Rhodium-catalyzed oxidative C-H/C-H cross-coupling of aniline with heteroarene: N-nitroso group enabled mild conditions

Article abstract of DOI:10.1039/C8CC04027C

The development of transition metal-catalyzed oxidative C-H/C-H cross-coupling between two (hetero)arenes to forge aryl-heteroaryl motifs under mild conditions is an appealing yet challenging task. Herein, we disclose a rhodium-catalyzed oxidative C-H/C-H cross-coupling reaction of an N-nitrosoaniline with a heteroarene under mild conditions. The judicious choice of the N-nitroso group as a directing group enables heightened reactivity. The coupled products could be transformed expediently to (2-aminophenyl)heteroaryl skeletons.

Full text of DOI:10.1039/C8CC04027C

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
first methanofullerene derivatives of Sc N@D5h-C80
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DOI: 10.1039/C8CC04027C
Journal Name
COMMUNICATION
Rhodium-catalyzed oxidative C–H/C–H cross-coupling of aniline
with heteroarene: N-nitroso group enabled mild conditions
Shuang He, Guangying Tan, Anping Luo, and Jingsong You*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
F
N
The development of transition metal-catalyzed oxidative C–H/C–H
cross-coupling between two (hetero)arenes to forge aryl-
heteroaryl motifs under mild conditions is an appealing, yet
challenging task. Herein, we disclose a rhodium-catalyzed oxidative
C–H/C–H cross-coupling reaction of a N-nitrosoaniline with a
heteroarene under mild conditions. The judicious choice of the N-
nitroso group as a directing group enables heightened reactivity.
The coupled products could be transformed expediently to (2-
aminophenyl)heteroaryl skeletons.
F
N
CN
O
O
F
S
O
tBu
HN
N
HN
S
S
N
histamine
modulator
microbicide
F
receptor
C-FMS kinase inhibitor
F
F
O
F
HN
N
N
N
N
N
Cl
O
O
N
S
N
H
HN
H
O
OH
Aryl-heteroaryl motifs are highly valuable scaffolds widely existed
in organic functional materials, pharmaceuticals, agrochemicals,
organic synthetic intermediates, ligands and natural products.1
Therefore, their synthesis has attracted much attention in the
organic synthesis community. Among various synthetic approaches
to aryl-heteroaryl motifs, transition metal-catalyzed oxidative C–
H/C–H cross-coupling reactions between two (hetero)arenes are
regarded as one of the most straightforward approaches to aryl-
heteroaryl motifs in terms of step- and atom-economy.2 Over the
past decade, various oxidative C–H/C–H cross-coupling reactions
between two (hetero)arenes have been reported for the efficient
synthesis of aryl-heteroaryl scaffolds, as exemplified by the
pioneering works of Miura, Glorius, Zhang, Su, and You et al.3-7
Despite significant advance, the vast majority of these established
reactions need relatively harsh reaction conditions, and particularly
elevated temperatures (often above 120 °C) owing to high
dissociation energies of the cleavage of heteroarene C−H bonds,
which may be incompatible with some sensitive functional groups.
Thus, it is highly desirable to develop an innovative strategy to realize
this type of cross-coupling reactions under mild conditions.
antimicrobial
kinase modulator
antitumor
agent
agent
protein
Scheme 1. Pharmaceutical and biologically active molecules
containing the (2-aminophenyl)heteroaryl motifs.
(2-Aminophenyl)heteroaryls are an important class of aryl-
heteroaryl motifs (Scheme 1).8 We recently demonstrated rhodium-
catalyzed oxidative C–H/C–H cross-coupling reactions of aromatic
amines with heteroarenes
to rapidly construct (2-
aminophenyl)heteroaryl frameworks using the pivaloyl group as the
directing group.9 However, this reaction is nagged by harsh reaction
conditions, such as extremely high temperature (160 °C), which limits
the synthetic utility of this strategy to a certain extent. Recently, the
N-nitroso moiety proves to be a versatile directing group for mild C−H
functionalization because of its moderate coordination effect.10 As a
part of our ongoing efforts in the construction of aryl-heteroaryl
motifs, we herein wish to disclose a rhodium-catalyzed oxidative C–
H/C–H cross-coupling of a N-nitrosoaniline with a heteroarene under
mild condition. In contrast with our previous work, using the N-
nitroso group as the directing group enables heightened reactivity.
