Copper and palladium co-catalyzed highly regio-selective 1,2-hydroarylation of terminal 1,3-dienes

Article abstract of DOI:10.1039/d0cc06007k

A practical copper and palladium co-catalyzed highly regio-selective hydroarylation of terminal 1,3-dienes has been developed. This chemistry afforded the terminal alkenyl group containing products, which are a kind of versatile precursor for organic synthesis, from 1,3-dienes by a practical one-step reaction. With good functional group tolerance, this protocol could be used to make a series of bio-active compounds using readily accessible starting materials. The mechanism of this reaction was explored by control experiments and kinetics studies. This journal is

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Copper and Palladium Co-catalyzed Highly Regio-selective 1,2-
Hydroarylation of Terminal 1,3-Diene
Received 00th January 20xx,
Accepted 00th January 20xx
Rumeng Zhang,a Qifan Li,a Min Zhang,a Sida Chai,a,b Yuqi Duan,a Jingfei Su,a Qian Zhao,a and Chun
Zhang*,a
DOI: 10.1039/x0xx00000x
A practical copper and palladium co-catalyzed highly regio- development of highly efficient strategy for one step 1,2-
selective hydroarylation of terminal 1,3-dienes have been functionalization of terminal 1,3-diene is still imperative.
developed. This chemistry afforded the terminal alkenyl group Herein, we present a novel and practical one-step method for
containing products, which are a kind of versatile precursors for highly regio-selective hydroarylation of 1,3-diene. (2, Scheme
organic synthesis, from 1,3-dienes by the practical one-step 1).
1. General strategy: multiple steps to make 1,2-product.
reaction. With good functional group tolerance, this protocol
R2
could be used to make a series of bio-active compounds using
readily accessible starting materials. The mechanism of this
reaction was explored by control experiments and kinetics
studies.
R1
1
3
multiple steps
R
R
R1
X
R2
X
+
+
4
2
1,2-product
This work
2.
R
: one step to make 1,2-product.
Ar
The selective reaction to construct different molecular
skeletons from simple starting material is a powerful and
challenging strategy for organic synthesis.1 Recently, terminal
1,3-dienes, which could afford multiple complex isomeric
products, have caught more and more attentions.2 A lot of
breakthrough employed 1,3-dienes as substrates to offer
elegant paths for the synthesis of complicated molecules.3
However, it is noticed that overwhelming majority of these
works focused on 1,4- or 3,4-functionalization of terminal 1,3-
diene.2,3 Because of disadvantaged steric hindrance and
relative poor stability of intermediates, the practical protocols
to make 1,2-products, which could afforded ingenious
molecular structure, were not well studied. Till now, the cases
of 1,2-functionalization of terminal 1,3-diene are limited by
using intramolecular strategy,4 employing isoprene derivatives
1
3
One Step
H
I
R
+
+
H2O
Ar
4
2
[Cu], [Pd], B2Pin2
1,2-product
Scheme 1. Highly selective functionalization of terminal 1,3-dienes.
The allyl 1,2-diaryl group are important motif for various
medicinally relevant compounds.8 So various synthetic
methods have been developed to synthesize this kind of
compounds, including Tisuji-Trost reaction,9 intramolecular
rearrangement reaction10 and other strategies.11 Despite these
advances, the catalytic protocols from easily available starting
materials with good substrate scope and without inseparable
linear byproduct are still critically needed. Our study provided
a practical way to make this kind of important compounds
from readily prepared 1,3-dienes and commercialized aryl
iodides with good selectivity.
6
as starting material,5 or adopting specially chelating regant.
Our study commenced with the copper and palladium co-
catalyzed reaction of phenylbutadiene (1a), iodobenzene (2a),
H2O, and B2Pin2 (Table 1). Interestingly, this practical one step
cascade reaction afforded but-3-ene-1,2-diyldibenzene (3a)
and linear product (4a) with 10% yield and 9:1 regio-selectivity
(Entry 1, Table 1). The efficiency of this reaction could be
facilitated by using CuCl as catalyst (Entry 2, Table 1, and SI).
