Selective and efficient synthesis of trans-arylvinylboronates and trans-hetarylvinylboronates using palladium catalyzed cross-coupling

Article abstract of DOI:10.1039/C6NJ03984G

trans-Arylvinylboronate derivatives are important synthesis blocks in natural products, pharmaceuticals and organic materials. There are only a few reaction conditions that could selectively provide trans-arylvinylboronates by Heck coupling of pinacol vin

Full text of DOI:10.1039/C6NJ03984G

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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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Selective and efficient synthesis of trans-arylvinylboronates and
trans-hetarylvinylboronates using palladium catalyzed cross-
coupling†
Received 00th January 20xx,
Accepted 00th January 20xx
Zhihao Liua, ‡, Wei Weia, ‡, Lu Xionga, Qiang Fengb, Yaojie Shia, Ningyu Wang*a, Luoting Yu*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
Trans-arylvinylboronates derivatives are important synthesis blocks in natural products, pharmaceuticalsm and organic
materials. There are only a few reaction conditions that could selectivly provided trans-arylvinylboronates by Heck
coupling of pinacol vinylboronate and aryl halides. Here we report an efficient and versatile method with the palladium
catalyzed cross-coupling between pinacol vinylboronate and various aryl or hetaryl bromides to get the corresponding
trans-(het)arylvinylboronates in excellent yields and selectivitiy. 30 examples have been synthesized by this protocol which
offers an alternative method to prepare these useful building blocks.
Introduction
Palladium-catalyzed cross-coupling reactions to construct carbon- anti-cancer activities by targeting the stress response to ROS
carbon bonds and carbon-heteroatom bonds have attracted great (reactive oxygen species) in several representative cancer cells4c as
attention since their extremely significance in synthetic organic well as anti-inflammatory properties4f. 2 (Axitinb), a small molecule
chemistry. Using these reactions, a large number of complicated tyrosine kinase inhibitor, has been approved for renal cell
molecules closely related to human life have been successfully carcinoma (RCC) by the U.S. Food and Drug Administration4d, 4g. It
synthesized, including medicines, agricultural chemicals, high-tech contains a linear chain of vinyl pyridine which could potentially fit
polymer materials and natural products1. The Heck coupling into the solvent-exposed side of the adenine binding pocket4a. 3
reaction involves the palladium catalyzed coupling of alkenyl or aryl (CFI-400945),
a selective Polo-like Kinase 4 inhibitor, has
halides or triflates with olefins in the presence of a base to form demonstrated efficacy in vitro and in vivo against breast and
conjugated arenes as products which result from the substitution of ovarian cancers and entered clinical trials4e, 4h. 4, has an IC50 value of
a hydrogen atom in the alkene coupling partner2. The Heck coupling 1.1 nM for the inhibition of PKC and could block the production of
reaction is of great importance and a valuable tool routinely IL-2 in both stimulated murine T cells and human whole blood4b
employed in both academic research and industrial production.
.
Richard Heck was thus awarded the 2010 Nobel Prize in Chemistry
for the discovery and development of this reaction3.
Aryl olefins and heteroaryl olefins are important structural motifs in
bioactive derivatives4 and organic materials5 because of their
conjugated rich electronic and linear characteristics6. The chemical
structures of the representative bioactive derivatives containing
arylvinyl or hetarylvinyl groups are shown in Figure 1.
1
(Piperlongumine) is a natural product which has shown selective
a.Sichuan University, State Key Laboratory of Biotherapy/Collaborative Innovation
Center of Biotherapy and Cancer Center, West China Hospital, West China
Medical School, Sichuan University, Chengdu 610041, China.
Corresponding authors: Luoting Yu yuluot@scu.edu.cn; Ningyu Wang
232914292@qq.com.
‡ These authors contributed equally.
† Electronic Supplementary Informaꢀon (ESI) available: Optimum of
copolymerization conditions; Intrinsic viscosity of copolymer. See
DOI: 10.1039/x0xx00000x
Figure 1 Chemical structures of representative bioactive derivatives
containing arylvinyl or hetarylvinyl groups.
