Efficient Pd-Catalyzed C—H Oxidative Bromination of Arenes with Dimethyl Sulfoxide and Hydrobromic Acid?

Article abstract of DOI:10.1002/cjoc.202000055

We have developed an efficient Pd-catalyzed directed C—H bromination protocol, in which dimethyl sulfoxide (DMSO) is employed as oxidant with hydrobromic acid aqueous solution (HBr_(aq)) as bromide source. The DMSO/HBr_(aq) system, which is novelly and efficiently utilized in transition-metal catalyzed C—H activation, illustrates its practicability by the operational simplicity, inexpensive and readily available starting materials, and high bromide-atom economy.

Full text of DOI:10.1002/cjoc.202000055

Chinese Journal
of Chemistry
CJC
中 国 化 学 - An International Journal
Accepted Article
Title: Efficient Pd-catalyzed C-H Oxidative Bromination of Arenes with DMSO and
Hydrobromic Acid
Authors: Yizhi Yuan, Yujie Liang, Shihui Shi, Yu-Feng Liang, and Ning Jiao*
This manuscript has been accepted and appears as an Accepted Article online.
This work may now be cited as: Chin. J. Chem. 2020, 38, 10.1002/cjoc.202000055.
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published online in Early View: http://dx.doi.org/10.1002/cjoc.202000055.
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DOI: 10.1002/cjoc.201900XXX
Breaking Report
Efficient Pd-catalyzed C-H Oxidative Bromination of Arenes with DMSO
and Hydrobromic Acid
Yizhi Yuan,a Yujie Liang,a Shihui Shi, a Yu-Feng Liang,a and Ning Jiao *,a,b
a State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191, China
b State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200062, China
Dedicated to the 70th Anniversary of Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences
Cite this paper: Yuan, T.; Liang, Y.; Liang, Y.-F.; Jiao, N. Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX
Summary of main observation and conclusion We have developed an efficient Pd-catalyzed directed C-H bromination protocol, in which dimethyl
sulfoxide (DMSO) is employed as oxidant with hydrobromic acid aqueous solution (HBr(aq)) as bromide source. The DMSO/HBr(aq) system, which is novelly
and efficiently utilized in transition-metal catalyzed C-H activation, illustrates its practicability by the operational simplicity, inexpensive and readily available
starting materials, and high bromide-atom economy.
cheaper nucleophilic bromide source have been scarcely realized.[13]
In this context, HBr is considered as an ideal bromide source with
Background and Originality Content
Transition-metal-catalyzed directed C-H funtionalization has
excellent atom economy. In 2009, a breakthrough was achieved by
emerged as an powerful and atom-economic strategy in organic
Kakiuchi and coworkers who demonstrated a green-sustainable Pd-
synthesis over the past several decades.[1] In recent years, the
catalyzed bromination strategy using aqueous HBr solution via
utility of oxidizing coupling reagents[2] and oxidizing directing
groups[3] has allowed the reactions performed under redox-neutral
conditions, but this maneuver demands pre-functionalized
substrates resulting in low atom economy. Nevertheless, most of
transition-metal catalyzed C-H functionalizations generally require
stoichiometric external oxidants (e.g. metal salts, hypervalent
iodine reagents, quinones, selectfluor, oxone, K2S2O8) to
regenerate the catalytically active metal species, which suffers
from relatively high cost and the low atom economy.[1,4] Thus, the
pursuit of green, mild and inexpensive oxidant for C-H activation
has drawn significant attention of synthetic chemists.
electrochemical process (Scheme 1b).[14] But the employment of 80
equivalent of HBr(aq) and complex electrochemical device hinders its
application. Therefore, the development of a more operationally
convenient, benign and cost-effective oxidant for C-H bromination
with HBr(aq) is desired. Motivated by previous literatures that DMSO
can oxidize HBr in acidic conditions into electrophilic brominating
species,[15] and our group’s recent contribution in the efficient
halogenation of a range of alkenes, alkynes, ketones, and arenes,[16]
here, we report a Pd-catalyzed direct ortho C-H bromination
method with DMSO as a mild oxidant and HBr as the bromide
source, which allows the incorporation of bromide atom in a
distinct selectivity from the previous metal-free electrophilic
aromatic halogenation reactions (Scheme 1c).
Despite some green oxidants such as dioxygen[5] and hydrogen
peroxide[6] have been utilized in transition-metal catalyzed C-H
functionalization reaction, cost-effective and abundant small
molecule oxidants are relatively underdeveloped. In this regard,
dimethyl sulfoxide (DMSO), as an inexpensive common solvent, can
not only be employed as versatile building blocks in organic
synthesis, but also as an ideal oxidant due to its inherent oxidability
(Scheme 1a).[7] However, DMSO was rarely used as an oxidant in
transition-metal catalyzed oxidative C-H activation.
Scheme 1
Transition-metal catalyzed directed C-H bromination with
Aryl bromides, as an important class of chemicals, are widely
employed in organic synthesis as coupling partners and also in
various other fields.[8] In contrast to conventional electrophilic
methodologies for aryl bromides preparation that utilize Br2,[9] N-
bromosuccinimide (NBS)[10] or the combination of nucleophilic
bromide source with stoichiometric oxidant,[11] transition-metal
catalyzed directed C-H bromination has become an alternative
approach to aryl bromides leading to distinct substrate scope and
regioselectivity.[12] However, in this area, C-H brominations with
This article has been accepted for publication and undergone full peer review but has not been through
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First author et al.