We then surveyed the effect of different solvents. Compared
with 1,4-dioxane, some of them could promote the yield or
selectivity (Entries 3 and 4, Table 1, and SI). Especially, when
DCE was chosen as solvent, the product could be given with
73% yield and better than 30:1 regio-selectivity (Entry 4, Table
1). Using other kinds of bases, this reaction still worked well
As far as we know, based on the dynamic difference of each
reactions, the method of using transition metals co-catalyzed
tandem catalysis to realize such one step transformation were
not reported, which is a novel and practical strategy. Although
there are numerous efforts toward the synthesis of 1,2-
product from 1,3-diene with multiple steps (1, Scheme 1),7 the
a. Institute of Molecular Plus, Tianjin Key Laboratory of Molecular Optoelectronic
Science, Department of Chemistry, School of Sciences, Tianjin University, Weijin
Rd. 92, Tianjin 300072, China.
b. Department of Chemical Engineering and Technology, School of Chemical
Engineering, Sichuan University, Chengdu, 610207, China.
†
Electronic
Supplementary
Information
(ESI)
available:
See
DOI: 10.1039/x0xx00000x
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with slightly lower yield (SI). Further studies indicated different
Journal Name
Once the optimized reaction conditions wereVieewstAartbiclleisOhnelidne,
DOI: 10.1039/D0CC06007K
kinds of palladium-salts could affect the result of this reaction the substrate scope of terminal 1,3-dienes was investigated
(Entries 4, 5 and 6, Table 1). Among them, PdCl2(COD) was the (Table 2). In general, all of these examples afforded great
best one. As expected, ligand is another important parameter regio-selectivity (branch : linear > 30:1). Furthermore, good to
to this transformation (SI). SPhos was approved as the best excellent yields were observed when electron-rich (-OMe and
choice, which could afford 80% yield and better than 30:1 –NMe2) or electron-deficient (-F and -CF3) aryl substituted 1,3-
regio-selectivity (Entry 7, Table 1). Furthermore, using dienes were used (3a to 3v, Table 2). The functional group at
bromobenzene or chlorobenzene to replace 2a, this reaction para-, meta-, and ortho-position of arene ring did not affect
still worked but with lower yield (Entry 7, Table 1). The data of the efficiency (3b to 3f, Table 2). Interestingly, when -Cl and -
entry 8 and 9 (Table 1) proved this reaction did not work OTs group substituted aromatic 1,3-dienes were used as
without copper catalyst or palladium catalyst (Table 1).
starting material, the corresponding products could be
afforded with moderate isolated yield, which could be used for
further transformation (3m and 3n, Table 2). Notably,
heterocyclic group containing 1,3-dienes worked well under
this reaction condition, such as oxygen-containing
heterocyclic-, thienyl-, fural- and indol-group (3o to 3u, Table
2). Further studies indicated the corresponding products could
be obtained from 1,2-disubstituted diene and alkyl diene, but
poor conversion of these kinds of starting materials induced
low yield (3v and 3w, Table 2).
Table 1. The effect of different reaction conditions.a
[Pd] (2 mol%)
[Cu] (10 mol%)
Ligand (14 mol%)
B2Pin2 (1.5 equiv.)
Ph
Ph
+
+
Ph
Ph
2a
I
Ph
KOHaq (4.5 equiv., 8 M in H2O)
Base (2.0 equiv.)
Ph
3a
1a
4a
Solvent, 70 o
C
3a:4ab
Entry
[Cu]
Solvent
[Pd]
Yield%c
1
2
CuO
CuCl
CuCl
CuCl
CuCl
CuCl
CuCl
None
CuCl
1,4-Dioxane
1,4-Dioxane
DME
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PdCl2
9:1
13:1
21:1
>30:1
>30:1
>30:1
>30:1
--
10
62
35
73
58
79
Table 3. Substrate scope of aryl iodides (2).a
3
4
DCE
CuCl (10 mol%), PdCl2(COD) (2 mol%)
SPhos (14 mol%), B2Pin2 (1.5 equiv.)
Ph
5
DCE
+
Ar
I
Ph
LiOtBu (2.0 equiv.)
KOHaq ( 4.5 equiv., 8 M in H2O)
DCE (2.0 mL), 70 oC, N2
Ar
6
DCE
PdCl2(COD)
PdCl2(COD)
PdCl2(COD)
None
b
1a
2
3
: yield%
7d
8d
9d
DCE
80 (71)e (61)f
DCE
0
0
Ph
Ph
Ph
DCE
--
a
1a (0.25 mmol), 2a (0.75 mmol), B2Pin2 (0.375 mmol), LiOt-Bu (0.5
mmol), [Pd] (2 mol%), [Cu] (10 mol%), RuPhos (14 mol%), KOHaq (1.125
CH3
t-Bu
Ph
mmol, 8 M in H2O), DCE (2.0 mL), 70 ℃, 24 h. Determined by 1H-
b
3x
3y
3z
: 72%
: 73%
: 73%
c
d
e
NMR. Isolated yield of 3a and 4a. RuPhos was replaced by SPhos.
