC
ligand and activator-free
simple system
high efficiency
wide FG group tolerance
Results and Discussion
We began our studies by examination of the direct coupling reaction of cinnamyl
alcohol 1a with 4-fluorophenylboronic acid in the presence of 5 mol % Ni(cod)2, and the
results are shown in Table 1. As the bases are often used to facilitate the transmetalation
step by forming “ate” complexes with the organoboron reagents,[13] the effects of base
t
were first investigated. While the commonly used BuOK did not afford the desired
coupling product, other inorganic bases such as Cs2CO3, K3PO4 and K2CO3 improved the
reaction efficiency significantly to give the 1-cinnamyl-4-fluorobenzene 2a in 85-92%
o
yields in the presence of 10 mol % PMe2Ph as the ligand at 80 C in MeCN (Table 1,
entries 1-4). With Et3N as the base, a lower yield of 76% was observed (entry 5). It was
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noted that trace amounts (ca. 2-4%) of the geometric isomer (Z-2a) were also observed in
these cases. In order to avoid the formation of the Z-isomer and other byproducts, we next
investigated the ligand effects by running the reaction at 50 oC. It was found that in general,
monophosphine ligands provided higher product yields than that obtained using
bisphosphine ligands (entries 6-10). For example, high yields of 2a (89-92%) could be
observed using PMe2Ph, PPh3 or PBu3 as the ligands, whereas only 68-75% yields were
observed using dppp or dppf as the ligands. It was noted that a small amounts of the
regioisomer 1-fluoro-4-(1-phenylallyl)benzene 3a was also formed in the case of dppf. The
use of IPr or 2,2’-bipyridine as the ligands provided 2a in lower yields (entries 11-12). The
reaction proceeded also very well in THF or 1,4-dioxane, but less efficiently in toluene
(entries 13-15). Interestingly, decreasing the amounts of K2CO3 to 0.2 equiv did not reduce
the yield of 2a (entry 16 vs 6). It was noted that in most of the transition metal-catalyzed
reactions involving organoborons, one or more than one equivalent of bases were usually
required. In our reaction, only catalytic amounts of bases were enough, demonstrating the
“greener” process of this method. Remakably, in the absence of a ligand, the reaction also
proceeded efficiently and cleanly to give 2a in 92% yield, while the Z-isomer or
1
regioisomer were not observed according to the H NMR analysis of the crude reaction
mixture (entry 18). The use of 0.2 equiv of Cs2CO3 or K3PO4 as the base provided 2a also
in high yields, indicating that these two bases displayed similar reactivity compared with
K2CO3 (entries 19-20, see also entries 2-4). 2a was not observed in the absence of either a
base or the nickel catalyst as expected (entries 21-22). Interestingly, the reaction could also
proceed in the presence of 5.0 equiv of water, albeit with a lower product yield (79%, entry
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23). The use of Ni(II) complex such as NiCl2(DME) or NiCl2·6H2O significantly decreased
the yield of 2a (entries 24-25).
Table 1. Optimization of the Reaction Conditions
5 mol % catalyst
ligand
base
Ph
+
OH
F
B(OH)2
Ph
solvent
1a
2a
F
yield
(%)a
temp.
base
(equiv)
time
(h)
ligand
(mol %)
entry
catalyst
solvent
(oC)
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
MeCN
MeCN
MeCN
MeCN
80
80
80
80
8
0
PMe2Ph (10)
PMe2Ph (10)
PMe2Ph (10)
PMe2Ph (10)
PMe2Ph (10)
PMe2Ph (10)
PPh3 (10)
1
tBuOK (1)
Cs2CO3 (1)
8
85
90
92
76
89
92
89
75
68b
78
78
89
83
2
8
K3PO4 (1)
K2CO3 (1)
NEt3 (1)
3
8
4
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
THF
8
80
50
50
50
50
5
6
K2CO3 (1)
K2CO3 (1)
K2CO3 (1)
K2CO3 (1)
K2CO3 (1)
K2CO3 (1)
K2CO3 (1)
K2CO3 (1)
K2CO3 (1)
24
24
24
24
7
8
PBu3 (10)
dppp (6)
9
10
dppf (6)
50
50
50
50
50
24
24
24
24
24
IPr (10)
11
12
13
14
15
16
2,2'-bipy (6)
PMe2Ph (10)
PMe2Ph (10)
1,4-dioxane
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
toluene
MeCN
MeCN
MeCN
MeCN
MeCN
65
89
0
PMe2Ph (10)
K2CO3 (1)
K2CO3 (0.2)
-
50
50
24
24
24
3
PMe2Ph (10)
17
18
19
20
21
22
PMe2Ph (10)
50
50
50
50
50
50
50
-
-
K2CO3 (0.2)
Cs2CO3 (0.2)
K3PO4 (0.2)
-
92
92
92
0
3
-
-
-
-
-
-
3
3
3
3
3
3
MeCN
MeCN
MeCN
Ni(cod)2
-
K2CO3 (0.2)
K2CO3 (0.2)
K2CO3 (0.2)
K2CO3 (0.2)
0
23c Ni(cod)2
79
NiCl2(DME)
NiCl2 6H2O
MeCN
MeCN
50
50
67
62
24
25
aDetermined by 1H NMR of the crude reaction mixture using 1,3,5-trimethoxybenzene
as the internal standard. b6% of the branched product 1-fluoro-4-(1-phenylallyl)benzene
3a was also formed. c5.0 equiv H2O was added.