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Scheme 1 The palladium catalyzed cross-coupling of arylbromides with pinacol vinylboronate in two alternative mechanisms.
Organoboron reagents have been proved to be useful building in favour of Suzuki coupling, as 5D was the major product in all
blocks in organic chemistry and are widely applied in palladium attempts without regard to the palladium sources (Table 1, entry 1,
catalyzed cross-coupling reactions for their stability, commercial 2, 10, 17 and 19). The reaction did not proceed in the presence of
availability and synthetic versatility7. Boronate moietys can be (±)-BINAP as ligand (Table 1, entry 3). Using phenanthroline as
further transformed into other functional groups such as halides8, ligand offered good selectivity for the Heck product 5C (Table 1,
ketones9, amines9b and alkyl groups10
. Most notably, trans- entry 4, 11, 18) but the yields were far from being satisfactory. It se-
arylvinylboronates are important intermediates to construct
arylvinyl derivatives via Suzuki cross-coupling reactions. There are
mainly two distinctive methods for the synthesis of
arylvinylboronates. 1) Arylvinylboronates can be accessed by direct
hydroboration of arylethynylenes with pinacol borane by using
Table 1 Optimization of the reaction conditionsa
various transition metal catalysts11 and metal-free catalysts12
However, it often needs several steps to prepare terminal
arylethynylenes which also lack inherent reactivity13
2) Vinyl
.
Entry [Pd]
Ligand
Base
Yield (%, 5C+5D)b
.
1
Pd(OAc)2
PPh3
Et3N
Et3N
Et3N
12+61
21+54
NA
pinacol boronic esters can react with aryl halides to get
alkenylboronates via the Heck coupling reaction14. The reaction of
alkenylboronates with aryl halides could potentially provide either a
Heck coupling product by the palladium (0) adds across the alkene
or a Suzuki coupling product by the palladium (0) inserts into the C-
B bond (Scheme 1). However, there is only a few conditions with
limited scope of application that could selectively offer the Heck
2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PdCl2
PCy3
3
(±)-BINAP
4
phenanthroline Et3N
49+7
55+17
5
P(t-Bu)3
P(t-Bu)3
P(t-Bu)3
P(t-Bu)3
P(t-Bu)3
PPh3
Et3N
6
DIPEA 68+14
TMEDA 49+28
7
8
AcOK
42+27
products14a, 14c
.
9
Cs2CO3 55+8
DIPEA 6+54
As a part of our ongoing research program on construction of
(het)arylvinyl compound library for developing potential protein
kinase inhibitors, we have found an efficient and versatile condition
for the Heck coupling of pinacol vinylboronate with various
(het)arylbromides in excellent yields and selectivity in this study.
10
11
12
13
14
15
16
17
18
19
20
21
PdCl2
phenanthroline DIPEA 48+12
PdCl2
P(t-Bu)3
DIPEA 55+17
DIPEA 17+68
DIPEA 7+83
DIPEA 12+69
DIPEA 75+17
DIPEA 29+46
Pd(PPh3)4
PdCl2(dppf)
Pd(PPh3)2Cl2
Pd(P(t-Bu)3)2
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
/
/
/
/
Experimental
PPh3
Initially, pinacol vinylboronate and bromobenzene were selected as
model substrates for optimizing the reaction conditions. A range of
bases, common palladium sources and ligands were tested
respectively for their influence on the yield and selectivity between
the Heck reaction versus the Suzuki reaction (Table 1). The reaction
performed in the presence of Pd(OAc)2 (5 mol%), Et3N (2 equiv.) and
various ligands (5 mol%) provided 5C with yields of less than 50%
(Table 1, entry 1-4) except P(t-Bu)3 (Table 1, entry 5) as the ligand.
