A Facile Route to Ortho-Hydroxyanilnes through an IrIII-Catalyzed Direct C?H Amidation of 2-Phenoxypyridines

Article abstract of DOI:10.1002/asia.201701028

A highly efficient and regioselective Ir^III-catalyzed C?H amidation of 2-phenoxypyridines has been developed by using sulfonyl azides as an amino source. The amidated products were provided in good-to-excellent yields with broad functional-group tolerance. Furthermore, the 2-pyridyl moiety in the amidated products could be readily removed, thus offering an efficient route to synthetically useful ortho-hydroxyanilnes, which are important building blocks in organic synthesis.

Full text of DOI:10.1002/asia.201701028

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: A Facile Access to Ortho-Hydroxyanilnes Based on Ir(III)-
Catalyzed Direct C−H Amidation of 2-Phenoxypyridines
Authors: Lianhui Wang, Zi Yang, Mengqi Yang, Miaodou Tian,
Changshen Kuai, and Xiuling Cui
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Asian J. 10.1002/asia.201701028
Link to VoR: http://dx.doi.org/10.1002/asia.201701028
A Journal of
A sister journal of Angewandte Chemie
and Chemistry – A European Journal

10.1002/asia.201701028
Chemistry - An Asian Journal
FULL PAPER
A Facile Access to Ortho-Hydroxyanilnes Based on Ir(III)-
Catalyzed Direct C−H Amidation of 2-Phenoxypyridines
Lianhui Wang,[a] Zi Yang,[a] Mengqi Yang,[a] Miaodou Tian,[a] Changsheng Kuai[a] and Xiuling Cui*[a]
Dedication ((optional))
Abstract: A highly efficient and regioselective C−H amidation of 2-
phenoxypyridines catalyzed by Ir(III) has been developed using
sulfonyl azides as readily amino source. The amidated products
were provided in good to excellent yields with broad functional group
tolerance. Furthermore, the 2-pyridyl moiety in the amidated
products can readily be removed, offering an efficient route to the
synthetically useful ortho-hydroxyanilnes, which is important building
block in organic synthesis.
directing group has become an efficient strategy to improve the
region-selectivity. However, the structural diversity of the
corresponding products is severely limited because it is
nontrivial to remove and functionalize the coordinating
moieties.[13] Thus, the development of removable or modifiable
directing groups would be highly desirable.[14] In our continuing
efforts to develop highly efficient amination reaction as well as
removable directing groups,[15] we herein explored an iridium-
catalyzed direct C‒ H amination of 2-phenoxypyridines[16] with
sulfonyl azides as amino source and internal oxidant. Notably,
the 2-pyridyl group can be removed to deliver the corresponding
ortho-hydroxy-(N-sulfonyl)anilnes (Scheme 1, c).
Introduction
Nitrogen-containing molecules are widely present in natural
products, pharmaceuticals, agrochemicals, and functional
materials.[1] Especially, ortho-hydroxyaniline and its derivatives
are one of the important intermediates for organic synthesis.[2]
As a result, the development of efficient and selective amination
procedures has been the focus of intensive research in the past
decades. Traditional procedures to syethesize ortho-
hydroxyanilines usually start from aromatic nitration, followed by
reduction (Scheme 1, a),[3] which suffer from side reaction and
harsh reaction conditions and fussy chemical process.[4]
Recently,
transition
metal-catalyzed
amination
of
aryl(preudo)halides,[5] typically palladium-catalyzed Buchwald-
Hartwig coupling reactions[6] and copper-catalyzed Ullman-type
transformations,[7] are among the most reliable and widely used
methods (Scheme 1, b). However, aryl (pseudo)halides are
required and they are not always readily accessible. Moreover,
stoichiometric amounts of (preodo)halogen salt as by-product
are generated in these process.[8,9]
Scheme 1. Strategies for the preparation of ortho-hydroxyanilines
As a consequence, the direct amination of C‒ H bonds to form
C‒ N bonds represents
a straightforward and promising
approach, which obviates the pre-functionalization of substrates
and greatly improves the reaction efficiency.[10] Very recently,
inspired by the work from Chang group,[11] a new catalyst system
using Ir(III) species was rapidly developed for the direct C−H
amination of arenes or alkenes with organic azides under
exceptionally mild conditions, in which molecular nitrogen is
released as a sole by-product external oxidants are avoided.[12]
Among these reports, the use of coordinating moieties as
Results and Discussion
Initially, we commenced our study to examine the various
reaction conditions in
a
model reaction of 2-(2-
fluorophenoxy)pyridine (1a) with tosyl azide (TsN3, 2a) (Table 1).