2a was replaced by bromobenzene.
Ph
H3C
Ph
Ph
f
2a was replaced by
Ph
CH3
chlorobenzene.
OCH3
CH3
OPh
Table 2. The substrate scope of 1,3-dienes (1).a
3aa
3ab
3ac
: 83%
: 65%
: 70%
CuCl (10 mol%), PdCl2(COD) (2 mol%)
SPhos (14 mol%), B2Pin2 (1.5 equiv.)
R1
Ph
Ph
R1
+
Ph
2a
I
LiOtBu (2.0 equiv.)
KOHaq ( 4.5 equiv., 8 M in H2O)
DCE (2.0 mL), 70 oC, N2
Ph
1
b
3
: yield%
OCH3
: 87%
CF3
F
3c
R = m-Me ( : 80%)
3i
3j
R = p-NMe2
R = p-OCF3
(
(
: 65%)
3ad
Ph
3ae
3af
: 69%
: 71%
3d
R = o-Me ( : 76%)
: 67%)
: 77%)
R
Ph
3e
3k
R = p-CF3 (
R = o,m,p-3-Me ( : 78%)
Ph
i-
3l
R = p-F ( : 73%)
Ph
3f
R = p- Pr ( : 70%)
t-
3a
R = H ( : 80%)
3m
R = p-Cl ( : 51%)
3g
R = p- Bu ( : 72%)
3b
3h
3n
R = p-Me ( : 58%)
R = p-OMe ( : 93%)
R = p-OTs ( : 43%)
O
Cl
O
F
F
O
O
3ah
3ai
: 77%
: 95%
3ag
: 74%
Ph
Ph
Ph
O
O
O
Ph
3o
3p
3q
: 63%
: 82%
: 81%
: 73%
Ph
NH2
O
O
S
Ph
O
N
Ph
: 68%
H3C
Ph
O
3aj
3ak
3al
: 68%
: 69%
: 57%
3r
3s
3v
3t
: 61%
1a (0.25 mmol), 2 (0.75 mmol), B2Pin2 (0.375 mmol), LiOt-Bu (0.5 mmol),
a
PdCl2(COD) (2 mol%), CuCl (10 mol%), SPhos (14 mol%), KOHaq (1.125 mmol,
Ph
N
Ph
8 M in H2O), DCE (2.0 mL), 70 ℃, 24 h. b Isolated yields.
Ph
Me
3u
3w
: 22%
: 64%
: 36%
The substrate scope of this transformation was further
expanded to a variety of aryl iodides (2) (Table 3). These
results indicated that substrates with both electron-donating (-
OMe and -OPh) and electron-withdrawing groups (-CF3, -F and
-Cl) proceeded well with good yields and great regio-selectivity
1 (0.25 mmol), 2a (0.75 mmol), B2Pin2 (0.375 mmol), LiOt-Bu (0.5 mmol),
a
PdCl2(COD) (2 mol%), CuCl (10 mol%), SPhos (14 mol%), KOHaq (1.125 mmol,
8 M in H2O), DCE (2.0 mL), 70 ℃, 24 h. b Isolated yields.
2 | J. Name., 2012, 00, 1-3
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(3x to 3al, Table 3). And the substituents at ortho-position of process of the allyl copper intermediate might bVeiewinAvroticllveeOdnlinine
the arene group did not affect the efficiency (3aa and 3ab, this transformation. Using D2O as D+ source, the D-labeled
DOI: 10.1039/D0CC06007K
Table 3). Besides phenyl substrate, the naphthyl iodide worked product could be detected (Eq.2, Scheme 3), which proved D2O
well, which afforded 95% yield of desired product (3ah, Table was the stoichiometric D atom donor for this reductive
3). Interestingly, oxygen-containing heterocyclic group could transformation. Furthermore, allyl boron ester 12 could be
be survived in this reaction system (3ai and 3aj, Table 3). detected from the standard reaction system without 2a and
Importantly, amino-group was tolerated with this Pd-catalyst (Eq.3, Scheme 3). Notably, 12 could be converted
transformation, which might be problematic function group into desired product 3a with 82% yield under the standard
for transition metal catalyzed reaction (3ak, Table 3). reaction conditions without 1a (Eq.4, Scheme 3). The above
Furthermore, the intramolecular reaction worked well and results could suggest that 12 should be the key intermediate of
afforded desired cyclization product with 68% yield (3al, Table present transformation. To detect the detail role of metal
3).
