Synthesis of β-heteroaryl carbonyl compounds via direct cross-coupling of allyl alcohols with heteroaryl boronic acids under cooperative bimetallic catalysis

Article abstract of DOI:10.1016/j.tetlet.2018.02.021

The eco-friendly cooperative Cu/Pd-catalyzed oxidative Heck reaction of allyl alcohols with heteroaryl boronic acids under air was described. The ready availability of starting materials and the mild reaction conditions made this protocol a safe and operationally convenient strategy for the efficient synthesis of β-heteroaryl carbonyl compounds.

Full text of DOI:10.1016/j.tetlet.2018.02.021

Accepted Manuscript
Synthesis of β-heteroaryl carbonyl compounds via direct cross-coupling of allyl
alcohols with heteroaryl boronic acids under cooperative bimetallic catalysis
Mingxiang Zhu, Hongli Du, Jingya Li, Dapeng Zou, Yusheng Wu, Yangjie Wu
PII:
S0040-4039(18)30189-8
https://doi.org/10.1016/j.tetlet.2018.02.021
TETL 49706
DOI:
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
24 December 2017
7 February 2018
8 February 2018
Please cite this article as: Zhu, M., Du, H., Li, J., Zou, D., Wu, Y., Wu, Y., Synthesis of β-heteroaryl carbonyl
compounds via direct cross-coupling of allyl alcohols with heteroaryl boronic acids under cooperative bimetallic
catalysis, Tetrahedron Letters (2018), doi: https://doi.org/10.1016/j.tetlet.2018.02.021
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Synthesis of β-heteroaryl carbonyl
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compounds via direct cross-coupling of allyl
alcohols with heteroaryl boronic acids under
cooperative bimetallic catalysis
Mingxiang Zhu, Hongli Du, Jingya Li, Dapeng Zou,∗ Yusheng Wu,∗ and Yangjie Wu,∗

1
Tetrahedron Letters
journal homepage: www.els evier.com
Synthesis of β-heteroaryl carbonyl compounds via direct cross-coupling of allyl
alcohols with heteroaryl boronic acids under cooperative bimetallic catalysis
,a
Mingxiang Zhu,a Hongli Du,a Jingya Li,b Dapeng Zou,∗,a,b Yusheng Wu,∗,a,b,c and Yangjie Wu,∗
aThe College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450052, P. R. China.
b Tetranov Biopharm, LLC. And Collaborative Innovation Center of New Drug Research and Safety Evaluation, Zhengzhou, 450052, P. R. China.
cTetranov International, Inc. 100 Jersey Avenue, Suite A340, New Brunswick, NJ 08901, USA.
ARTICLE INFO
ABSTRACT
Article history:
Received
The eco-friendly cooperative Cu/Pd-catalyzed oxidative Heck reaction of allyl alcohols with
heteroaryl boronic acids under air was described. The ready availability of starting materials and
the mild reaction conditions made this protocol a safe and operationally convenient strategy for
the efficient synthesis of β-heteroaryl carbonyl compounds.
Received in revised form
Accepted
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
β-heteroaryl carbonyl compounds
allyl alcohols
heteroaryl boronic acids
photocatalysis reaction
Introduction
The traditional methods for the synthesis of aryl/heteroaryl
carbonyl compounds usually need multistep with lower yields.
Functionalized β-aryl/heteroaryl carbonyl derivatives are one of
the most important organic motifs for chemical synthesis and
drug discovery.1 Especially, the ‘β-heteroaryl carbonyl’ motifs
have attracted much attention for their widespread prevalence in
the medicinally important natural products and agrochemicals
(Fig. 1).2 For example, 4-(4-hydroxy-3-methoxyphenyl)-4-
(pyridin-3-yl)butan-2-one (a1) is widely used as PDE4 inhibitor
to treat asthma and chronic obstructive pulmonary disease.3
Usp14 is known to exhibit antidiabetic, antitumor, anti-alzheimer
and antiparkinsonian activities.4
Since Heck and coworkers first reported the synthesis of β-
heteroaryl carbonyl compounds through the cross-coupling
reaction of allyl alcohols with heteroaryl halides under Pd
catalysis in 1975,5 several such reactions have been reported by
many scientists.6 In 1998, Lazzaroni first reported rhodium-
catalyzed
hydroformylation
of
vinylheteroaryl
cyclic
compounds.7 In 2016, Li and coworkers reported the rhodium-
catalyzed cross-dehydrogenative-coupling reaction of conjugated
alkenes,8 which are also regarded as convenient methods to
provide the β-heteroaryl carbonyl derivatives.