We were pleased to find that a cationic Ir species generated in
situ from [Cp*IrCl2]2 (0.5 mol%) and AgSbF6 (2.0 mol%)
displayed catalytic activity, and the amidated product 3aa was
obtained in 92% yield in 1,2-DCE at 80 °C (entry 1). 3aa was not
formed in the absence of either [Cp*IrCl2]2 or AgSbF6 (entries 2
and 3), implying that both [Cp*IrCl2]2 and AgSbF6 are crucial in
this current transformation. While increasing the amount of
[Cp*IrCl2]2 from 0.5 mol% to 1.0 mol% did not significantly
improve the yield of the target product (entry 4), reducing the
catalytic loadings to 0.1 mol% yet afforded 3aa in a moderate
yield (entry 5). In view of the importance of AgSbF6 in the
catalytic system, various metal additives were screened as well.
As shown in Table 1, AgNTf2 behaved similar to AgSbF6 in
[a]
Dr. L. Wang, Z. Yang, M. Yang, M. Tian, C. Kuai, Prof. Dr. X. Cui
Engineering Research Center of Molecular Medicine of Ministry of
Education, Key Laboratory of Fujian Molecular Medicine, Key
Laboratory of Xiamen Marine and Gene Drugs, School of
Biomedical Sciences, Huaqiao University, Xiamen, Fujian 361021,
P. R. China
E-mail: cuixl@hqu.edu.cn
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201xxxxxx
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201701028
Chemistry - An Asian Journal
FULL PAPER
efficiency, leading to 3aa in 91% yield (entry 6). Whereas, other
metal salts, such as AgOAc, AgBF4 and KPF6, resulted in
complete inefficiency (entries 7−9). Using the combination of
[Cp*IrCl2]2 and AgSbF6, several nonpolar (1,2-DCE, PhMe and
DCM) and polar (DMF and t-AmOH) solvents were then
evaluated (entries 10−13). The most efficient catalysis was
accomplished in nonpolar reaction media, with 1,2-DCE being
ideal (entry 1). In previous observation by Chang and co-
workers, acetate additives can promote the C−H bond
activation.[11g] However, to our disappointment, the use of
catalytic amounts of NaOAc or a combination of AcOH and
Li2CO3 in this case solely resulted in decreased product yield
(entries 14−15). Finally, the reaction temperature and time were
evaluated. The yield was reduced to some extent when the
reaction temperature decreased to 70 °C (entry 18), and the
yield was not improved evidently by prolonging or shortening the
reaction time (entry 5 vs. entries 16 and 17). It should be
mentioned that several popular transition metal catalysts
including Pd(OAc)2, [RuCl2(p-Cymene)]2, [Cp*RhCl2]2 and
[Cp*CoI2(CO)] were explored as well, however, were totally
unsuccessful for the present reaction. Thus, the optimal
conditions were identified as following: 0.5 mol% [Cp*IrCl2]2, 2.0
mol% AgSbF6, 1.2 equiv. of TsN3 in 1.2-DCE at 80°C for 12 h.
With the optimized reaction conditions in hand, we next
investigated the scope of diaryl ethers with tosyl azide (TsN3, 2a)
and representative data are shown in Scheme 2. A variety of
functional groups, such as halide (1b-d, 1j and 1p), nitro (1e and
1k), aldehyde (1l), ketone (1m) and ester (1n), were well
tolerated with this transformation. To investigate the influence of
substituents at the arene core, sulfonyl azide 2a was reacted
with various substrates 1b-h with electron-withdrawing or -
donating groups, equipped at the ortho position. Diaryl ethers
(1b-f) with electron-withdrawing substituents worked well,
providing the desired products in good to excellent yields.