catalyst, further studies suggested without copper salt, the
The feasibility of gram-scale reaction was detected under efficiency of 12 converted into 3a was not diminished (Eq.5,
standard reaction conditions. The above reaction afforded Scheme 3). This result suggested copper-catalyst might not
1.25 g of 3a (75% yield) with great regio-selectivity (A, Scheme involve in the above step.
Standard Conditions
Ph
2). The products of this chemistry, which contain a terminal
alkenyl group, are a kind of versatile intermediates for organic
transformation (for examples of further transformations, see
SI). Furthermore, the 1,2-diaryl motif are ubiquitous structural
scaffold that can be found in many drugs and bio-active
compounds,8 the present method provides a practical way for
the construction of bio-active compounds from readily
available starting materials. For example, 8 was reported as a
fungicide8a, which could be prepared from 3ac by well-
established transformations (B, Scheme 2, and SI).
Furthermore, an anti-tumor agent 118b could be made from
+
+
Ph
I
I
Ph
(Eq. 1)
Ph
: 77%
1a-mix
Z : E = 1.3:1
2a
3a
D
Standard Conditions
(Eq.2)
Ph
Ph
Ph
D O
replace H2O
2
Ph
: 78 %
D-3a
D% = 82%
1a
1a
2a
Standard Conditions
2a
(Eq. 3)
(Eq. 4)
Ph
Ph
Ph
Ph
BPin
Without [Pd] and
12
: 84 %
Standard Conditions
Ph
3a
+
Ph
2a
I
I
BPin
a
Withou1
Ph
12
: 82 %
3ai with practical protocols (C, Scheme 2, and SI).
Standard Conditions
Without [Cu]
Ph
3a
+
(Eq. 5)
Ph
2a
CuCl (10 mol%), PdCl2(COD) (2 mol%)
BPin
Ph
SPhos (14 mol%), B2Pin2 (1.5 equiv.)
Ph
+
(A)
Ph
2a
I
Ph
1a:
LiOtBu (2.0 equiv.), KOHaq ( 4.5 equiv.)
12
: 71 %
Ph
DCE (2.0 mL), 70 oC, N2
3a
1.04 g
:
75%
1.25 g
Scheme 3. Control experiments.
8 mmol scale
OH
CHO
The monitoring of kinetic experiments clearly illustrated the
different reaction rates of the formation and transformation of
intermediate 12 (Figure 1). As shown in the curve, the
concentration of 12 increased quickly at the initial stage of this
transformation. After that, the signal of this intermediate
decreased under the same reaction conditions. These dynamic
monitoring data proved the hydroboration step to form
intermediate 12 is faster than the step of 12 turn into 3a under
the optimized conditions, which could ensure the generation
of 1,2-product from 1,3-diene.
1) 9-BBN (2.0 equiv.), THF
2) EtOH, NaOH (1M in H2O)
H2O2 (30% in H2O, 10 equiv.)
0 oC to rt
PCC, DCM
rt
OPh
OPh
OPh
3ac
5
6
: 84%
: 86%
CONH2
COOH
PyBOP, HOBt
KMnO4, NaHCO3
acetone, rt
DIPEA, NH4Cl
DMF, rt
(B)
OPh
OPh
: 83%
7
8
: 82%
fungicide
OH
I
1) 9-BBN (2.0 equiv.), THF
I2, PPh3
imidazole
2) EtOH, NaOH (1M in H2O)
H2O2 (30% in H2O, 10 equiv.)
0 oC to rt
O
℃
O
CH2Cl2, 20
O
O
O
O
9:
3ai
10:
92%
93%
H
N
H2N
NMe2
(C)
℃
K2CO3, MeCN, 70
O
O
NMe2
11
: 61%
IPR series anti-tumor agent
Scheme 2. Gram scale reaction and synthesis of bio-active
molecules.