Recently, the oxidative Heck reactions have attracted much
more attentions due to their moderate reaction conditions and
higher selectivity in comparison with traditional Heck reactions.9
Compared with aryl halides, organoborane reagents are usually
readily prepared, eco-friendly and without any unpleasant odor.10
In 2012, the method for the synthesis of β-aryl ketones and
aldehydes by the Pd-catalyzed oxidative Heck reaction has been
first reported by the group of Kommu et al.11 (a) Pd(OAc)2 and
Ag2CO3 were used as catalyst and oxidant in this condition
respectively, and a wide range of aryl boronic acids could be
used in their system. In the same year, Lei11 (c) and coworkers
reported another Pd-catalyzed oxidative Heck reaction of allyl
Figure 1. Molecules containing β-aryl/heteroaryl carbonyl moiety.
———
∗ Corresponding author.
Tel.: +1 732 253 7326; fax: +1 732 253 7327; e-mail: yusheng.wu@tetranovglobal.com, zdp@zzu.edu.cn, wyj@zzu.edu.cn.

2
jThe reaction was performed with 10 mol% of additive.
kThe reaction was performed with 5 mol% of catalyst.
alcohols with aryl boronic acids, in which pure O2 instead of
Ag2CO3 was used as an eco-friendly oxidant. In 2014, Kommu et
al updated their reaction condition by using air as oxidant instead
(b)
of their previously reported Ag2CO3,11
which makes this
reaction easy to handle and environmental friendly.
In our laboratory, we are interested in development of new
conditions for the synthesis of various functional organoborane
reagents12 and various valuable compounds by using
organoborane reagents, especially using the heteroaryl boronic
acids as reaction reagents.13 Although the reported methods
offered convenient catalytic system for the synthesis of β-aryl
carbonyl derivatives, to the best of our knowledge, using
heteroaryl boronic acids as a reaction partner to synthesize these
derivatives is not reported so far. Herein, we report the first
example of Cu/Pd-catalyzed oxidative Heck reaction of allyl
alcohols with heteroaryl boronic acids for the synthesis of β-
heteroaryl carbonyl derivatives under air.
Fig 2. The structures of nitrogen ligands.
Initially, 3-pyridyl boronic acid and allyl alcohol were chosen
as model compounds to optimize the reaction conditions. The
results are summarized in Table 1.
At the very begining, the bimetallic catalysis systems reported
by Kommu11 (a) (b) et al and Lei11 (c) et al were used to start the
conditional optimization. The results indicated that their
conditions were not suitable for the cross-coupling reaction of
allyl alcohol and 3-pyridyl boronic acid (Table 1, entries 1-3).
After screening various catalytic conditions, a convenient process
to obtain the desired product by cooperative Cu/Pd-catalyzed
oxidative Heck reaction was found. The reaction could be
achieved smoothly when using Pd(OAc)2 (10 mol%) as catalyst,
CuCl (5 mol%) as additive, and 1, 10-phenanthroline (L1) 20
mol% as ligand in DMSO (0.17 M) at 80 oC under air atmosphere
for 12 h (Table 1, entry 4). Then, the reaction temperature and
time were optimized, and the best yield was obtained under 80 oC
for 12 h (Table 1, entries 4-6; see Supporting Information for
details). After various solvents were screened, DMSO was found
to give the desired product in 66 % yield (See supporting
information). Then, a list of nitrogen ligands (Fig 2, L1-L9) were
investigated. When 2,2'-dipyridyl (L4) (30 mol%) was used, the
desired product was obtained in 86%. In the absence of ligands,
the reactions could not take place (Table 1, entries 7-9; please see
the Supporting Information for details). Next, various additives
were tested. Cuprous salts were proved to perform better than
cupric and silver salts. The reaction performed well in the
presence of 5 mol% of CuCl (Table 1, entries 10-19). In the
absence of CuCl, a large amount of byproduct 3-(pyridin-3-yl)
prop-2-en-1-ol was generated and the yield of the target product
was low. Investigation of palladium catalysts indicated that
Pd(OAc)2 (10 mol%) was indispensable for the cross-coupling
reaction (Table 1, entries 20-23). Next, the effect of gaseous
environment was also studied (Table 1, entries 24 and 25). When
the reaction was performed under O2 atmosphere, almost no
target product was produced, and the main byproduct was found
to be 3, 3'-oxydipyridine. Finally, the optimum reaction condition
was obtained as follows: Pd(OAc)2 (10 mol%) as catalyst, CuCl
(5 mol%) as additive, and L4 (30 mol%) as ligand in DMSO 3
mL at 80 oC under air atmosphere for 12 h.