Report
a
nucleophilic bromide source
Table 2 Substrate scope of Pd-catalyzed bromination with DMSO/HBr(aq)
a
u
e c em ca ro er es o
M ltipl
h
i
l p
p
ti
f DMSO
)
Br
X
X
X
R2
R2
R2
•
•
•
•
x
a
uc eo
phili y
PdCl2
O
t
t
N
P
l
O id bili y
ea ac
N
+
N
N
S
t
t
t
i l
t
t
R1
R1
R1
o en a e ec ro
W
k
idi y
l
phili y
Br
DMSO/H
open
H3C
CH3
air(aq)
Br
Br
•
•
se as ox an an
verse
u
n
oc s n or an c s n es s
t
t
h
U
d
id
d di
b ildi g bl
k
i
g
i
y
i
1
2
2'
-
ever use as ox an
n
ac
va on c em s r
t
i
C H
t
t
t
i
y
N
d
id
i
i
h
yieldb
product
yieldb
entry
entry
product
-
-
ca a ze
rom na on w
r
v a e ec roc em ca rocess
b Pd t ly d C H b
)
i
ti
ith HB (a
i
l
t
h
i
l p
q
)
R
ano e:
ca o e:
r
PdB 2
d
N
N
.
r
DG
D
G
B
th d 2 0 M H
-
,
e ce
(
a
q
(
)
Br
Me
OMe
Br
R
,
di id d ll Pt Pt 90 o
C
r
B
v
H
) ( )
17d,e
18e
R
R
,
2q
93%
=
=
•
=
=
=
=
=
=
=
=
=
=
=
=
=
1
R
H
2a, 87%
om ex e ec roc em ca ev ce
n
e u v o
r
a
e a e
m n
) d d d
C
p
l
l
t
h
i
l d
i
d
80 q i f HB
a
q
,
(
,
2r
94%
2
3c
R
R
R
R
R
R
R
R
R
R
R
R
Me
tBu
2b 89%
(11%)
c
s wor
,
Thi
k
)
2c 81%
R
,
4
Ph
2d 69%
DG
DG
(16%)
(9%)
(9%)
N
Pd
]
[
,
r
B
5
OMe
OBn
OCF3
OH
2e 86%
DM
SO H
/
o en a r(a
q
r
B
)
Br
3-Me
4-Me
5-Me
6-Me
H
,
p
i
,
2f 83%
6
19c e
R
R
R
R
96%
86%
80%
,
=
=
=
=
2s
•
•
•
7e
8c
9c
10
11
12
2g 74%
,
r
as rom e source
id
as
o
ox an an so ven
HB (a
b
DMSO
b th id
t
d
l
t
q
,
)
2t
20
21
22
(8%)
-
,
rom e a om econom an monose ec v
High b id
t
y
d
l
ti ity
2h 65%
,
2u
2v,
,
2i 65%
CH2OH
F
trace
,
2j 86%
,
OMe
2k 85%
Cl
Results and Discussion
,
Br
2l 83%
N
23c
24c
93%
,
,
,
f
13d e
CO2Me
2m 61%
,
2w
(16%)
Table 1 Optimization of the reaction conditionsa
Br
catalyst
O
,
N
N
R
2x
81%
90%
Br
H
equiv)
(aq) (1.2
DMSO, 80 o
air, 36 h
N
N
N
O
Br
Br
C
Br
Br
2a
open
,
=
=
=
2n
2o
2p
14
R
R
R
Me
OMe
Cl
83%
72%
71%
1a
15e
25
,
,
,
2y
16d,e
Entry
1c,d
2d
3
Catalyst
PdBr2
PdBr2
PdBr2
Pd(OAc)2
PdCl2
PdCl2
DMSO
Yield/%b
16
1.2 equiv
3 mL
3 mL
3 mL
3 mL
3 mL
3 mL
---
N
N
Br
66
N
N
N
N
iPr
Br
(11%)
N
N
Br
Br
82
,
,
,
e
,
c
,
e
,
2ac
87%
d f
88%d
84%
84%
2z
2aa
2ab
4
79
a Standard Conditions: 1 (0.3 mmol), PdCl2 (10 mol%), HBr(aq) (48% aqueous
solution, 0.36 mmol), DMSO (3 mL), under air stirred at 80 oC for 36 h.
5
87
b
6e
87
c
Isolated yield. The number in parentheses is the yield of 2'. The reaction
was carried out at 90 oC. The reaction was carried out at 100 oC. e The
d
7
8c
---
N.R.
N.R.
reaction was stirred for 48 h. f 20 mol% of PdCl2 was used.
PdCl2
a
Reaction conditions: 1a (0.3 mmol), HBr(aq) (48% aqueous solution, 0.36
To test this hypothesis, we initially investigated the
bromination of 2-phenylpyridine 1a in DMF as solvent using 1.2
equivalent of aqueous HBr solution (48%) as bromide source, 1.2
equivalent of DMSO as oxidant and 10 mol% of PdBr2 as catalyst,
respectively. Notably, 2-(2-bromophenyl)pyridine 2a was obtained
in 16% yield (entry 1, Table 1). The yield increased drastically when
DMSO was applied as solvent (entry 2). Prolonging the reaction
time to 36 h gave 2a in 82% yield (entry 3). The screening of other
palladium catalysts showed that PdCl2 led to the optimal outcome
with 87% yield (entries 4-5). It is noteworthy that identical yield was
acquired when the reaction was performed under argon, which
demonstrated that DMSO is the real oxidant. Remarkably, in the
absence of PdCl2 or DMSO, the transformation did not work (entries
7-8). These results indicate that both PdCl2 and DMSO are
indispensable in this chemistry.
mmol) and catalyst (10 mol%), under air at 80 oC for 36 h. b Isolated yields. c
3 mL DMF was employed as solvent. The reaction was stirred for 12 h.
The reaction was carried out under Ar. N.R. = No reaction.
d
e
With the optimal conditions in hand (entry 5, Table 1), we
evaluated the substrate scope of this transformation (Table 2).
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Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.

Running title
Chin. J. Chem.
Notably, the C-H bromination reaction of 2-phenylpyridine
derivatives was achieved with good to excellent efficiency and high
selectivity (2a-2ac). Among them, the substrates with unprotected
hydroxyl group were compatible in this brominating system (2h-2i).
It is noteworthy that substrates bearing halogen groups could also
afford the corresponding products in good yield (2j-2l, 2p). Besides,
the efficiency of reaction was not affected by the methyl group on
the pyridine ring, while the reaction of 1v was very sluggish
probably due to steric hindrance. In addition, other nitrogen-
containing directing groups were also tested (1z-1ac). Among them,
this Pd-catalyzed bromination system could also be utilized in the
functionalization of 6-aryl purine derivative. For instance, 9-
(Scheme 2, e). Furthermore, a kinetic isotopic effect (KIE) study was
conducted (see Supporting Information for details). The
intramolecular and intermolecular KIE value were determined to be
about 2.28 and 6.11, respectively, which indicates that C-H bond
activation is probably involved in the rate-limiting step.[18]
Based on previous reports and our experimental data, a
plausible mechanism is proposed in Scheme 3 although it was not
completely clear yet. Initially, the coordination of directing group
to Pd(II) center leads to complex B, which undergoes C-H activation
to form intermediate C. This species may exist in an equilibrium as
complex A. According to previous reports, the Br+ species could be
coordinated by DMSO to deliver (DMSO)nBr+ (n = 1 or 2).[16f,19] Thus,
isopropyl-6-phenyl-9H-purine 1ac was smoothly brominated in 87% we assumed that, under the acidic conditions, DMSO could oxidize
yield.