As a result, the reaction temperature is reduced from 160 °C to 60 °C
(even 40 °C and room temperature) (Scheme 2).
R
R
O
[Cp*RhCl2
]
2/AgSbF6
N
mild reaction conditions
easily available starting materials
to excellent
O
N
N
Ag
PivOH
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College
of Chemistry, Sichuan University, 29 Wangjiang Road, Chengdu 610064,
P. R. China. E-mail: jsyou@scu.edu.cn.
2O,
N
Ar
+
H
HetAr
Ar
NaOAc, THF
good
yields
40-60 oC, 24 h
groups
H
HetAr
tolerance of reactive functional
Electronic Supplementary Information (ESI) available: Experimental procedures and
characterization data. CCDC 1838256. For ESI and crystallographic data in CIF or
other electric format See DOI: 10.1039/x0xx00000x
Scheme 2. N-Nitroso group enabled mild oxidative C–H/C–H
cross-coupling of aniline with heteroarene.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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COMMUNICATION
Journal Name
Table 1. Optimization of the reaction conditionsa
Table 2. Scope of N-nitrosoanilinesa,b,c
View Article Online
DOI: 10.1039/C8CC04027C
R2
mol
%)
R2
N
[RhCp*Cl2]2 (5.0
O
N
mol
%)
%)
equiv)
[RhCp*Cl2]2 (5.0
mol
%)
O
N
S
AgSbF6 (20
Ag O
N
O
S
O
N
H
N
S
mol
S
AgSbF6 (20
+
N
equiv)
R1
N
(2.0
2
H
R1
H
+
oxidant
(2.0
PivOH
NaOAc
THF, 60 ο
equiv)
(1.0
(30
H
mol
%)
additive
(1.0
equiv)
solvent, 100 o 24 h
24 h
C,
C
,
1
2a
3
1a
2a
3a
Bn
N
O
O
O
N
N
O
N
Yieldb (%)
N
S
N
S
N
S
Entry
Oxidant
Additive
Solvent
N
S
1
2
Ag2CO3
AgOAc
PivOH
PivOH
toluene/1.0
toluene/1.0
14
11
3a 82%
3b 85%
3c 83%
(1:0.57)
3d trace
,
,
,
,
(13:1)
(1:0.37)
3
4
Ag2O
Cu(OAc)2
Ag2O
Ag2O
Ag2O
Ag2O
Ag2O
Ag2O
Ag2O
Ag2O
Ag2O
Ag2O
PivOH
PivOH
PivOH
PivOH
PivOH
PivOH
PivOH
PivOH
toluene/1.0
toluene/1.0
DCE/1.0
23
8
OMe
O
O
O
O
N
N
N
N
N
N
S
N
S
N
S
S
5
43
16
52
43
71
75
84
82
51
24
6
DMF/1.0
7
dioxane/1.0
MeOH/1.0
THF/1.0
3e 81%
,
3f 78%
,
3g 78%
,
3h 81%
,
(10:1)
(10:1)
(14:1)
(12:1)
8
O
O
O
O
N
N
N
N
N
Br
N
N
N
S
9
S
S
S
MeO
Cl
10
11
12c
13d
14e
THF/0.5
F
PivOH/NaOAc
PivOH/NaOAc
PivOH/NaOAc
PivOH/NaOAc
THF/0.5
3l 82%
,
3i 77%
,
3j 76%
,
3k 84%
,
(13:1)
(10:1)
(10:1)
(10:1)
N
THF/0.5
O
O
O
N
N
N
N
N
O
THF/0.5
N
N
S
H
S
S
S
Br
F3C
THF/0.5
O
O
a Reaction conditions: 1a (0.2 mmol, 1.0 equiv), 2a (0.6 mmol, 3.0
equiv), [Cp*RhCl2]2 (5.0 mol %), AgSbF6 (20 mol %), oxidant (2.0
equiv), acid (1.0 equiv), and base (30 mol %) at 100 °C for 24 h under
3o 74%
,
3m 86%
3p 51%
,
,
(15:1)
3n,
72%
(15:1)
(13:1)
(14:1)
N
O
O
O
N
O
O
O
N
Cl
N
c
an N2 atmosphere. b Isolated yield. At 60 °C. d At 40 °C. e At room
N
N
S
N
N
S
S
S
temperature for 36 h.