Results and discussion
Table 1. Cross-coupling of allyl alcohol and 3-pyridyl
boronic acid: variation of reaction conditions.a
entry
1c
catalyst
additive
Ag2CO3
CuCl
CuCl
CuCl
CuCl
CuCl
CuCl
CuCl
CuCl
--
ligand
L7
L7
-
atm.
air
yield (%)b
trace
23
Pd(OAc)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
Pd(OAc)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
Pd(OAc)2
PdCl2
2d
air
O2
3e
4f
trace
66
trace
46
L1
L1
L1
L4
L4
-
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
O2
5f, g
6f, h
7
86
77
8 c
9
trace
38
83
10
11
12
13
14
15i
16j
17
18
19
20
21
22
23k
24
25
L4
L4
L4
L4
L4
L4
L4
L4
L4
L4
L4
L4
L4
L4
L4
L4
CuBr
CuI
79
64
Cu2O
CuCl2
CuCl
CuCl
Ag2O
AgTFA
Ag2CO3
CuCl
CuCl
CuCl
CuCl
CuCl
CuCl
80
29
55
trace
trace
trace
trace
trace
18
Pd(acac)2
Pd(dba)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
38
trace
trace
Ar
aAll reactions were performed with 2.0 mmol of 1a, 1.0 mmol of 2a, 5 mol%
of additive, 10 mol% of catalyst, 30 mol% of ligand, 3 mL of solvent at 80 oC
for 12 h under air.
bYields were determined by GC-MS using Di-N-pentyl phthalate as internal
standard.
With the optimized reaction condition in hand, the coupling
reactions between various allyl alcohols and 3-pyridine boronic
acid were carried out to explore the scope of this catalytic
system, and the results were summarized in Table 2.
cThe reaction was performed with 2.0 mmol of 1a, 1.0 mmol of 2a , 5 mol%
of Pd(OAc)2, 10 mol% of L7, and 2.0 eq of Ag2CO3, at 60 °C in MeCN 3.0
mL for 24 h.
dThe reaction was performed with 1.0 mmol of 2a, 1.5 mmol of 1a, 10 mol%
of Pd(OAc)2, 20 mol% of L7, 5 mol% of CuCl, at 50 °C in DMSO 3 mL for
12 h under an air balloon (1 atm).
eThe reaction was performed with 1.0 mmol of 1a, 1.2 mmol of 2a, 2.5 mol%
of Pd(OAc)2, 5 mol% of CuCl, at 50 °C in DMSO/HOAc (3 mL, v/v=1/1) for
20 h under O2 (1 atm).
fThe reaction was performed with 20 mol% of ligand.
gThe reaction was performed under 70 oC.
hThe reaction was performed under 90 oC.
iThe reaction was performed with 2.5 mol% of additive.

3
Table 2. Scope of allyl alcohols and 3-pyridine boronic acid.a,
b
Table 4. Scope of allyl alcohols and heteroaromatic boronic
acids.a, b
aAll reactions were performed with 1.0 mmol of heteroaryl boronic acids, 0.5
mmol of allyl alcohols, 5 mol% of CuCl, 10 mol% of Pd(OAc)2, 30 mol% of
L4, 3 mL of DMSO at 80 oC for 12 h under air.
aAll reactions were performed with 2.0 mmol of 3-pyridyl boronic acid, 1.0
mmol of allyl alcohols, 5 mol% of CuCl, 10 mol% of Pd(OAc)2, 30 mol% of
L4, 3 mL of DMSO at 80 oC for 12 h under air.
bIsolated yields.
cThe reactions were performed with 2.0 mmol of heteroaryl boronic acids, 1.0
mmol of allyl alcohols,
bIsolated yields.
dThe reaction was performed at 60 oC.
cThe reaction was performed with 1.0 mmol of 3-pyridyl boronic acid, 0.5
mmol of allyl alcohols.