To get insight into the mechanism, some control experiments
Br- to BDMS or [(DMSO)nBr+(DMS)]Br-, which acted as the
electrophilic brominating reagent to execute direct electrophilic
cleavage of Pd-C bond leading to the bromination product.[14,20]
Finally, the dissociation of product from Pd(II) center regenerates
Pd(II) catalyst to complete the catalytic circle.
were conducted. Firstly, when catalytic amount of complex A was
employed instead of PdCl2, 2a was obtained in 90% yield (Scheme
2, a), which demonstrated that complex A may act as an
intermediate in this transformation. However, when stoichiometric
complex A or PdCl2 was subjected to the system, only 43% and 31%
of 2a was afforded, respectively (Scheme 2, b and c). The failure in
ligand dissociation to monomeric Pd(II) species may result in the
descent of yields.[5g,17] According to previous literature,[15a] the
combination of DMSO and HBr(aq) may form dimethyl sulfide (DMS)
and Br2 in situ, which would lead to the formation of
bromodimethylsulfonium bromide (BDMS) (Scheme 2, d). We then
used 0.6 equiv of BDMS as bromide source
Scheme 3 Proposed reaction mechanism
H2O
r
B
r-
B
n
r-
DMSO
r+
+
r
B
DMSO n
DMS
( )]
DMSO
2HB
B
[(
)
S
=
n
or
2
1
BDMS
a
1
a
2
PdX2
N
N
PdX2L
PdX2L
r
B
Scheme 2 Mechanistic studies
B
+
DMSO DMS
D
n
om ex
C
pl
A
or
DMS
A
mol%)
(5
Br
H
equiv)
(aq) (1.2
DMSO, 80 o
1a
A
2a
(a)
(b)
C
90%
N
air, 36 h
open
Cl
Pd
Pd
HX
Cl
Br
H
equiv)
(aq) (1.2
N
2a
DMSO, 80 o
air, 36 h
C
r+
B
r-
B
DMS
)
]
DMSO n
A
43%
[
(
)
(
...
a
,
,
=
N
open
1
L
H2O DMSO
,
or
BDMS X
,
r
=
Pd
X
X
Cl B
PdCl
equiv)
equiv)
2 (1.0
C
L
Br
H
(aq) (1.2
1a
2a
DMSO, 80 o
C
(c)
(d)
31%
air, 36 h
open
Conclusions
O
S
OH
S
OH2
S
H+
Br-
H+
Br
S
In summary, we have demonstrated an efficient Pd-catalyzed
highly selective C-H bromination protocol of arenes, in which
inexpensive and readily available DMSO and HBr aqueous solution
are utilized as a mild oxidant and bromide source, respectively.
Mechanistic studies supported that DMSO oxidized Br- to BDMS or
[(DMSO)nBr+(DMS)]Br- under the acidic conditions, which serves as
the electrophilic brominating reagent for subsequent Pd-catalyzed
C-H bromination reaction. We believe this protocol should find
broad application in bromination reaction due to the cost-effective
and operationally simple features. Further investigation of de-
tailed reaction mechanism and its application is ongoing in our lab.
-H
Br-
2O
Br
BDMS
solvent
DMSO
DMF
PdCl
mol%)
equiv)
yield
71%
2 (10
BDMS
(0.6
N
N
(e)
solvent
80 o
C
(3 mL),
12%
12%
Br
2a
air, 36 h
open
1a
DCE
instead of HBr(aq) in different solvents. We found that 1a could be
smoothly converted to 2a in 71% yield when DMSO was employed
as solvent. However, reactions resulted in poor yields when
conducted either in DMF or DCE, which demonstrated that BDMS
may be the active bromide source, and DMSO was crucial for the
reoxidization of bromide anion and the dissociation of BDMS
Experimental
General procedure for the reactions of 2-phenylpyridine
derivatives with HBr(aq)
PdCl2 (0.03 mmol, 5.3 mg, 0.1 equiv) was added to a 25 mL
Chin. J. Chem. 2019, 37, XXX－XXX
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First author et al.
Report
oven-dried Schlenk tube with a stirring bar. 2-Phenylpyridine
derivative or analogue (0.3 mmol, 1.0 equiv) was added followed
by the addition of 3 mL of DMSO and 48% (w/w) HBr aqueous
solution (0.36 mmol, 60.8 mg, 1.2 equiv). The mixture was heated
to specified temperature (80-100 oC) under air for specified amount
of time (36-48 h). Upon cooling, 8 mL of brine was added followed
by extraction with ethyl acetate (10 mL). The aqueous layer was
further extracted with ethyl acetate twice (2 × 10 mL) and the
combined organic layer was dried over anhydrous magnesium
sulfate and filtered. The filtrate was concentrated under reduced
pressure giving the resulting residue, which was purified by column
chromatography to afford brominated product.
CDCl3) δ 159.9, 157.9, 149.2, 135.6, 133.6, 132.0, 124.7, 121.9,
118.3, 113.6, 55.5.
2-(2,6-Dibromo-4-methoxyphenyl)pyridine (2e') was prepared
o
1
as a white solid (9.0 mg, 9% yield), m.p. 143.7-145.9 C. H NMR
(400 MHz, CDCl3) δ 8.73 (d, J = 4.4 Hz, 1H), 7.78 (td, J = 7.6, 2.0 Hz,
1H), 7.32-7.27 (m, 2H), 7.19 (s, 2H), 3.82 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 159.8, 158.5, 149.3, 136.2, 134.3, 125.1, 123.6, 122.8,
117.7, 55.8. HRMS m/z (ESI) calcd for C12H10Br2NO (M + H)+,
341.9124, found 341.9115.