Our investigation commenced with the reaction between N-
methyl-N-phenylnitrous amide 1a and benzothiophene 2a (For
detailed optimization, see Table S1, ESI†). Initially, the reaction
3r 83%
3s 78%
3t 66%
,
3q 76%
,
,
,
(12:1)
(15:1)
(1:0.13)
a Reaction were performed with 1 (0.2 mmol, 1.0 equiv), and 2a (0.6
mmol, 3.0 equiv) in THF (0.5 mL) at 60 °C for 24 h under an N2
atmosphere. b Isolated yield. c The ratio of the syn to anti isomers
relative to N–N bond, determined by the 1H NMR spectrum.
was performed in toluene (1 mL) at 100 °C for 24 h in the
presence of [RhCp*Cl2]2 (5 mol %), AgSbF6 (20 mol %), PivOH (1.0
equiv), and Ag salt (2.0 equiv) as the oxidant (Table 1, entries 1-3).
Gratifyingly, the coupled product N-(2-(benzo[b]thiophen-2-
yl)phenyl)-N-methylnitrous amide 3a was obtained in 23% yield by
using Ag2O as the oxidant (Table 1, entry 3). Replacing Ag2O with
Cu(OAc)2, 3a was delivered in only 8% yield (Table 1, entry 4). After
the solvents were examined, THF proved to be superior to toluene,
DCE, DMF, dioxane and MeOH (Table 1, entries 3 and 5-9). Reducing
the dosage of THF to 0.5 mL, 3a could be afforded in 75% yield (Table
1, entry 10). The addition of 30 mol % of NaOAc could further
improve the yield to 84% (Table 1, entry 11). Furthermore, an equal
yield of 3a could be obtained when running the reaction mixture of
1a and 2a at 60 °C (Table 1, entry 12). In addition, we were surprised
to find that the cross-coupling reaction could occur at 40 °C and even
room temperature, albeit in reduced yields (Table 1, entries 13 and
14). Finally, we established the optimal catalytic system composed of
[RhCp*Cl2]2 (5 mol %), AgSbF6 (20 mol %), Ag2O (2.0 equiv), PivOH
(1.0 equiv), and NaOAc (30 mol %) in 0.5 mL of THF at 60 °C for 24 h.
In addition, we performed the reaction of N-phenylpivalamide
instead of N-nitrosoaniline with 2a under the standard conditions,
and the coupled product 3u was obtained in only 32% yield (ESI†,
Part IV).
With the optimal conditions in hand, the scope of N-
nitrosoanilines was firstly examined. As shown in Table 2, various N-
alkyl-substituted substrates could smoothly react with
benzothiophene 2a, delivering the corresponding products in good
yields (Table 2, 3a-3c). Due to steric hindrance effect, N-(tert-butyl)-
N-phenylnitrous amide was not tolerated and only a trace amount of
3d was detected. N-Methyl-N-phenylnitrous amides bearing an
electron-donating group on the benzene ring could react with 2a in
good yields (Table 2, 3e-3i). This protocol was also compatible with a
variety of electron-withdrawing groups such as halide (F, Cl and Br),
CF3, acyl, formyl, and ester (Table 2, 3j-3q). The N-methyl-N-
phenylnitrous amide possessing two substituent groups could be
engaged in this arylation, delivering 3r in 83% yield. N-Methyl-N-
(naphthalen-2-yl)nitrous amide provided the coupled product at the
C3 position (Table 2, 3s). Moreover, 1-nitroso-1,2,3,4-
tetrahydroquinoline participated in this coupling reaction in 66%
yield (Table 2, 3t).