PPh3 (Table 1, entry 1) and PCy3 (Table 1, entry 2) were shown to be
phenanthroline DIPEA 50+13
PCy3
DIPEA 37+54
DIPEA 81+11
DIPEA 75+9
P(t-Bu)3
P(t-Bu)3
·HBF4
a
Reaction conditions: bromobenzene (0.5 mmol, 1.0 equiv.),
pinacol vinylboronate (0.55 mmol, 1.1 equiv.), toluene (5.0 mL),
85oC, 3 h, under N2 atmosphere. b Determined by the analysis of
HPLC results.
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Entry
Solvent
Time (h) Temp (o
C)
Yield (%, 5C+5D)b
1
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
CH3CN
3
3
3
3
3
1
6
12
3
3
3
3
75
85
95
105
115
95
95
95
95
95
95
95
62+13
71+9
2
3
83+10
79+10
69+14
67+6
4
5
6
7
58+8
8
53+14
54+11
68+13
63+11
61+16
9
10
11
12
Dioxane
DMF
DMA
a Reaction conditions: bromobenzene (0.5 mmol, 1.0 equiv.), pinacol
vinylboronate (0.55 mmol, 1.1 equiv.), DIPEA (1 mmol, 2.0 equiv.),
b
slovent (5.0 mL), under N2 atmosphere.
Determined by the
analysis of HPLC results.
Table 2 Optimization of the reaction conditionsa.
emed that the ligand P(t-Bu)3 tended to give the greatest yield than
other ligands (Table 1, entry 5 versus 1-4). And next different bases
were employed in the reaction in the presence of Pd(OAc)2 (5 mol%)
and P(t-Bu)3 (10 mol%) to investigated their effects on the yields
and selectivity (Table 1, entry 5-9). The addition of DIPEA (Table 1,
entry 6) or Cs2CO3 (Table 1, entry 9) as bases offered greater yield
and selectivity to 5C compared with that addition of Et3N, but more
impurities were offered when Cs2CO3 was used. Subsequently, a
variety of palladium sources and ligands were screened in the
presence of DIPEA as base in the reaction. PdCl2 showed similar
reactivity and lower selectivity compared with Pd(OAc)2 (Table 1,
entry 10-12). It was also found that P(t-Bu)3 tended to give greater
a Reaction conditions: bromobenzene (2 mmol, 1.0 equiv.), pinacol
vinylboronate (2.2 mmol, 1.1 equiv.), toluene (8.0 mL), DIPEA (4
b
mmol, 2.0 equiv.), 95oC, 3 h, under N2 atmosphere. Isolated yield
after silica gel chromatography.
Table 3 Substrate scope for Heck coupling of pinacol vinylboronate
with various arylbromides a,b
.
Scheme 2 Two possible ways for the formation of by-product 5D in
the optimised reaction.
yield than other ligands (Table 1, entry 10-12). Palladium (0)
catalysts such as Pd(PPh3)4 (Table 1, entry 13), PdCl2(dppf) (Table 1,
entry 14) and Pd(PPh3)2Cl2 (Table 1, entry 15) gave more 5D than
Heck reaction product 5C. While Pd(P(t-Bu)3)2 gave a higher yield
and selectivity of 5C (Table 1, entry 15) the air and moisture
sensitivity made it inconvenient to be used. Pd2(dba)3 offered the
best combination of yield and selectivity to 5C especially in the
presence of DIPEA as base and P(t-Bu)3 (81%) or P(t-Bu)3·HBF4 (79%)
as ligands (Table 1, entry 20-21).
Br
O
Suzuki reaction
B
O
5A
5B
5D
Protodeborylation
Heck reaction
O
B
O
As surmised from the results shown in Table 1, Pd2(dba)3 and P(t-
Bu)3 related ligands may be good combinations for this reaction
5C
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from 1 h to 12 h, the yield of Heck product 5C declined, but the
yields of 5D increased over time (Table 2, Entry 3, 6-8). Next, we
investigated the influence of solvents on the reaction. The
substrates could be efficiently transformed in a number of solvents.