2-(4-(Benzyloxy)-2-bromophenyl)pyridine (2f) was prepared as
1
a yellow oil (85.0 mg, 83% yield). H NMR (400 MHz, CDCl3) δ 8.67
(d, J = 4.0 Hz, 1H), 7.69 (td, J = 7.8, 1.6 Hz, 1H), 7.57 (d, J = 7.6 Hz,
1H), 7.47 (d, J = 8.4 Hz, 1H), 7.43-7.29 (m, 6H), 7.24-7.21 (m, 1H),
7.00 (dd, J = 8.4, 2.4 Hz, 1H), 5.07 (s, 2H). 13C NMR (100 MHz, CDCl3)
δ 159.0, 157.9, 149.2, 136.2, 135.6, 133.9, 132.0, 128.6, 128.1,
127.4, 124.7, 122.0, 121.9, 119.4, 114.3, 70.2. HRMS m/z (ESI) calcd
for C18H15BrNO (M + H)+ 340.0332, found 340.0324.
2-(2-Bromophenyl)pyridine (2a)[21] was prepared as a pale
1
yellow oil (60.8 mg, 87% yield). H NMR (400 MHz, CDCl3) δ 8.72-
8.70 (m, 1H), 7.75 (td, J = 7.8, 2.0 Hz, 1H), 7.67 (dd, J = 8.0, 1.2 Hz,
1H), 7.60 (d, J = 8.0 Hz, 1H), 7.53 (dd, J = 7.6, 2.0 Hz, 1H), 7.40 (td, J
= 7.6, 1.2 Hz, 1H), 7.30-7.23 (m, 2H). 13C NMR (100 MHz, CDCl3) δ
158.3, 149.4, 141.2, 135.8, 133.2, 131.4, 129.7, 127.5, 124.7, 122.4,
121.7.
2-(4-(Benzyloxy)-2,6-dibromophenyl)pyridine
(2f')
was
1
prepared as a colorless oil (10.9 mg, 9% yield). H NMR (400 MHz,
CDCl3) δ 8.72 (d, J = 4.4 Hz, 1H), 7.77 (td, J = 7.8, 1.6 Hz, 1H), 7.41-
7.26 (m, 9H), 5.06 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 158.9, 158.5,
149.3, 136.2, 135.7, 134.6, 128.7, 128.3, 127.4, 125.1, 123.7, 122.8,
118.5, 70.5. HRMS m/z (ESI) calcd for C18H14Br2NO (M + H)+
417.9437, found 417.9423.
2-(2-Bromo-4-methylphenyl)pyridine (2b)[21] was prepared as a
yellow oil (66.4 mg, 89% yield). 1H NMR (400 MHz, CDCl3) δ 8.69 (d,
J = 4.8 Hz, 1H), 7.71 (td, J = 7.6, 1.6 Hz, 1H), 7.58 (d, J = 7.6 Hz, 1H),
7.49 (s, 1H), 7.42 (d, J = 7.6 Hz, 1H), 7.26-7.23 (m, 1 H), 7.19 (d, J =
7.6 Hz, 1H), 2.36 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 158.2, 149.2,
139.9, 138.2, 135.6, 133.6, 131.1, 128.3, 124.7, 122.1, 121.3, 20.7.
2-(2,6-Dibromo-4-methylphenyl)pyridine (2b')[21] was prepared
2-(2-Bromo-4-(trifluoromethoxy)phenyl)pyridine (2g)[21] was
prepared as a colorless oil (70.5 mg, 74% yield). 1H NMR (400 MHz,
CDCl3) δ 8.72-8.71 (m, 1H), 7.77 (td, J = 7.8, 2.0 Hz, 1H), 7.60-7.56
(m, 3H), 7.33-7.27 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 157.0, 149.5,
149.0 (q, J = 1.7 Hz), 140.0, 135.9, 132.3, 125.6, 124.6, 122.7, 122.0,
1
as a white solid (10.8 mg, 11% yield). H NMR (400 MHz, CDCl3) δ
8.74 (d, J = 4.0 Hz, 1H), 7.79 (td, J = 7.8, 1.6 Hz, 1H), 7.46 (s, 2H),
7.34-7.31 (m, 1H), 7.29 (d, J = 8.0 Hz, 1H), 2.36 (s, 3H). 13C NMR (100
MHz, CDCl3) δ 158.7, 149.4, 141.1, 138.8, 136.4, 132.4, 124.8, 123.2, 120.3 (q, J = 256.6 Hz), 119.9.
122.9, 20.6. 3-Bromo-4-(pyridin-2-yl)phenol (2h) was prepared as a white
2-(2-Bromo-4-(tert-butyl)phenyl)pyridine (2c) was prepared as
solid (48.4 mg, 65% yield). m.p. 174.5-176.3 oC. 1H NMR (400 MHz,
DMSO-d6) δ 10.10 (brs, 1H), 8.63 (d, J = 4.4 Hz, 1H), 7.86-7.82 (m,
1H), 7.56 (d, J = 8.0 Hz, 1H), 7.38-7.33 (m, 2H), 7.11 (d, J = 1.6 Hz,
1H), 6.90-6.87 (m, 1H). 13C NMR (100 MHz, DMSO-d6) δ 158.2, 157.6,
149.1, 136.1, 132.4, 131.8, 124.4, 122.2, 121.1, 119.3, 115.0. HRMS
m/z (ESI) calcd for C11H9BrNO (M + H)+ 249.9862, found 249.9861.
(3-Bromo-4-(pyridin-2-yl)phenyl)methanol (2i) was prepared as
a white solid (51.8 mg, 65% yield). m.p. 98.9-100.4 oC. 1H NMR (400
MHz, CDCl3) δ 8.67 (d, J = 4.4 Hz, 1H), 7.78 (td, J = 7.8, 2.0 Hz, 1H),
7.54-7.51 (m, 2H), 7.34-7.32 (m, 2H), 7.17 (d, J = 7.6 Hz, 1H), 5.05
(brs, 1H), 4.61 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 158.2, 148.8,
144.4, 138.9, 136.3, 130.8, 130.3, 125.1, 124.8, 122.6, 121.5, 62.8.
HRMS m/z (ESI) calcd for C12H11BrNO (M + H)+ 264.0018, found
264.0016.
a colorless oil (70.3 mg, 81% yield). 1H NMR (400 MHz, CDCl3) δ 8.70
(d, J = 4.4 Hz, 1H), 7.73 (td, J = 7.6, 1.6 Hz, 1H), 7.67 (d, J = 1.6 Hz,
1H), 7.60 (d, J = 8.0 Hz, 1H), 7.47 (d, J = 8.0 Hz, 1H), 7.42 (dd, J = 8.2,
2.0 Hz, 1H), 7.28-7.25 (m, 1H), 1.34 (s, 9H). 13C NMR (100 MHz,
CDCl3) δ 158.3, 153.3, 149.3, 138.3, 135.7, 131.0, 130.2, 124.72,
124.66, 122.2, 121.5, 34.7, 31.1. HRMS m/z (ESI) calcd for C15H17BrN
(M + H)+, 290.0539, found 290.0535.