Then, the substrates with electron donating and electron
withdrawing group on the phenyl (2h and 2i) were examined to
give the coupling products 3h and 3i in 63% and 60% yield,
respectively. When 2j and 2k were investigated in the condition,
the desired products 3j and 3k were obtained in 61% and 58%
yield indicated that the steric hindrance might have a little
influence on the reactivity. Moreover, heteroaryl propanol 2l
could give the target product 3l in 66% yield under these reaction
conditions.
dThe reaction was performed with visible light.
A wide variety of allyl alcohols including 2b, 2c, 2d and 2e
afforded the desired products 3b, 3c, 3d and 3e with yields
ranging from 54% to 77%. 2f gave the coupling product 3f in
81% yield indicated that the steric hindrance of the allyl alcohol
is beneficial for this reaction. Next, 1-arylpropenols with various
substitutions (electron-withdrawing, electron-donating and
halogen groups) were investigated. To begin with, 2g was tested.
When the reaction of 2g with 1a was repeated, the yields ranged
from 42% to 58%. Further research indicated that when the
reaction started in the daytime, a higher yield was obtained.
When the reaction started at night time, a lower yield was got.
We speculate that the reaction is probably affected by light. So
various light sources were employed in this reaction and the
results indicated that 20W visible light source is a better choice
(Table 3). This phenomenon was only found in the reaction of the
aryl substituted allyl alcohols. It is probable that visible light has
the ability to excite the copper salt to its excited condition,14
which may do good to the cross-coupling of 1-arylpropenols with
allyl alcohols.
And then, a list of heteroaryl boronic acids were tested (Table
4). Firstly, 3-pyridine boronic acids including electron-donating
and electron-withdrawing group (1m and 1o) were investigated.
The high yield (83%) was acquired when 1m was used as
substrate. Unfortunately, 1o underwent the reaction to afford the
desired 3o in lower yield (21%). Then, 1n gave the
corresponding product 3n with a good isolated yield. Next, 1q
was examined in this condition, and the desired product 3q was
obtained in 82% yield. To further extend the reaction scope, the
coupling reactions of allyl alcohols with other heteroaryl boronic
acids such as 1r and 1s were also examined under the optimized
conditions, and the target products 3r and 3s were obtained in
moderate yields. Moreover, the reaction of unsubstituted
phenylboronic acid proceeded smoothly to give the desired
aldehyde 3t and 3u in 62% and 53% yield respectively. Finally,
compared with aromatic allyl alcohols, the aliphatic ones were
found to perform better in the reactions.
Table 3. Cross-coupling of 1-phenylprop-2-en-1-ol and 3-
pyridyl boronic acid: variation of light source.a
Yield (%)b
Conclusion
Entry
Light source
1
2
3
4
5
6
dark
42
45
44
58
58
58
In conclusion, an efficient and eco-friendly procedure for the
synthesis of β-heteroaryl ketones and aldehydes starting from
heteroaryl boronic acids and allyl alcohols was established. In
this condition, β-heteroaryl carbonyl derivatives, especially
halogen-appended β-heteroaryl carbonyl derivatives could be
easily synthesized in our discovered method with moderate to
good yields by using the inexpensive ligand under air
atmosphere. And visible light was found to be positive for the
reaction when 1-arylpropenols were used as reactants.
Additionally, a wide range of substrates were used in this system
and the desired β-heteroaryl carbonyl derivatives could prove to
254 nm UV light
365 nm UV light
Led light source
20W visible light source
Sunlight
aAll reactions were performed with 1.0 mmol of 3-pyridyl boronic acid, 0.5
mmol of 1-phenylprop-2-en-1-ol, 5 mol% of CuCl, 10 mol% of Pd(OAc)2, 30
mol% of L4, 3 mL of DMSO at 80 oC for 12 h under air.
bYield were determined by GC-MS using Di-N-pentyl phthalate as internal
standard.