2 | J. Name., 2012, 00, 1-3
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Table 3. Scope of heteroarenesa,b,c
COMMUNICATION
of 2a with CD3OD (0.1 mL) in either the presence or absence of 1a did
View Article Online
DOI: 10.1039/C8CC04027C
not led to any deuterated [D]-2a (Scheme 4, (b) and (c)), suggesting
mol
%)
[RhCp*Cl2]2 (5.0
mol
that the C−H metalation of 2a is an irreversible process. Then, the
kinetic isotope effect (KIE) experiments for both coupling partners
were investigated (Scheme 4, (d) and (e)). Two parallel competition
reactions between 1a and [D5]-1a with 2a did not give a significant
KIE value (kH/kD = 1.02) (Scheme 4, (d)). A significant KIE value of 2.93
was observed for 2a and [D]-2a with 1a (Scheme 4, (e)). These above
results reveal that the C−H cleavage of 2a might be related to the
rate-determining step.12 Subsequently, we prepared the
cyclometalated rhodium complex 6 according to the previous work
by Zhu and coworkers (Scheme 4, (f)).10a,13 When running the
reaction of 1m and 2a in the presence of 10 mol % of 6, the coupled
product 3m could be afforded in 63% yield (Scheme 4, (g)), indicating
that the complex 6 could be a possible intermediate.
%)
O
AgSbF6 (20
N
O
N
H
N
N
Ag2
O
equiv)
(2.0
+
H
HetAr
PivOH
NaOAc
THF, 60 ο
equiv)
mol
%)
(1.0
(30
HetAr
1a
2
4
C
,
24 h
O
O
O
O
O
O
O
O
N
N
N
N
N
S
N
N
S
N
S
S
R
Ph
Cl
Br
=
=
4a
R
R
Me, 89%
4c 93%
4d 87%
4e 88%
,
(12:1)
,
,
,
(15:1)
(15:1)
(12:1)
4b
OMe, 90%
,
(13:1)
O
O
N
N
N
N
N
N
N
S
N
O
O
S
S
S
CO2Et
Br
H
Br
4f 85%
,
4g 54%
,
4h 53%
4i 51%
,
(12:1)
,
(10:1)
(12:1)
(12:1)
mol
%)
[RhCp*Cl2
]
2 (5.0
O
N
mol
%)
O
AgSbF6 (20
Ag O
N
N
S
S
O
O
N
N
N
N
N
N
N
N
equiv)
(2.0
2
N
S
H
+
(a)
PivOH
(1.0
equiv)
H
O
O
mol
NaOAc
THF
%)
C
,
24 h
(30
60 ο
(10 mL),
(gram-scale production)
mmol)
NH
1a
2a
(4.0
3a, 76%
N
O
N
N
Cl
Fe
4j 85%
,
equiv)
4k 86%
,
4l 71%
,
4m 45%
(11:1)
powder (4.0
NH4Cl
Zn
,
N
S
equiv)
equiv)
NH2
S
(12:1)
powder (2.0
NH4Cl
(12:1)
(12:1)
equiv)
(3.0
(1.2
S
(b)
:
=
:
3
1
EtOH
100 ο 24 h
H
2O
:
=
:
3
1
MeOH
H
2O
45 ο 8 h
a Reaction were performed with 1a (0.2 mmol, 1.0 equiv), and 2 (0.6
mmol, 3.0 equiv) in THF (0.5 mL) at 60 °C for 24 h under an N2
atmosphere. b Isolated yield. c The ratio of the syn to anti isomers
relative to N–N bond, determined by the 1H NMR spectrum.
C,
C,
3a
5a 86%
5b 64%
,
,
Bn
NH2
5% Pd/C
O
N
N
S
NaH2
PO2•H2O
S
(c)
:
=
:
3
1
MeOH
140 ο 24 h
H
2O
C,
5c 78%
,
3b
Next, we employed 1a as the coupling partner to investigate the
scope of heteroarenes (Table 3). To our delight, various thiophene
derivatives possessing a wide range of functional groups such as
methyl, methoxy, chloro, bromo, acyl, ester, and formyl were
compatible with this protocol (Table 3, 4a-4i). 5-
Chlorobenzothiophene was engaged in this reaction (Table 3, 4j). 2,5-
Substituted thiophene such as 2-bromo-5-methylthiophene (2o) and
2,5-dichlorothiophene (2p) did not give the desired product except
for the recovery of starting materials. This methodology could also
be extended to furan and indole derivatives (Table 3, 4k-4m), but 3-
substituted indoles, such as 1-(1H-indol-3-yl)ethan-1-one (2q), 1-
benzyl-1H-indole-3-carbaldehyde (2r), and methyl 1-benzyl-1H-
indole-3-carboxylate (2s), failed to deliver the desired products.