2-(3-Bromo-[1,1'-biphenyl]-4-yl)pyridine (2d)[21] was prepared
as a yellow oil (63.9 mg, 69% yield). 1H NMR (400 MHz, CDCl3) δ 8.72
(ddd, J = 4.8, 1.6, 0.8 Hz, 1H), 7.90 (t, J = 0.8 Hz, 1H), 7.74 (td, J = 7.8,
2.0 Hz, 1H), 7.64 (dt, J = 7.8, 1.0 Hz, 1H), 7.62-7.59 (m, 4H), 7.46-
7.43 (m, 2 H), 7.37 (m, 1H), 7.27 (ddd, J = 7.6, 4.8, 1.2 Hz, 1H). 13
C
NMR (100 MHz, CDCl3) δ 157.9, 149.4, 142.8, 139.8, 139.1, 135.7,
131.75, 131.68, 128.9, 128.0, 127.1, 126.2, 124.7, 122.3, 122.0.
2-(2-Bromo-4-fluorophenyl)pyridine (2j)[13e] was prepared as a
1
2-(3,5-Dibromo-[1,1'-biphenyl]-4-yl)pyridine
(2d')[21]
was
yellow oil (64.8 mg, 86% yield). H NMR (400 MHz, CDCl3) δ 8.71-
prepared as a white solid (18.7 mg, 16% yield). 1H NMR (400 MHz,
CDCl3) δ 8.78-8.76 (m, 1H), 7.86-7.81 (m, 3H), 7.60-7.57 (m, 2H),
7.50-7.46 (m, 2H), 7.44-7.40 (m, 1H), 7.38-7.35 (m, 2H). 13C NMR
(100 MHz, CDCl3) δ 158.6, 149.6, 144.0, 140.3, 138.0, 136.4, 130.5,
129.1, 128.5, 127.2, 124.7, 123.9, 123.0.
8.69 (m, 1H), 7.75 (td, J = 7.8, 2.0 Hz, 1H), 7.58 (d, J = 8.0 Hz, 1H),
7.53 (dd, J = 8.6, 6.4 Hz, 1H), 7.42 (dd, J = 8.4, 2.4 Hz, 1H), 7.29 (ddd,
J = 7.4, 4.8, 0.8 Hz, 1H), 7.12 (td, J = 8.4, 2.8 Hz, 1H). 13C NMR (100
MHz, CDCl3) δ 162.1 (d, J = 250.2 Hz), 157.3, 149.4, 137.5 (d, J = 4.2
Hz), 135.8, 132.5 (d, J = 9.0 Hz), 124.7, 122.5, 121.9 (d, J = 9.2 Hz),
120.3 (d, J = 23.5 Hz), 114.7 (d, J = 21.4 Hz).
2-(2-Bromo-4-methoxyphenyl)pyridine (2e)[13f] was prepared
1
as a yellow oil (67.9 mg, 86% yield). H NMR (400 MHz, CDCl3) δ
2-(2-Bromo-4-chlorophenyl)pyridine (2k)[22] was prepared as a
1
8.68-8.67 (m, 1H), 7.71 (td, J = 7.8, 2.0 Hz, 1H), 7.58 (d, J = 7.6 Hz,
1H), 7.48 (d, J = 8.4 Hz, 1H), 7.25-7.22 (m, 1H), 7.21 (d, J = 2.4 Hz,
1H), 6.95 (dd, J = 8.6, 2.4 Hz, 1H), 3.82 (s, 3H). 13C NMR (100 MHz,
white solid (68.4 mg, 85% yield). H NMR (400 MHz, CDCl3) δ 8.71
(d, J = 3.6 Hz, 1H), 7.76 (t, J = 7.0 Hz, 1H), 7.69 (d, J = 1.2 Hz, 1H),
7.59 (d, J = 8.0 Hz, 1H), 7.49 (d, J = 8.0 Hz, 1H), 7.39 (dd, J = 8.2, 1.2
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Running title
Chin. J. Chem.
Hz, 1H), 7.31-7.28 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 157.2, 149.5, yellow oil (71.3 mg, 96% yield). 1H NMR (400 MHz, CDCl3) δ 8.51 (d,
139.7, 135.9, 134.8, 132.8, 132.2, 127.8, 124.6, 122.6, 122.0.
2-(2,4-Dibromophenyl)pyridine (2l)[23] was prepared as a white
solid (77.7 mg, 83% yield). 1H NMR (400 MHz, CDCl3) δ 8.70 (d, J =
4.4 Hz, 1H), 7.84 (d, J = 2.0 Hz, 1H), 7.75 (td, J = 7.8, 2.0 Hz, 1H), 7.58
(d, J = 7.6 Hz, 1H), 7.53 (dd, J = 8.2, 2.0 Hz, 1H), 7.42 (d, J = 8.4 Hz,
1H), 7.29 (ddd, J = 7.6, 5.0, 1.2 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ
157.2, 149.5, 140.1, 135.9, 135.5, 132.5, 130.7, 124.5, 122.7, 122.6,
122.3.
J = 4.0 Hz, 1H), 7.65 (dd, J = 8.0, 0.8 Hz, 1H), 7.58 (d, J = 7.6 Hz, 1H),
7.39 (td, J = 7.4, 0.8 Hz, 1H), 7.30-7.21 (m, 3H), 2.14 (s, 3H). 13C NMR
(100 MHz, CDCl3) δ 158.4, 146.5, 141.4, 137.7, 132.5, 131.7, 130.1,
129.4, 127.4, 122.8, 122.4, 18.8.
2-(2-Bromophenyl)-4-methylpyridine (2t)[21] was prepared as a
yellow oil (64.3 mg, 86% yield). 1H NMR (400 MHz, CDCl3) δ 8.57 (d,
J = 5.2 Hz, 1H), 7.67 (d, J = 8.0 Hz, 1H), 7.51 (d, J = 7.6 Hz, 1H), 7.41-
7.38 (m, 2H), 7.26-7.22 (m, 1H), 7.12 (d, J = 4.8 Hz, 1H), 2.42 (s, 3H).