4
Qiu, Z.; Zhang, Y.; Du, H.; Li, J.; Zou, D.; Wu, Y.; Wu, Y.
Tetrahedron Lett., 2017, 58, 2255-2257.
be valuable building blocks in material science and drug
discovery.
14. (a) Hara, M.; Kondo, T.; Komoda, M.; Ikeda, S.; Shinohara, K.;
Tanaka, A.; Kondo, J. N. K. Domen. Chem. Commun., 1998, 0,
357-358; (b) Chen, J.; Zhou, P.; Li, J.; Wang, Y. Carbohydr.
Polym., 2008, 72, 128-132; (c) Gao, Z.; Liu, J.; Xu, F.; Wu, D.;
Wu, Z.; Jiang, K. Solid State Sci., 2012, 14, 276-280.
Acknowledgments
We are grateful to the National Natural Science Foundation of
China (21172200, 21702191) for financial support.
References and notes
1. (a) Liu, J.; He, S.; Jian, T.; Dobbelaar, P. H.; Sebhat, I. K.; Lin, L.
S.; Goodman, A.; Guo, C.; Guzzo, P. R.; Hadden, M.; Henderson.,
A. J. Bioorg. Med. Chem. Lett., 2010, 20, 2074-2077; (b)
Gesinski, M. R.; Tadpetch, K.; Rychnovsky, S. D. Org. Lett.,
2009, 11, 5342-5345; (c) Boros, E. E.; Edwards, C. E.; Foster, S.
A.; Fuji, M.; Fujiwara, T.; Garvey, E. P.; Golden, P. L.; Hazen, R.
J.; Jeffrey, J. L.; Johns, B. A.; Kawasuji, T.; Kiyama, R.; Koble, C.
S.; Kurose, N.; Miller, W. H.; Mote, A. L.; Murai, H.; Sato, A.;
Thompson, J. B.; Woodward, M. C.; Yoshinaga, T. J. Med. Chem.,
2009, 52, 2754-2761; (d) Mathiesen, L.; Malterud, K. E.; Sund, R.
B. Free Radicals Biol. Med., 1997, 22, 307-311; (e) Benavente-
Garcia, O.; Castillo, J.; Del Baño, M. J.; Lorente, J. J. Agric. Food
Chem., 2001, 49, 189-191.
2. (a) Woodruff, T. M.; Taylor, S. M. PCT Int. Appl., WO
2012174591 A1, 2010; (b) Aktas, H.; Halperin, J. A.; Chorev, M.
PCT Int. Appl., WO 2010138820 A2, 2010.
3. Zheng, S.; Kaur, G.; Wang, H.; Li, M.; Macnaughtan, M.; Yang,
X.; Reid, S.; Prestegard, J.; Wang, B.; Ke, H. J. Med. Chem.,
2008, 51, 7673-7688.
4. Cullen, M.; Hauck, S.; Geng, B.; Foley, M.; Bastos, C.; Munoz, B.;
Haeberlein, M. PCT Int. Appl., WO 2015073528 A1, 2015.
5. Melpolder, J. B.; Heck, R. F. J. Org. Chem., 1976, 41, 265-272.
6. (a) Hagen, S. E.; Domagala, J.; C. Gajda,; M. Lovdahl,; Tait, B.
D.; Wise, E.; Holler, T.; Hupe, D.; Nouhan, C.; Urumov, A.;
Zeikus, G.; Zeikus, E.; Lunney, E. A.; Pavlovsky, A.; Gracheck, S.
J.; Saunders, J.; VanderRoest, S.; Brodfuehrer, J. J. Med. Chem.,
2001, 44, 2319-2332; (b) Yum, E. K.; Seung, K.; Choi, J. K. B.