To further highlight the synthetic utility of our strategy, we
illustrated the scalability of the reaction. Under the standard
conditions, 3a could be obtained without problem on a gram scale in
76 % yield (Scheme 3, (a)). Furthermore, the N-nitroso group could
be removed from the coupled product 3a or be converted into amino,
delivering 2-(benzo[b]thiophen-2-yl)-N-methylaniline 5a and 1-(2-
(benzo[b]thiophen-2-yl)phenyl)-1-methylhydrazine 5b in 86% and 64%
yields, respectively (Scheme 3, (b)).10d,11a Notably, treatment of 3b
with Pd/C and NaH2PO2•H2O, the nitroso and benzyl groups could be
removed in one pot, affording 2- (benzo[b]thiophen-2-yl)aniline 5c in
78% yield (Scheme 3, (c)).11b
Scheme 3. Gram-scale reaction and the conversion of 3a and 3b.
H
H/D
mol
mol
%), AgSbF6 (20
%)
%)
O
[Cp*RhCl2]2 (5
Ag O
N
H
O
N
N
PivOD
equiv)
N
(2.0 equiv),
(1.0
2
+
+
CD3OD
mL
(a)
(b)
mol
NaOAc
THF, 60 oC, 2 h
(30
%),
H/D
0.1
1a
10%
1a
n
[D ]-
mol
mol
[Cp*RhCl2]2 (5
Ag O
%), AgSbF6 (20
PivOD
S
S
equiv)
(2.0 equiv),
mol
(1.0
THF, 60 oC, 2 h
2
H
CD3OD
mL
H/D
NaOAc
(30
%),
0.1
2a
[D]-
2a
no
deuteration
mol
mol
%)
[Cp*RhCl2]2 (5
Ag O
%), AgSbF6 (20
PivOD
equiv)
(2.0 equiv),
mol
(1.0
2
+
+
+
+
1a
2a
[D]-
3a
CD3OD
1a
2a
3.0
n
[D ]-
(c)
(d)
NaOAc
THF, 60 oC, 2 h
%),
(30
no
mL
0.1
deuteration
4%
21%
equiv
O
N
O
N
S
N
standard condition
2 h
N
D4/H4
+
H
D5/H5
S
=
K
H/KD 1.02
1a/
1a
2a
3a/
3a
[D4]-
[D5]-
O
N
O
S
N
N
standard condition
2 h
N
+
D/H
(e)
S
H
=
K
H/KD 2.93
1a
2a
2a
3a
/[D]-
1)
equiv)
[RhCp*Cl2]2 (0.5
equiv)
AgSbF6 (2.1
AgOAc (1.1
N
O
N
equiv)
O
N
N
overnight
rt,
MeOH,
Rh
Cl
Cp*
Br
(f)
2)
NaCl
equiv)
(1.5
rt, 3 h
Br
To gain some insights into the reaction mechanism,
hydrogen/deuterium exchange experiments were performed
(Scheme 4, (a)-(c)). Under the standard conditions, N-methyl-N-
phenylnitrous amide 1a reacted with CD3OD (0.1 mL) in either the
absence or present of 2a for 2 h, the H/D exchange ratios of 1a were
10% and 4%, respectively (Scheme 4, (a) and (c)), suggesting that the
cleavage of the C−H bond of 1a was a reversible process. Treatment
MeOH,
1m
6
47%
,
O
N
mol
mol
6
%)
N
S
(10
%), AgSbF6 (10
PivOH
O
N
S
N
Ag O
equiv)
(1.0
(2.0 equiv),
mol
2
H
Br
(g)
+
THF, 60 o 24 h
C,
%),
Br
H
NaOAc
(30
1m
2a
3m 63%
,
equiv)
(3.0
Scheme 4. Mechanistic study.
This journal is © The Royal Society of Chemistry 20xx
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COMMUNICATION
Journal Name
Commun., 2015, 51, 6190; (f) Y. Zhang, H. Zhao, VMie.wZAhrtaicnlegOanlninde
W. Su, Angew. Chem., Int. Ed., 2015, 54D,O3I:81107.1;0(3g9)/CX8. CQCin0,4X02. 7LCi,
Q. Huang, H. Liu, D. Wu, Q. Guo, J. Lan, R. Wang and J. You,
Angew. Chem., Int. Ed., 2015, 54, 7167; (h) B. Li, J. Lan, D. Wu
and J. You, Angew. Chem., Int. Ed., 2015, 54, 14008; (i) S.-T.