13C NMR (100 MHz, CDCl3) δ 158.1, 149.0, 146.9, 141.3, 133.1, 131.3,
129.5, 127.4, 125.4, 123.3, 121.7, 21.0.
Methyl 3-bromo-4-(pyridin-2-yl)benzoate (2m)[21] was
prepared as a white solid (53.4 mg, 61% yield). 1H NMR (400 MHz,
CDCl3) δ 8.73 (d, J = 4.4 Hz, 1H), 8.36 (d, J = 1.6 Hz, 1H), 8.06 (dd, J =
8.4, 1.6 Hz, 1H), 7.78 (td, J = 7.8, 1.6 Hz, 1H), 7.62 (dd, J = 8.0, 2.4
Hz, 2H), 7.34-7.31 (m, 1H), 3.95 (s, 3H). 13C NMR (100 MHz, CDCl3)
δ 165.5, 157.3, 149.5, 145.2, 135.9, 134.4, 131.4, 131.3, 128.4,
124.6, 122.8, 121.7, 52.4.
2-(2,6-Dibromophenyl)-4-methylpyridine (2t')[21] was prepared
as a white solid (7.5 mg, 8% yield). 1H NMR (400 MHz, CDCl3) δ 8.59
(d, J = 3.6 Hz, 1H), 7.62 (d, J = 7.6 Hz, 2H), 7.16-7.08 (m, 3H), 2.43 (s,
3H). 13C NMR (100 MHz, CDCl3) δ 158.5, 149.2, 147.6, 141.9, 131.8,
130.4, 125.2, 123.9, 123.7, 21.1.
Methyl 3,5-dibromo-4-(pyridin-2-yl)benzoate (2m')[21] was
prepared as a white solid (17.4 mg, 16% yield). 1H NMR (400 MHz,
CDCl3) δ 8.77 (d, J = 4.4 Hz, 1H), 8.29 (s, 2H), 7.84 (t, J = 7.2 Hz, 1H),
2-(2-Bromophenyl)-5-methylpyridine (2u)[25] was prepared as a
yellow oil (59.3 mg, 80% yield). 1H NMR (400 MHz, CDCl3) δ 8.54 (s,
1H), 7.66 (d, J = 8.0 Hz, 1H), 7.56 (d, J = 7.6 Hz, 1H), 7.50 (t, J = 8.2
7.38 (dd, J = 6.8, 5.2 Hz, 1H), 7.31 (d, J = 7.6 Hz, 1H), 3.96 (s, 3H). 13
C
Hz, 2H), 7.38 (t, J = 7.4 Hz, 1H), 7.26-7.21 (m, 1H), 2.39 (s, 3H). 13
C
NMR (100 MHz, CDCl3) δ 164.6, 158.1, 149.7, 145.7, 136.6, 132.9,
132.3, 124.3, 123.8, 123.3, 52.8.
NMR (100 MHz, CDCl3) δ 155.5, 149.7, 141.1, 136.4, 133.2, 132.0,
131.4, 129.5, 127.5, 124.1, 121.8, 18.2.
2-(2-Bromo-5-methylphenyl)pyridine (2n)[24] was prepared as a
2-(2-Bromo-6-methoxyphenyl)-5-methylpyridine (2w) was
1
1
yellow oil (62.1 mg, 83% yield). H NMR (400 MHz, CDCl3) δ 8.72-
prepared as a yellow oil (77.9 mg, 93% yield). H NMR (400 MHz,
8.70 (m, 1H), 7.74 (td, J = 7.8, 2.0 Hz, 1H), 7.60 (d, J = 8.0 Hz, 1H),
7.54 (d, J = 8.4 Hz, 1H), 7.37 (d, J = 2.0 Hz, 1H), 7.30-7.26 (m, 1H),
7.06 (dd, J = 8.0, 2.0 Hz, 1H), 2.35 (s, 3H). 13C NMR (100 MHz, CDCl3)
δ 158.3, 149.3, 140.7, 137.4, 135.7, 132.9, 132.0, 130.5, 124.7,
122.3, 118.2, 20.7.
CDCl3) δ 8.56 (s, 1H), 7.56 (dd, J = 7.8, 2.0 Hz, 1H), 7.25 (d, J = 7.6 Hz,
1H), 7.21-7.17 (m, 2H), 6.90 (d, J = 8.0 Hz, 1H), 3.70 (s, 3H), 2.38 (s,
3H). 13C NMR (100 MHz, CDCl3) δ 158.2, 153.4, 149.7, 136.5, 131.7,
130.8, 129.9, 124.7, 124.6, 124.0, 109.9, 55.9, 18.2. HRMS m/z (ESI)
calcd for C13H13BrNO (M + H)+, 278.0175, found 278.0172.
2-(2-Bromo-5-methoxyphenyl)pyridine (2o)[24] was prepared as
2-(6-Bromobenzo[d][1,3]dioxol-5-yl)pyridine (2x) was prepared
1
o
1
a white oil (57.3 mg, 72% yield). H NMR (400 MHz, CDCl3) δ 8.71-
as a white solid (67.6 mg, 81% yield). m.p. 67.4-68.7 C. H NMR
(400 MHz, CDCl3) δ 8.69-8.68 (m, 1H), 7.73 (td, J = 7.6, 1.6 Hz, 1H),
7.57 (d, J = 8.0 Hz, 1H), 7.28-7.25 (m, 1H), 7.11 (s, 1H), 7.03 (s, 1H),
6.02 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 158.1, 149.4, 148.4, 147.5,
135.7, 134.7, 124.9, 122.2, 113.0, 112.6, 111.0, 101.9. HRMS m/z
(ESI) calcd for C12H9BrNO2 (M + H)+ 277.9811, found 277.9809.
2-(3-Bromonaphthalen-2-yl)pyridine (2y)[13f] was prepared as a
white solid (77.0 mg, 90% yield). 1H NMR (400 MHz, CDCl3) δ 8.75-
8.73 (m, 1H), 8.17 (s, 1H), 8.00 (s, 1H), 7.83-7.81 (m, 1H), 7.76-7.72
(m, 2H), 7.62 (dt, J = 8.0, 1.0 Hz, 1H), 7.51-7.45 (m, 2H), 7.28 (ddd, J
=7.6, 5.2, 1.2 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 158.2, 149.3,
138.5, 135.7, 133.9, 132.1, 131.8, 130.6, 128.1, 127.2, 126.61,
126.56, 124.9, 122.3, 119.1.