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With the optimized reaction conditions in hand, the scope of this coupling reaction
with respect to various substituted arylboronic acids was first evaluated using cinnamyl
alcohol 1a as the reaction partner. As shown in Scheme 2, a wide range of arylboronic
acids were suitable for this reaction. Both of the electron-rich and -deficient aryl boronic
acids serve as efficient nucleophiles in this reaction, furnishing the corresponding products
2a-2j in generally good to excellent yields within short reaction time. The results indicated
that the electronic nature of aryl substituents on boronic acids had little influence on the
reaction efficiency. A variety of functional groups such as fluoro, acyl, cyanide,
trifluoromethyl, ester, chloro, methyl and methoxy groups were tolerated. Especially, the
reaction tolerated C-Cl bond in arylboronic acid (2f). Aryl boronic acids bearing sterically
demanding ortho-methyl and 1- or 2-naphthyl groups coupled well with 1a to give 2h and
2k-2l in high yields, indicating that the reaction is not sensitive to the steric effects. In the
cases of 3-thienyl or 3-furanyl boronic acids, good yields of the corresponding 2n and 2o
could be achieved only after increasing the catalyst/base loading with the use of PMe2Ph as
o
the ligand, and stirring at 80 C. The use of vinyl boronic acid gave the desired 2p in
moderate yield.
Scheme 2. Scope of Arylboronic Acidsa
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5 mol % Ni(cod)2
20 mol % K2CO3
+ Ar B(OH)2
Ph
OH
Ph
Ph
Ar
MeCN, 50 oC
1a
2
Ph
CN
Ph
Ph
O
CF3
F
H
2a, 3 h, 92%
2b, 4 h, 85%
2c, 5 h, 98%
2d, 3 h, 91%
Cl
Ph
Ph
Ph
Ph
CO2Et
Me
Me
Cl
2g, 3 h, 86%
2e, 3 h, 94%
2f, 3 h, 63%
2h, 5 h, 95%
Ph
Ph
Ph
Ph
OMe
OMe
S
2j, 5 h, 88%
2i, 24 h, 76%
2m, 6 h, 95%
2k, 18 h, 86%
2l, 3 h, 98%
Ph
Ph
Ph
2o, 10 h, 89%b
O
Ph
Ph
Ph
2n, 12 h, 72%b
2p, 12 h, 50%
aIsolated yields. b10 mol % Ni(cod)2, 20 mol % PMe2Ph and 40 mol % K2CO3 were used, and the
reaction was carried out at 80 oC.
The present method could also be applied successfully to various types of allylic
alcohols to provide the corresponding coupling products in moderate to high yields (Table
2). For cinnamyl alcohol derivatives, the parent phenyl ring bearing no substituent or
4-OMe, 3-Cl or 4-CF3 substituents worked well to afford 4a-4d in 89-94% yields (Table 2,
entries 1-4). In the case of sterically bulkier 1-naphthyl-substituted allylic alcohol, the
corresponding product 4e was formed smoothly in 86% yield (entry 5). Substrates bearing
a furan ring or a TMS substituent at the alkene terminus were also suitable for this reaction,
leading to 4f and 4g as a mixture of E/Z isomers (entries 6-7). Introduction of a methyl
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group at the C-2 position of cinnamyl alcohol resulted in a lower yield of 4h (59%, entry 8).