Electron-donating groups, such as methyl- (1g) and tert-Butyl-
(1h), only afforded moderate yields presumably due to the steric
hindrance. Moreover, functional groups at the para position were
examined. It should be emphasized that the two reactants,
namely 2-phenoxypyridine 1 and azide 2, were used in a ratio of
1.5:1.0 to reduce the diamidation quantities in these
transformations. The amidation of 2-phenoxypyridine (1i) and 2-
(4-bromophenoxy)pyridine (1j) with TsN3 (2a) produced the
target products 3ia and 3ja in 59% and 51% yields. Interestingly,
some substrates with 2-methyl pyridyl group (1k-n) could
perform with good regioselectivity, and deliver to the
monoamidation products 3ka−3na in moderate to good yields.
Aldehyde, ketone and ester in substrates 1l, 1m and 1n did not
act as a directing group, with the ortho-aminated product 3
relative to 2-pyridyl formed exclusively. To our delight, the
amidation occurred selectively at the steric C−H bonds when the
meta position was substituted by a methyl group (1o), affording
the sole regioisomer 3oa in 70% yield. Finally, dichloro-
substituted substrate 1p was also facile (3pa), indicating that the
amidation was not significantly influenced by the electronic
variation of substrates.
Table 1. Optimization of various reaction parameters[a]
Entry
1
[Cp*IrCl2]2/mol %
Additive/mol %
AgSbF6/2.0
—
Solvent
1,2-DCE
1,2-DCE
1,2-DCE
1,2-DCE
1,2-DCE
1,2-DCE
1,2-DCE
1,2-DCE
1,2-DCE
t-AmOH
DMF
3aa/%
92
0
0.5
0.5
—
2
3
AgSbF6/2.0
AgSbF6/4.0
AgSbF6/0.4
AgNTf2/2.0
AgOAc/2.0
AgBF4/2.0
KPF6/2.0
0
4
1.0
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.5
94
54
91
0
5
6
7
8
0
9
0
10
11
12
13
14[b]
15[c]
16[d]
17[e]
18[f]
AgSbF6/2.0
AgSbF6/2.0
AgSbF6/2.0
AgSbF6/2.0
AgSbF6/4.0
AgSbF6/4.0
AgSbF6/1.0
AgSbF6/1.0
AgSbF6/2.0
35
0
DME
56
0
PhMe
1,2-DCE
1,2-DCE
1,2-DCE
1,2-DCE
1,2-DCE
42
9
56
47
76
Encouraged by the successful results in Scheme 1, we further
explored the scope of organic azides
2
with 2-(2-
[a] Reaction conditions: 1a (0.5 mmol), 2a (0.6 mmol), [Cp*IrCl2]2 (0.1-1.0
mol %), Additive (0.4-4.0 mol %), Solvent (2.0 mL), 80 °C, 12 h, isolated yields
based on substrate 1a; [b] NaOAc (30 mol %) was added; [c] AcOH (30
mol %) and Li2CO3 (30 mol %) were added. [d] 16h. [e] 10h. [f] 70 °C.
nitrophenoxy)pyridine (1e) in the presence of 1.0 mol% of
[Cp*IrCl2]2 (Scheme 3). Likewise, versatile functional groups,
such as fluoro (2d, 2g and 2i) and chloro (2e) were compatible
under the standard reaction conditions. In regard to para-
substituted arenesulfonyl azides, both electron-donating and -
withdrawing groups readily participated in the amidation with
excellent efficiency (3eb−3ee). Similarly, substrates substituted
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201701028
Chemistry - An Asian Journal
FULL PAPER
with methyl (2f) or fluoro (2g) group at the meta-position
proceeded
smoothly.
Treatment
of
1e
with
2-
fluorobenzenesulfonyl azide (2i) afforded the desired product 3ei
in 96% yield. 2-Me substituted substrate 1h gave 39% yield,
probably owing to steric effect. We are pleased to find that the
yield of 3eh steadily increased to 97% with a higher [Cp*IrCl2]2
loading (2.0 mol%). Furthermore, aliphatic sulfonyl azide 2j was
also successfully applied to the current iridium-catalyzed
conditions and afforded the product 3ej in 63% yield. Other
amino sources, such as acyl and aryl azides, were not reactive,
leading to negligible product yields (3%). Only benzyl sulfonyl
azide exihibited moderate reactivity (39% yield).