8.70 (m, 1H), 7.74 (td, J = 7.6, 1.6 Hz, 1H), 7.60 (d, J = 8.0 Hz, 1H),
7.53 (d, J = 8.8 Hz, 1H), 7.30-7.27 (m, 1H), 7.09 (d, J = 3.2 Hz, 1H),
6.82 (dd, J = 8.8, 3.2 Hz, 1H), 3.81 (s, 3H). 13C NMR (100 MHz, CDCl3)
δ 158.9, 158.1, 149.3, 141.8, 135.7, 133.9, 124.7, 122.4, 116.2,
112.0, 55.5.
2-(2-Bromo-5-chlorophenyl)pyridine (2p) was prepared as a
o
1
white solid (57.2 mg, 71% yield). m.p. 73.7-75.2 C. H NMR (400
MHz, CDCl3) δ 8.71 (d, J = 4.8 Hz, 1H), 7.76 (td, J = 7.8, 1.6 Hz, 1H),
7.60-7.57 (m, 2H), 7.55 (d, J = 2.4 Hz, 1H), 7.30 (ddd, J = 7.4, 5.0, 0.8
Hz, 1H), 7.22 (dd, J = 8.4, 2.8 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ
157.0, 149.5, 142.5, 135.9, 134.3, 133.6, 131.3, 129.6, 124.6, 122.8,
119.6. HRMS m/z (ESI) calcd for C11H8BrClN (M + H)+ 267.9523,
found 267.9521.
2-(2-Bromophenyl)pyrimidine (2z)[13f] was prepared as a yellow
oil (62.2 mg, 88% yield). 1H NMR (400 MHz, CDCl3) δ 8.88 (d, J = 5.2
Hz, 2H), 7.72-7.69 (m, 2H), 7.43 (td, J = 7.6, 1.2 Hz, 1H), 7.32-7.28
(m, 2H). 13C NMR (100 MHz, CDCl3) δ 166.5, 157.0, 139.6, 133.7,
131.5, 130.5, 127.3, 121.5, 119.3.
2-(2-Bromo-6-methylphenyl)pyridine (2q)[14] was prepared as a
colorless oil (69.0 mg, 93% yield). 1H NMR (400 MHz, CDCl3) δ 8.72
(d, J = 4.4 Hz, 1H), 7.77 (td, J = 8.0, 2.0 Hz, 1H), 7.49 (d, J = 8.0 Hz,
1H), 7.30-7.26 (m, 2H), 7.21 (d, J = 7.6 Hz, 1H), 7.13 (t, J = 7.8 Hz,
1H), 2.08 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 159.0, 149.5, 141.0,
138.5, 136.2, 130.0, 129.2, 129.1, 124.6, 122.9, 122.3, 20.6.
2-(2-Bromo-6-methoxyphenyl)pyridine (2r)[14] was prepared as
a white oil (74.4 mg, 94% yield). 1H NMR (400 MHz, CDCl3) δ 8.72 (d,
J = 4.8 Hz, 1H), 7.74 (td, J = 7.6, 1.6 Hz, 1H), 7.29-7.25 (m, 3H), 7.20
(t, J = 8.0 Hz, 1H), 6.92 (d, J = 8.0 Hz, 1H), 3.69 (s, 3H). 13C NMR (100
10-Bromobenzo[h]quinolone (2aa)[26] was prepared as a white
solid (65.0 mg, 84% yield). 1H NMR (400 MHz, CDCl3) δ 9.10 (dd, J =
4.2, 1.6 Hz, 1H), 8.14 (dd, J = 8.0, 2.0 Hz, 1H), 8.09 (dd, J = 7.6, 1.2
Hz, 1H), 7.87-7.85 (m, 1H), 7.75 (d, J = 8.8 Hz, 1H), 7.68 (d, J = 8.8
Hz, 1H), 7.54 (dd, J = 8.0, 4.0 Hz, 1H), 7.44 (t, J = 7.8 Hz, 1H). 13C
NMR (100 MHz, CDCl3) δ 147.0, 146.0, 136.2, 135.6, 135.5, 128.3,
MHz, CDCl3) δ 158.0, 156.3, 149.2, 135.9, 130.9, 130.0, 125.3, 124.7, 128.1, 127.9, 127.3, 126.5, 121.8, 119.5.
123.7, 122.2, 109.9, 55.9.
3-(2-Bromophenyl)isoquinoline (2ab) was prepared as a yellow
oil (71.2 mg, 84% yield). H NMR (400 MHz, CDCl3) δ 9.34 (s, 1H),
1
2-(2-Bromophenyl)-3-methylpyridine (2s)[21] was prepared as a
Chin. J. Chem. 2019, 37, XXX－XXX
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This article is protected by copyright. All rights reserved.

First author et al.
Report
8.00 (d, J = 8.4 Hz, 1H), 7.93 (s, 1H), 7.86 (d, J = 8.4 Hz, 1H), 7.72-
7.68 (m, 2H), 7.64-7.59 (m, 2H), 7.41 (td, J = 7.6, 0.8 Hz, 1H), 7.25
(td, J = 7.8, 1.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 152.0, 151.8,
141.3, 135.7, 133.3, 131.81, 131.76, 130.5, 129.4, 127.49, 127.46,
127.4, 126.8, 122.2, 121.0. HRMS m/z (ESI) calcd for C15H11BrN (M
+ H)+ 284.0069, found 284.0066.
Bidentate, Monoanionic Auxiliary-Directed Functionalization of
Carbon-Hydrogen Bonds. Acc. Chem. Res. 2015, 48, 1053–1064. (j)
Park, Y.; Kim, Y.; Chang, S. Transition Metal-Catalyzed C-H Amination:
Scope, Mechanism, and Applications. Chem. Rev. 2017, 117, 9247–
9301; (k) Liu, Y.; Yi, H.; Lei, A. Oxidation-Induced C-H Functionalization:
A Formal Way for C-H Activation. Chin. J. Chem. 2018, 36, 692–697; (l)
Hummel, J. R.; Boerth, J. A.; Ellman, J. A. Transition-Metal-Catalyzed C-
H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds.