Kor. Chem. Soc., 2001, 22, 644-646; (c) Berthiol, F.; Doucet, H.;
Santelli, M. Tetrahedron Lett., 2004, 45, 5633-5636; (d) Berthiol,
F.; Doucet, H.; Santelli, M. Appl. Organomet. Chem., 2006, 20,
855-868; (e) Berthiol, F.; Doucet, H.; Santelli, M. Tetrahedron,
2006, 62, 4372-4383; (f) Kadzimirsz, D.; Kramer, D.; Sripanom,
L.; Oppel, I. M.; Rodziewicz, P.; Doltsinis, N. L.; Dyker, G. J.
Org. Chem., 2008, 73, 4644-4649; (g) Tay, D. W.; Jong, H.; Lim,
Y. H.; Wu, W.; Chew, X.; Robins, E. G.; Johannes, C. W. J. Org.
Chem., 2015, 80, 4054-4063; (h) Colbon, P.; Ruan, J.; Purdie, M.;
Mulholland, K.; Xiao, J. Org. Lett., 2011, 13, 5456-5459.
7. (a) Caiazzo, A.; Settambolo, R.; Pontorno, L.; Lazzaroni, R. J.
Organomet. Chem., 2000, 599, 298-303; (b) Settambolo, R.;
Scamuzzi, S.; Caiazzo, A.; Lazzaroni, R. Organometallics, 1998,
17, 2127-2130.
8. Zhang, Z.; Tang, M.; Han, S.; Ackermann, L.; Li, J. J. Org.
Chem., 2017, 82, 664-672.
9. (a) Heck, R. F. J. Am. Chem. Soc., 1968, 90, 5526-5531; (b)
Matoba, K.; Motofusa, S. I.; Cho, C. S.; Ohe, K.; Uemura, S. J.
Organomet. Chem., 1999, 574, 3-10.
10. (a) Delcamp, J. H.; Brucks, A. P.; White, M. C. J. Am. Chem. Soc.,
2008, 130, 11270-11271; (b) Werner, E. W.; Sigman, M. S. J. Am.
Chem. Soc., 2010, 132, 13981-13983; (c) Karimi, B.; Behzadnia,
H.; Elhamifar, D.; Akhavan, P. F.; Esfahani, F. K.; Zamani, A.
Synthesis, 2010, 9, 1399-1427; (d) Zhang, Y. H.; Shi, B.; Yu, J. J.
Am. Chem. Soc., 2009, 131, 5072-5074.
11. (a) Vellakkaran, M.; Andappan, M. M. S.; Kommu, N. Eur. J.
Org. Chem., 2012, 25, 4694-4698; (b) Vellakkaran, M.; Andappan,
M. M. S.; Kommu, N. Green Chem., 2014, 16, 2788-2797; (c)
Chen, M.; Wang, J.; Chai, Z.; You, C.; Lei, A. Adv. Synth. Catal.,
2012, 354, 341-346.
12. Lu, H.; Wang, S.; Li, J.; Zou, D.; Wu, Y.; Wu, Y. Tetrahedron
Lett., 2017, 58, 839-842.
13. (a) Liang, A.; Li, X.; Liu, D.; Li, J.; Zou, D.; Wu, Y.; Wu, Y.
Chem. Commun., 2012, 48, 8273-8275; (b) Leng, F.; Wang, Y.;
Li, H.; Li, J.; Zou, D.; Wu, Y.; Wu, Y. Chem. Commun., 2013, 49,
10697-10699; (c) Liang, A.; Han, S.; Wang, L.; Li, J.; Zou, D.;
Wu, Y.; Wu, Y. Adv. Synth. Catal., 2015, 357, 3104-3108; (d) Li,
X.; Zou, D.; Zhu, H.; Wang, Y.; Li, J.; Wu, Y.; Wu, Y.; Org. Lett.,
2014, 16, 1836-1839; (e) Zhang, Y.; Geng, Z.; Li, J.; Zou, D.; Wu,
Y.; Wu, Y. Adv. Synth. Catal., 2017, 359, 390-394; (f) Zhu, M.;

5
Highlights
A facile and efficient strategy for the construction
of β-heteroaryl carbonyl derivatives has been
developed.
A broad range of β-heteroaryl carbonyl derivatives
can be prepared from heteroaryl boronic acids and
allyl alcohols.
An eco-friendly cooperative Cu/Pd-catalyzed
oxidative Heck reaction was described.