Secondary alcohol with a methyl group at C-1 position reacted with phenylboronic acid
efficiently (4i), however, a phenyl-substituted secondary alcohol resulted in the formation
of 4j in low yield (entries 9-10). Allyl alcohol 1k, a regioisomer of 1a, also coupled well
with phenylboronic acid to give the same product 4a in 80% yield (entry 11). The results
suggest that a common -allylnickel intermediate was formed in both reactions using 1a or
1k as the substrates. In the case of 2-benzothienyl-substituted alcohol 1l, increasing the
catalyst loading and the addition of phosphine ligand were required in order to achieve
higher product yield (entry 12). When allylic alcohols bearing an alkyl group at the C-1
position such as 1m and 1n were used as the substrates, the corresponding linear products
4m and 4n were obtained as the major isomers (entries 13-14). Coupling of
cis-but-2-ene-1,4-diol with phenyl boronic acid afforded monophenylated product 4o in 43%
yield, together with 13% of branched product 3o. Simple allylic alcohol or
2-methyl-2-propen-1-ol were also proved to be perfect substrates, allowing the formation
of 4p and 4q in 70-87% yields upon coupling with 2-naphthylboronic acid (entries 16-17).
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Table 2. Scope of Allylic Alcohols
5 mol % Ni(cod)2
20 mol % K2CO3
R1
R1
OH
Ph
+
PhB(OH)2
R2
MeCN, 50 oC, 3-5 h
R2
1
4
yield(%)a
94
entry
1
product
allylic alcohol
OH
R = H (1a)
Ph
4a
R
R
R = 4-OMe (1b)
R = 3-Cl (1c)
4b
4c
4d
90
89
93
2
3
4
R = 4-CF3 (1d)
4e
4f
86
78
57
59
5
6
(1e)
(1f)
1-naphthyl
OH
1-naphthyl
Ph
OH
Ph
O
O
E/Z = 10:1
4g
(1g)
(1h)
7
8
TMS
Ph
TMS
OH
E/Z = 4.3:1
4h
Ph
OH
Ph
Ph
Me
Me
Me
E/Z = 2.5:1
Me
OH
Ph
9
(1i)
4i
4j
75
Ph
Ph
Ph
Ph
Ph
34b
80
10
11
(1j)
OH
Ph
Ph
OH
4a
(1k)
Ph
OH
Ph
79c
(1l)
4l
12
S
S
OH
Ph
62d,e
(1m)
(1n)
4m
13
14
E/Z = 20:1
Ph
OH
+
+
78d,f
Ph
Ph
Ph
Ph
4n, E/Z = 9.1:1
3n
56d
Ph
HO
15
(1o)
HO
OH
HO
Ph
4o, E/Z = 16.7:1, 43%
3o, 13%
OH
OH
87g
70g
4p
4q
16
17
(1p)
(1q)
aIsolated yields. b8 h. c10 mol % Ni(cod)2, 20 mol % PMe2Ph and 40 mol % K2CO3 were
used, 80 oC, 12 h. dOverall yields. eContaining trace amounts of 3m. f4n:3n = 6.9:1.
gnaphthalen-2-ylboronic acid was used.
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Inspired by the above results, we next investigated the reactivity of other organoboron
derivatives. Gratifyingly, the coupling reactions of organoboronic esters such as PhB(pin)
or PhB(nep) with 1a under the standard reaction conditions proceeded efficiently to afford
4a in excellent yields (Table 3, entries 1-2). Boroxine and triphenylboron also showed
excellent reactivities for this reaction, furnishing 4a in 91-97% yields (entries 3-4).
However, no coupling product was obtained using boronate anions such as potassium
phenyltrifluoroborate as the substrate (entry 5). The results indicated that the Lewis acidic
features of organoboronic acid derivatives are required for this reaction. Allylic alcohol
may be activated by the coordination with arylboron compounds[9] or forming a boronate[14]
to facilitate the oxidative addition step. It should be noted that the coupling methods that
could accommodate both organoboronic acid and other boron regents are quite rare.[5d] Our
method shows the wide compatibility for boron nucleophiles.