Chem. Rev. 2017, 117, 9163–9227. (m) Jiang, Z.-T.; Wang, B.-Q.; Shi, Z.-
J. Transition Metal Catalyzed Direct Oxidative Borylation of C-H Bonds.
Chin. J. Chem. 2018, 36, 950–954; (n) Gandeepan, P.; Müller, T.; Zell,
D.; Cera, G.; Warratz, S.; Ackermann, L. 3d Transition Metals for C-H
3-(2,6-Dibromophenyl)isoquinoline (2ab') was prepared as a
1
pale yellow oil (11.6 mg, 11% yield). H NMR (400 MHz, CDCl3) δ
9.39 (s, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.89 (d, J = 8.0 Hz, 1H), 7.75 (td,
J = 7.6, 1.2 Hz, 1H), 7.69-7.66 (m, 4H), 7.14 (t, J = 8.0 Hz, 1H). 13C
NMR (100 MHz, CDCl3) δ 152.3, 152.2, 141.9, 135.9, 131.9, 130.6,
130.5, 127.9, 127.8, 127.7, 127.0, 124.5, 121.2. HRMS m/z (ESI)
calcd for C15H10Br2N (M + H)+ 361.9174, found 361.9174.
Activation.
Chem. Rev. 2019, 119, 2192–2452; (o) Hartwig, J.
6-(2-Bromophenyl)-9-isopropyl-9H-purine (2ac) was prepared
as a pale yellow solid (83.2 mg, 87% yield). m.p. 109.4-111.2 oC. 1H
NMR (400 MHz, CDCl3) δ 9.09 (s, 1H), 8.19 (s, 1H), 7.76 (d, J = 8.0 Hz,
1H), 7.63 (dd, J = 7.4, 1.2 Hz, 1H), 7.47 (td, J = 7.4, 0.8 Hz, 1H), 7.35
(td, J = 7.8, 1.6 Hz, 1H), 4.99 (p, J = 6.8 Hz, 1H), 1.69 (d, J = 6.8 Hz,
6H). 13C NMR (100 MHz, CDCl3) δ 157.0, 151.7, 151.5, 142.6, 136.4,
133.4, 132.2, 131.6, 130.7, 127.2, 121.8, 47.4, 22.3. HRMS m/z (ESI)
calcd for C14H14BrN4 (M + H)+ 317.0396, found 317.0396.
Evolution of C-H Bond Functionalization from Methane to
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A Comparison of Transition-Metal-Catalyzed Activation, Hydrogen
Atom Transfer, and Carbene/Nitrene Transfer. Angew. Chem. Int. Ed.
2018, 57, 62–101.
For some examples of C-H bond functionalization with oxidizing
coupling reagents, see: (a) Ryu, J.; Kwak, J.; Shin, K,; Lee, D.; Chang, S.
Ir(III)-Catalyzed Mild C-H Amidation of Arenes and Alkenes: An Efficient
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Park, K. T.; Kim, J. G.; Chang, S. Mechanistic Studies on the Rh(III)-
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4534–4542; (d) Shin, K.; Park, S.-W.; Chang, S. Cp*Ir(III)-Catalyzed Mild
and Broad C-H Arylation of Arenes and Alkenes with Aryldiazonium
Salts Leading to the External Oxidant-Free Approach. J. Am. Chem. Soc.
2015, 137, 8584–8592; (e) Liang, Y.; Liang, Y.-F.; Tang, C.; Yuan, Y.; Jiao,
N. Cationic Cobalt(III)-Catalyzed Aryl and Alkenyl C-H Amidation: A
Mild Protocol for the Modification of Purine Derivatives. Chem. Eur. J.
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J. R.; Daniliuc, C. G.; Glorius, F. Redox-Neutral Manganese(I)-Catalyzed
C-H Activation: Traceless Directing Group Enabled Regioselective
Annulation. Angew. Chem. Int. Ed. 2017, 56, 12778–12782.
For some examples of C-H bond functionalization with oxidizing
directing groups, see: (a) Liu, G.; Shen, Y.; Zhou, Z.; Lu, X. Rhodium(III)-
Catalyzed Redox-Neutral Coupling of N-Phenoxyacetamides and
Alkynes with Tunable Selectivity. Angew. Chem. Int. Ed. 2013, 52,
6033–6037; (b) Zhang, H.; Wang, K.; Wang, B.; Yi, H.; Hu, F.; Li, C.; Wang,
J. Rhodium(III)-Catalyzed Transannulation of Cyclopropenes with N-
Phenoxyacetamides through C-H Activation. Angew. Chem. Int. Ed.
2014, 53, 13234–13238; (c) Liang, Y.; Jiao, N. Cationic Cobalt(III)
Catalyzed Indole Synthesis: The Regioselective Intermolecular
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Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2018xxxxx.
Acknowledgement
Financial support from the National Natural Science Foundation
of China (Nos. 21632001, 21772002, 81821004), the Drug
Innovation Major Project (2018ZX09711-001), and the Open
Research Fund of Shanghai Key Laboratory of Green Chemistry and
Chemical Processes are greatly appreciated.
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(The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2019
Manuscript revised: XXXX, 2019
Manuscript accepted: XXXX, 2019
Accepted manuscript online: XXXX, 2019
Version of record online: XXXX, 2019
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© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
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a Department, Institution, Address 1
E-mail:
c Department, Institution, Address 3
E-mail:
b Department, Institution, Address 2
E-mail:
Chin. J. Chem. 2018, template© 2018 SIOC, CAS, Shanghai,
&
WILEY-VCH Verlag GmbH
&
Co. KGaA,
Weinheim
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First author et al.
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Entry for the Table of Contents
Page No.
Efficient
Pd-catalyzed
C-H
Oxidative
DG
DG
Br
[Pd]
DMSO Br
Bromination of Arenes with DMSO and
Hydrobromic Acid
/H
H
(aq)
29
to 96%
examples, up
yield
economy and
monoselectivity
•
•
•
as
source
HBr solution
bromide
bromide-atom
and
strategy
efficient
Aqueous
as
High
•
mild oxidant
DMSO
the
Concise
We have developed an efficient Pd-catalyzed directed C-H bromination protocol, in which dimethyl
sulfoxide (DMSO) is employed as oxidant with hydrobromic acid aqueous solution (HBr(aq)) as
bromide source. The DMSO/HBr(aq) system, which is novelly and efficiently utilized in transition-
metal catalyzed C-H activation, illustrates its practicability by the operational simplicity, inexpensive
and readily available starting materials, and high bromide-atom economy.
Yizhi Yuan, Yujie Liang, Shihui Shi, Yu-Feng Liang,
Ning Jiao*
www.cjc.wiley-vch.de
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.