To get more detail information about the reaction
mechanism, a series of control experiments were investigated
(Scheme 3). First, the mixed Z and E version of buta-1,3-dien-1-
ylbenzene afforded as similar result as the example of 3a (Eq.1, Figure 1. Kinetics studies.
Scheme 3). This data approved the Z and E version of diene did
not affect the result, and also suggested that the isomerization
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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Journal Name
4
5
(a) J. M. Pierson, E. L. Ingalls, R. D. Vo andVFie.wEA.rtiMcleicOhnalienle,
Based on the above results, the proposed mechanism for
this copper and palladium co-catalyzed reaction was illustrated
in scheme 4. The tautomer copper complex 13 and 14 could be
generated from copper salt, B2Pin2 and 1a.12 This active metal
intermediate quenched by proton to give boron ester 12,13
which had been confirmed by control experiments.
Intermediate 12 reacted with 15, which generated from the
oxidative addition reaction of Pd0 and 2a, to formed 16.14h, m, p
The π-allyl palladium intermediate 17 could be potentially
produced. After went through reductive elimination step, the
desired product 3a could be afforded.14
Angew. Chem. Int. Ed., 2013, 52, 13311; (b) D. Xing and D.
DOI: 10.1039/D0CC06007K
Yang, Org. Lett., 2013, 15, 4370; (c) O. Kanno, W. Kuriyama,
Z. J. Wang and F. D. Toste, Angew. Chem. Int. Ed., 2011, 50,
9919.
(a) T. Jia, Q. He, R. E. Ruscoe, A. P. Pulis and D. J. Procter,
Angew. Chem. Int. Ed., 2018, 57, 11305; (b) D. Fiorito and C.
Mazet, ACS Catal., 2018, 8, 9382; (c) K. B. Smith and M. K.
Brown, J. Am. Chem. Soc., 2017, 139, 7721; (d) L. Jiang, P.
Cao, M. Wang, B. Chen, B. Wang and J. Liao, Angew. Chem.
Int. Ed., 2016, 55, 13854.
Examples about 1,2-functionalization of terminal 1,3-diene
using specially tactful diamination reagents, see: (a) B. Zhao,
X. Peng, Y. Zhu, T. A. Ramirez, R. G. Cornwall and Y. Shi, J.
Am. Chem. Soc., 2011, 133, 20890; (b) H. Du, B. Zhao and Y.
Shi, J. Am. Chem. Soc., 2007, 129, 762; (c) H. Du, W. Yuan,
B. Zhao and Y. Shi, J. Am. Chem. Soc., 2007, 129, 11688.
Our group focuses on the research of highly selective
boronation and further transformation. (a) Q.-F. Li, X.-Y. Jiao,
M.-M. Xing, P.-L. Zhang, Q. Zhao and C. Zhang, Chem.
Commun., 2019, 55, 8651; (b) P. Zhang, M. Xing, Q. Guan, J.
Zhang, Q. Zhao and C. Zhang, Org. Lett., 2019, 21, 8106; (c) P.
Zhang, Z. Zhou, R. Zhang, Q. Zhao, and C. Zhang, Chem.
Commun. 2020, 56, 11469. For some selected examples about
synthesis of 1,2-product from 1,3-diene with multiple steps,
see: (d) T. Iwasaki, R. Shimizu, R. Imanishi, H. Kuniyasu and
N. Kambe, Angew. Chem., Int. Ed., 2015, 54, 9347; (e) R. E.
Kyne, M. C. Ryan, L. T. Kliman and J. P. Morken, Org. Lett.,
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Pharm. Chem. Life Sci. 1999, 332, 333. (b) F. Wang, J. Li, A.
L. Sinn, W. E. Knabe, M. Khanna, I. Jo, J. M. Silver, K. Oh, L.
Li, G. E. Sandusky, G. W. Sledge, H. Nakshatri, D. R. Jones,
K. E. Pollok and S. O. Meroueh, J. Med. Chem., 2011, 54,
7193;
(a) P. J. Moon, Z. Wei, and R. J. Lundgren, J. Am. Chem. Soc.,
2018, 140, 17418; (b) H.-H. Zhang, J.-J. Zhao and S. Yu, J.
Am. Chem. Soc., 2018, 140, 16914; (c) N. Hussain, G. Frensch,
J. Zhang and P. J. Walsh, Angew. Chem. Int. Ed., 2014, 53,
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and R. Takeuchi, Adv. Synth. Catal., 2011, 353, 2013.