Table 3. Coupling of 1a with Other Organoboron Derivatives
5 mol % Ni(cod)2
20 mol % K2CO3
Ph
OH
+
Ph
Ph
Ph-BR2
MeCN, 50 oC
1a
4a
entry
yield (%)a
time (h)
Ph-BR2 (equiv)
1
2
PhB(pin) (1.5)
PhB(nep) (1.0)
(PhBO)3 (0.5)
Ph3B (0.5)
24
3
90
91
91
3
4
4
3
7
97
-(90)b
PhBF3K (1.5)
5
aIsolate yields.bThe yield of the recovered 1a is shown in parenthesis
A possible reaction mechanism is shown in Scheme 3. The reaction may proceed
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through oxidative addition of allylic alcohol to Ni(0) species assisted by a Lewis acid to
give an -allylnickel(II) complex 5. This process might also take place through a boronate
intermediate. Transmetalation of complex 5 with arylboronic acid promoted by a base
provides -allylarylnickel(II) species 6. This is followed by reductive elimination to
deliver the coupling product 2. During the transmetalation step, a base of KOH might be
formed, which reacts with KHCO3 derived through decomposition of B(OH)2(KCO3) to
regenerate the K2CO3, thus a catalytic amount of base is enough for this reaction. In
addition, no additional ligand is needed in this reaction, possibly due to the high reactivity
of intermediate 5 bearing an -allyl ligand, which undergoes the subsequent reaction
efficiently.
Scheme 3. Possible reaction mechanism
Ph
OH
1a
ArB(OH)2
Ph
OH
Ni(0)
ArB(OH)2
Ph
Ar
2
OH
Ni
reductive
elimination
oxidative
addition
Ph
Ar
Ni
5
Ph
6
ArB(OH)2
transmetalation
K2CO3
B(OH) (KCO )
KOH
+
3
2
HO
B
+ KHCO3
H2O
O
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Conclusions
In summary, we have developed an efficient nickel-catalyzed procedure for the direct
coupling of allylic alcohols with arylboronic acids or their derivatives, which provides an
easy access to a wide range of 3-arylated alkenes with excellent results. The use of
commercially available Ni(cod)2 as the catalyst, simple and easy operational procedure,
without the use of ligands or additional activators and mild reaction conditions make this
procedure an alternative and attractive approach for this type of coupling reactions. Further
studies to elucidate the reaction mechanism and to extend the scope of synthetic utility are
in progress in our laboratory.
Experimental
Typical procedure for the synthesis of cinnamyl-4-fluorobenzene (2a).
The reaction was conducted in an oven-dried screw-cap vial (4 mL) equipped with a
magnetic stir bar. In a nitrogen-filled glove box, Ni(cod)2 (4.1 mg, 0.015 mmol), K2CO3
(8.3 mg, 0.06 mmol), (4-fluorophenyl)boronic acid (42.0 mg, 0.3 mmol),
(E)-3-phenylprop-2-en-1-ol (40.3 mg, 0.3 mmol) and MeCN (1.5 mL) were added
sequentially to a screw-cap vial. The vial cap was then securely fitted and taken outside the
o
glove box. After the reaction mixture was stirred at 50 C for 3 h, the mixture was filtered
through a pad of silica gel and washed with ethyl acetate. The solvent was evaporated
under the reduced pressure and the residue was purified by column chromatography on
silica gel (eluent: petroleum ether) to give the desired product 2a in 92% yield (58.9 mg) as
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a colorless oil. 1H NMR (400 MHz, CDCl3): δ 3.50 (d, J = 6.4 Hz, 2H), 6.31 (dt, J = 15.6,
13
6.8 Hz, 1H), 6.42 (d, J = 16.0 Hz, 1H), 6.96-7.00 (m, 2H), 7.16-7.35 (m, 7H); C NMR
2
(100 MHz, CDCl3): δ 38.44, 115.18 (d, JC-F = 21.4 Hz), 126.09, 127.18, 128.51, 128.95,
3
4
2
130.00 (d, JC-F = 7.6 Hz), 131.15, 135.69 (d, JC-F = 3.1 Hz), 137.26, 161.45 (d, JC-F
=
243.4 Hz). The spectroscopic data are in accordance with the literature.[15]
Supporting Information
The supporting information for this article is available on the WWW under
https://doi.org/10.1002/cjoc.2018xxxxx.
Acknowledgement
We thank the National Key Research and Development Program (2016YFA0202900),
the National Natural Science Foundation of China (21772217), Science and Technology
Commission of Shanghai Municipality (18XD1405000), the Strategic Priority Research
Program of the Chinese Academy of Sciences (XDB20000000), and Shanghai Institute of
Organic Chemistry (sioczz201807) for financial support.
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