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O
N
N
IIIX2
Ag
Cp*Rh
- or
PivO-
H
=
X
OAc
1a
_
AgI
HX
N
+
X
2
N
O
Cp*RhI
RhIII
X
A
Cp*
O
You and J. You, ACS Catal., 2018, 8, 1796.
N
H
N
HetAr
4
5
For selected examples of palladium catalysis, see: (a) D. R.
Stuart and K. Fagnou, Science, 2007, 316, 1172; (b) D. R.
Stuart, E. Villemure and K. Fagnou, J. Am. Chem. Soc., 2007,
129, 12072; (c) P. Xi, F. Yang, S. Qin, D. Zhao, J. Lan, G. Gao, C.
Hu and J. You, J. Am. Chem. Soc., 2010, 132, 1822; (d) C.-Y. He,
S. Fan and X. Zhang, J. Am. Chem. Soc., 2010, 132, 12850; (e)
B. Liu, Y. Huang, J. Lan, F. Song and J. You, Chem. Sci., 2013, 4,
2163; (f) D.-W. Gao, Q. Gu and S.-L. You, J. Am. Chem. Soc.,
2016, 138, 2544.
N
O
2
N
HetAr
RhIII
Cp*
HetAr
HX
or
3
4
B
Scheme 5. Plausible mechanistic pathway.
Based on the above observations and previous works on Rh(III)-
catalyzed C(sp2)–H heteroarylation,3
plausible mechanistic
a
For selected examples of copper catalysis, see: (a) M.
Kitahara, N. Umeda, K. Hirano, T. Satoh and M. Miura, J. Am.
Chem. Soc., 2011, 133, 2160; (b) M. Nishino, K. Hirano, T.
Satoh and M. Miura, Angew. Chem., Int. Ed., 2012, 51, 6993;
(c) X. Qin, B. Feng, J. Dong, X. Li, Y. Xue, J. Lan and J. You, J.
Org. Chem., 2012, 77, 7677; (d) Z. Mao, Z. Wang, Z. Xu, F.
Huang, Z. Yu and R. Wang, Org. Lett., 2012, 14, 3854; (e) M.
Nishino, K. Hirano, T. Satoh and M. Miura, Angew. Chem., Int.
Ed., 2013, 52, 4457; (f) R. Odani, K. Hirano, T. Satoh and M.
Miura, J. Org. Chem., 2013, 78, 11045; (g) R. Odani, K. Hirano,
pathway is proposed (Scheme 5). First, the cyclorhodium
intermediate A is formed through the coordination of N-methyl-N-
phenylnitrous amide 1a with the Cp*Rh(III) species and the
subsequent ortho-C−H bond activation of arene. Next, the resulting
intermediate A reacts with heteroarene 2 to produce the
intermediate B, which further undergoes a reductive elimination to
release the desired product 3 or 4. Finally, the resulting Cp*Rh(I)
species is reoxidized to the Cp*Rh(III) species by Ag salt to furnish the
catalytic cycle.
In summary, we have disclosed a rhodium-catalyzed oxidative C–
H/C–H cross-coupling reaction of a N-nitrosoaniline with a
heteroarene to construct (2-aminophenyl)heteroaryl scaffolds. The
protocol features mild reaction conditions, broad substrate scope
and good tolerance of sensitive functional groups. The coupled
products could be easily transformed to various (2-
aminophenyl)heteroaryl derivatives. Further investigation to extend
the application of this methodology is in progress.
T. Satoh and M. Miura, Angew. Chem., Int. Ed., 2014, 53
,
10784; (h) S. Zhao, J. Yuan, Y.-C. Li and B.-F. Shi, Chem.
Commun., 2015, 51, 12823.
6
For examples of cobalt catalysis, see: (a) L. Grigorjeva and O.
Daugulis, Org. Lett., 2015, 17, 1204; (b) G. Tan, S. He, X. Huang,
X. Liao, Y. Cheng and J. You, Angew. Chem., Int. Ed., 2016, 55
10414.
,
7
8
For an example of nickel catalysis, see: Y. Cheng, Y. Wu, G. Tan
and J. You, Angew. Chem., Int. Ed., 2016, 55, 12275.