6
7
tBuO-Bpin
Ph
LCu-BPin
Pd
L
Ph
PhI
2a
I
1a
15
B2Pin2
O.A.
Ligand
+
LiOtBu
Base
PdII + L
[LPd0]
R.E.
[Cu]
[Cu]
Cu
Pd
BPin
KOH
Ph
Ph
3a
13
12
K
I
L
Ph
BPin
HO
Ph
Pd
BPin
14
Pd
Ar
17
[Cu]
L
H2O
16
Ph
Scheme 4. The proposed reaction mechanism.
In conclusion, we have demonstrated a novel and practical
copper and palladium co-catalyzed highly regio-selective
hydroarylation of terminal 1,3-diene by one step reaction. This
chemistry afforded the terminal alkenyl group containing
products, which is a kind of versatile precursors for bio-active
molecules synthesis. The reaction pathway was illustrated by
control experiments and kinetic experiments. Further studies
for more complicated synthetic applications are ongoing in our
laboratory.
8
9
We acknowledge financial support from Tianjin University,
National Natural Science Foundation of China (No. 21801181).
Conflicts of interest
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Dewese, M. M. Parsutkar, S. M. Jing, M. M. Mehta, J. C.
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The authors declare no competing financial interest.
Notes and references
1
(a) Transition Metals for Organic Synthesis, Building Block
and Fine Chemicals, ed. M. Beller and C. Bolm, Wiley-VCH,
Weinheim, 2nd edn, 2004; (b) Metal-Catalyzed Cross-
Coupling Reactions, ed. F. Diederich and A. de Meijere,
Wiley-VCH, Weinheim, 2nd edn, 2004.
2
3
For some reviews in recent 2 years, see: (a) G. J. P. Perry, T.
Jia and D. J. Procter, ACS Catal., 2020, 10, 1485; (b) N. J.
Adamson and S. J. Malcolmson, ACS Catal., 2020, 10, 1060;
(c) X. Wu and L.-Z. Gong, Synthesis., 2019, 51, 122.
For some selected examples on 1,3-dienes as building blocks
in recent 3 years, see: (a) E. P. Farney, S. J. Chapman, W. B.
Swords, M. D. Torelli, R. J. Hamers and T. P. Yoon, J. Am.
Chem. Soc., 2019, 141, 6385; (b) X.-W. Chen, L. Zhu, Y.-Y.
Gui, K. Jing, Y.-X. Jiang, Z.-Y. Bo, Y. Lan, J. Li and D.-G.
Yu, J. Am. Chem. Soc., 2019, 141, 18825; (c) X.-H. Yang, R.
T. Davison, S.-Z. Nie, F. A. Cruz, T. M. McGinnis and V. M.
Dong, J. Am. Chem. Soc., 2019, 141, 3006; (d) X.-H. Yang, R.
T. Davison and V. M. Dong, J. Am. Chem. Soc., 2018, 140,
10443; (e) L. Cheng, M.-M. Li, L.-J. Xiao, J.-H. Xie and Q.-L.
Zhou, J. Am. Chem. Soc., 2018, 140, 11627; (f) M.-S. Wu, T.
Fan, S.-S. Chen, Z.-Y. Han and L.-Z. Gong, Org. Lett., 2018,
20, 2485.
14 (a) B. Potter, E. K. Edelstein and J. P. Morken, Org. Lett.,
2016, 18, 3286; (b) C. H. Schuster, J. R. Coombs, Z. A. Kasun
and J. P. Morken, Org. Lett., 2014, 16, 4420; (c) Y. Yang and
S. L. Buchwald, J. Am. Chem. Soc., 2013, 135, 10642; (d) B.
W. Glasspoole, K. Ghozati, J. W. Moir and C. M. Crudden,
Chem. Commun., 2012, 48, 1230.
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/D0CC06007K
Ar
B2Pin2
Ar
I
[Cu]
2
4
R
R
1
+
2
4
1
3
3
H2O
H
[Pd]
1,2-Product
One Step Reaction
to Make
with High Regio-Selectivity
The novel and practical copper and palladium co-catalyzed 1,2-hydroarylation of terminal 1,3-dienes by one
step reaction have been developed, which could afford a kind of versatile precursors for organic synthesis.