Although polar solvents such as DMF or MeCN are commonly used
for Heck reaction, polar solvents decreased the yield of 5C
substantially (Table 9-12) and toluene turned out to be a much
better solvent than other solvents in this reaction (Table 2, Entry 3).
O
B
O
B
O
B
O
O
O
O
O
S
9A(0%)c
9B(64%)
9C(75%)
After examined a range of Pd catalysts, ligands, bases, solvents and
temperatures, the combination of 5 mol% of Pd2(dba)3, 10 mol% of
P(t-Bu)3·HBF4 and 2 equiv. of DIPEA in toluene at 95°C for 3 h under
nitrogen emerged as the best reaction condition.
O
O
O
O
S
B
B
B
N
O
B
O
N
9E(0%)d
9F(71%)
9D(82%)
In the optimised reaction conditions, Suzuki reaction of 5A with 5B
and protodeborylation of 5C are two possible ways for the
formation of by-product 5D (Scheme 2). To verify whether Suzuki
reaction could actually proceed in this condition, we treated 5C
with 1-bromo-4-methoxybenzene and obtained the Suzuki reaction
product (E)-1-methoxy-4-styrylbenzene. Besides, Heck reaction
product 5C was re-treated to the optimized reaction condition to
determine whether protodeborylation of 5C occurred, and about
6% of 5C was transformed into protodeborylation product in this
condition after reacting 3 h. These results indicated that by-product
5D might come from both Suzuki reaction and protodeborylation,
which also explained that the yields of 5D increased with the
reaction time extended from 1 h to 12 h (Table 2, Entry 3, 6-8).
O
O
O
O
O
O
O
B
B
NH
N
NH
O
9H(83%)
9G(67%)
9I(69%)
O
O
O
O
O
B
N
B
B
N
N
O
N
O
O
N
N
N
9J(76%)
9K(85%)
9L(80%)
O
O
O
N
B
N
N
B
O
O
O
NH
O
O
B
N
N
O
N
N
N
O
N
9M(70%)
9N(66%)
9O(68%)
a Reaction conditions: bromobenzene (2 mmol, 1.0 equiv.), pinacol
We next assessed the scope of this condition with various
arylbromides. As shown in Table 3, a variety of monosubstituted
bromo anisoles and bromo benzotrifluorides could be transformed
to their corresponding Heck coupling products (7B-7D, 7F-7H) in
moderate to good yields, and the yield of an electron-riched
substrate was slightly higher than an electron-defective substrate.
o-Bromoanisoles and o-bromobenzotrifluorides resulted in
significant decrease in yield (7B, 7F), suggesting that hindrance
would be detrimental to the reaction. 3-bromo-N-methylaniline and
1-(3-bromophenyl)-N,N-dimethylmethanamine were effective to
offer target products (7I, 7J). p-Bromoanilines and p-
bromobenzylamines were employed to couple with pinacol
vinylboronate to provide corresponding Heck coupling products
(7K-7Q) also in respectable yields (72-84%).
vinylboronate (2.2 mmol, 1.1 equiv.), toluene (8.0 mL), DIPEA (4
b
mmol, 2.0 equiv), 95oC, 3 h, under N2 atmosphere. Isolated yield
after silica gel chromatography. c Messy reaction. d No reaction.
Table 4 Substrate scope for Heck coupling of pinacol vinylboronate
with various hetarylbromides a,b
.
system that mainly provided the Heck reaction product 5C in better
yields. P(t-Bu)3 and P(t-Bu)3·HBF4 are usually used as bulky electron
rich phosphines in palladium catalyzed reactions15. P(t-Bu)3 is very
air sensitive which requires strict air-exclusion while P(t-Bu)3·HBF4 is
an air and moisture stable HBF4-phosphonium salt form of P(t-Bu)3
and allows easier manipulation. Hence, air and moisture stable
catalyst Pd2(dba)3 and ligand P(t-Bu)3·HBF4 in combination with
DIPEA as base were selected as the catalytic system for further
optimization to determine suitable temperature and solvent.