(a) M. P. Player, N. Baindur, B. Brandt, N. Chadha, R. J. Patch,
D. Asgari and T. Georgiadis, US 2005/0113566, 2005; (b) C.
Corsi, C. Lamberth, J. Ehrenfreund, H. Tobler and H. Walter,
WO 2005/123722, 2005; (c) K. Seno, T. Shinosaki, S. Hata, I.
Yamada, H. Sato and M. Kataoka, WO 2006/077901, 2006; (d)
S. Chakravarty, B. P. Hart and R. P. Jain, WO 2011/103430,
2011; (e) F. Pierre, M. Haddach, C. F. Regan and D. M.
Ryckman, WO 2011/025859, 2011; (f) K. Önder, R. Datema, D.
Mitchell and I. Kondratov, WO 2016/087618, 2016.
We thank the financial support from the National NSF of China
(No 21432005).
Conflicts of interest
There are no conflicts to declare.
9
Y. Huang, D. Wu, J. Huang, Q. Guo, J. Li and J. You, Angew.
Chem., Int. Ed., 2014, 53, 12158.
10 (a) B. Liu, Y. Fan, Y. Gao, C. Sun, C. Xu and J. Zhu, J. Am. Chem.
Soc., 2013, 135, 468; (b) B. Liu, C. Song, C. Sun, S. Zhou and J.
Zhu, J. Am. Chem. Soc., 2013, 135, 16625; (c) C. Wang and Y.
Huang, Org. Lett., 2013, 15, 5294; (d) T. Gao and P. Sun, J. Org.
Chem., 2014, 79, 9888; (e) J. Dong, Z. Wu, Z. Liu, P. Liu and P.
Sun, J. Org. Chem., 2015, 80, 12588; (f) Y. Liang and N. Jiao,
Angew. Chem., Int. Ed., 2016, 55, 4035; (g) Y. Wu, L. Sun, Y.
Chen, Q. Zhou, J.-W. Huang, H. Miao and H.-B. Luo, J. Org.
Chem., 2016, 81, 1244; (h) Y. Chen, R. Zhang, Q. Peng, L. Xu
and X. Pan, Chem. Asian J., 2017, 12,2804.
11 (a) C. Song, C. Yang, F. Zhang, J. Wang and J. Zhu, Org. Lett.,
2016, 18, 4510; (b) X. Huang, J. Huang, C. Du, X. Zhang, F. Song
and J. You, Angew. Chem., Int. Ed., 2013, 52, 12970.
12 E. M. Simmons and J. F. Hartwig, Angew. Chem., Int. Ed., 2012,
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Notes and references
1
(a) A. M. Boldi, Curr. Opin. Chem. Bio., 2004,
Surry and S. L. Buchwald, Angew. Chem., Int. Ed., 2008, 47
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,
6338; (c) J.-S. Wu, S.-W. Cheng, Y.-J. Cheng and C.-S. Hsu,
Chem. Soc. Rev., 2015, 44, 1113.
2
For selected reviews, see: (a) D. Zhao, J. You and C. Hu, Chem.
Eur. J., 2011, 17, 5466; (b) J. Yamaguchi, A. D. Yamaguchi and
K. Itami, Angew. Chem., Int. Ed., 2012, 51, 8960; (c) C. Liu, J.
Yuan, M. Gao, S. Tang, W. Li, R. Shi and A. Lei, Chem. Rev.,
2015, 115, 12138; (d) Y. Yang, J. Lan and J. You, Chem. Rev.,
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For selected examples of rhodium catalysis, see: (a) J. Wencel-
Delord, C. Nimphius, H. Wang and F. Glorius, Angew. Chem.,
Int. Ed., 2012, 51, 13001; (b) J. Dong, Z. Long, F. Song, N. Wu,
3
13 CCDC 1838256
(
6
)
contains the supplementary
Q. Guo, J. Lan and J. You, Angew. Chem., Int. Ed., 2013, 52
580; (c) X. Qin, H. Liu, D. Qin, Q. Wu, J. You, D. Zhao, Q. Guo,
X. Huang and J. Lan, Chem. Sci., 2013, , 1964; (d) Y. Shang, X.
,
crystallographic data for this communication.
4
Jie, H. Zhao, P. Hu and W. Su, Org. Lett., 2014, 16, 416; (e) D.
Qin, J. Wang, X. Qin, C. Wang, G. Gao and J. You, Chem.
4 | J. Name., 2012, 00, 1-3
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