After investigating the generality of this coupling reaction with
respect to a series of substituted arylbromides, various hetaryl
bromides were then studied to expand the scope of this method
(Table 4). When 2-bromofuran was used as substrate, almost no
corresponding Heck coupling product and Suzuki product were
obtained, which may be ascribed to the instablity of 2-bromofuran
under Pd catalyst and high temperature. However, 3-bromofuran
could be effectively converted to the (E)-2-(furan-3-yl) vinylboronic
Reactions conducted at lower temperatures (Table 2, Entry 1-2) led
to an evident decrease in yields, while a higher temperature
resulted in decline in both yield and selectivity (Table 2, Entry 4-5).
As mentioned above, it could be concluded that the Heck product
5C may be kinetically dominated. When the reaction time extended
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acid pinacol ester (9B). Both 2-bromothiophene and 3-
bromothiophene could react with pinacol vinylboronate to offer the
respective Heck coupling products (9C, 9D) in good yields and
pyridine species could also be transformed to the target Heck 2.
products (9F-9G) except 2-bromopyridine (no reaction). We suspect
that the electron density of C-Br bond in 2-bromopyridine is too low
for palladium catalyst to initiate oxidative addition. 5-Bromoindole
and 7-bromo-2H-benzo[b][1,4]oxazin-3(4H)-one were transformed
to corresponding Heck coupling products also in satisfying yield (9H-
9I). Then various 5-bromopyridines were used as substrates which
all gave the desired products in good yields (9J-9O).
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Conclusions
4.
In conclusion, we have developed an effective method to prepare
tran-(het)arylvinylboronates. Detailed studies have showed that the
consistant of Pd2(dba)3 (5 mol%), P(t-Bu)3·HBF4 (10 mol%) and of
DIPEA (2 equiv.) in toluene at 95oC for 3 h under nitrogen was the
best condition in the reaction. The present work provides an easy
manipulated and inexpensive protocol that is effective and selective
to the synthesis of trans-vinyl boronates with wide substrate scope.
We believe this work will greatly benefit the development of
bioactive molecules and organic functional materials.
Experimental
General procedure for the Heck coupling of pinacol
vinylboronate with (het)arylbromides
A mixture of vinylboronate pinacol ester (2.2 mmol, 1.1 equiv.), the
corresponding aryl and hetaryl bromides (2.0 mmol, 1.0 equiv.),
DIPEA (4.0 mmol, 2.0 equiv.), Pd2(dba)3 (0.1 mmol, 5 mol%) and P(t-
Bu)3·HBF4 (0.2 mmol, 10 mol%) in dry toluene (8.0 mL) was stirred
at 95°C for 3 h under N2 atmosphere. Then the reaction mixture
was evaporated under vacuum. H2O (5 mL) was added to the
residual mixture. The mixture was extracted with ethyl acetate (10
mL x 3), and the combined organic layer was dried over anhydrous
Na2SO4, filtered and the solvent was evaporated under vacuum. The
residue was purified by silica gel chromatography using EtOAc/n-
hexene as eluent to afford the products.
5.
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7.
(a) M. Oestreich, Chapter 16. The Asymmetric Intramolecular
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Acknowledgements
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This work was supported by Natural Science Foundation of China
(No. 81502919) and China Postdoctoral Science Foundation (No.
2015M570790, No. 2016T90860). We thank Lihua Zhou of State Key
Laboratory of Biotherapy (Sichuan University) for NMR
measurements.
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Table of contents entry
Selective and efficient synthesis of trans-arylvinylboronates and trans-
hetarylvinylboronates using palladium catalyzed cross-coupling
Zhihao Liu, Wei Wei, Lu Xiong, Qiang Feng, Yaojie Shi, Ningyu Wang and Luoting Yu
An versatile method of palladium catalyzed cross-coupling between pinacol vinylboronate and
(het)arylbromides to get trans-(het)arylvinylboronates in excellent yields and selectivity.