To gain insight into the reaction pathway, preliminary
mechanistic studies were investigated. The intermolecular
competition experiment between 2-phenoxypyridines 1q and 1e
with tosyl azide (2a) were performed (Scheme 4). The ratio of
products (3qa/3ea = 17) indicated that electron-rich substrate 1q
was transformed preferentially, hence rendering an electrophilic-
type iridiation manifold.
Scheme 2. Amidation of diaryl ethers 1 with TsN3 (2a).
Scheme 4. Intermolecular competition experiment with diaryl ethers 1q and 1e.
In addition, a competitive experiment between differently
substituted sulfonyl azides 2c/2d that differ in electronic effects
was conducted (Scheme 5). The ratio of products (3ec/3ed =
1.7) were obtained, which indicated electron-donating
substituents to be beneficial as well.
Scheme 5. Intermolecular competition experiment with azides 2c and 2d.
Scheme 3. Amidation of diaryl ether 1e with sulfonyl azides 2.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201701028
Chemistry - An Asian Journal
FULL PAPER
Furthermore, deuterium-labeling experiments were conducted.
The amidation of 2-phenoxypyridine (1i) with tosyl azide (2a) in
the presence of [D]4-AcOH under the standard reaction
conditions was conducted (Scheme 6). Significant deuterium
was observed for the product [D]n-3ia (28% D) or recycled
substrate [D]n-1i (25% D), being indicative of a reversible C−H
bond metalation step.
cationic Ir(III) species A, in situ generated by treating the dimeric
precursor [Cp*IrCl2]2 with AgSbF6, undergoes a reversible C−H
bond activation of diaryl ether 1a via the chelation assistance of
the pyridine nitrogen atom to generate
a six-membered
iridacycle B. Next, coordination of tosyl azide (2a) to the iridium
center gives the complex C, which may undergo extrusion of
one molecular N2 to provide an iridium−nitrenoid intermediate D.
The subsequent intramolecular insertion of nitrenoid moiety into
iridacycle forms a new C−N bond to deliver the seven-
membered iridacyclic species E. Finally, protonolysis of E
provides the amination product 3aa with the regeneration of the
active iridium species A.
Finally, we were pleased to find that the 2-pyridyl moiety can
be efficiently cleaved (Scheme 8).[16k,16n] Compound 3ia was
treated with methyl trifluoromethanesulfonate (MeOTf) to form 1-
methyl-2-{2-(4-methylphenylsulfonamido)phenoxy}pyridin-1-ium
in toluene. Then, the crude intermediate was added into a
refluxing Na/MeOH solution to generate N-(2-hydroxyphenyl)-4-
methylbenzenesulfonamide 4ia in one pot in 73% yields.
Scheme 6. Iridium-catalyzed direct ortho-C–H amidation azide 2a with diaryl
ether 1i in the presence of [D]4-AcOH.
Scheme 8. Removal of the 2-pyridyl moiety.
On the basis of the above mechanistic studies and the related
reports on iridium-catalyzed direct C−H amidation,[11,12]
a
possible mechanistic pathway is proposed in Scheme 7. First, a
Conclusions
In conclusion, an iridium-catalyzed direct C−H amidation of 2-
phenoxypyridines using a range of synthetically valuable sulfonyl
azides as amino source has been reported. Mild reaction
conditions, low catalyst loading as well as good tolerance of
various functional groups are the remarkable features of this
method. Another attractive feature of this present approach
turned out to be a facile route to the synthetically versatile ortho-
hydroxyaniline derivatives upon the removal of the 2-pyridyl
moieties.
Experimental Section
General information: Unless otherwise stated, all commercial materials
and solvents were used directly without further purification. Melting points
were determined in open glass capillaries and were uncorrected. 1H NMR
spectra were recorded on 400 MHz spectrometers, and 13C NMR spectra
were recorded on a 100 MHz spectrometer. Chemical shifts (δ in ppm)
were referenced to tetramethylsilane (δ = 0 ppm) in CDCl3 as an internal
standard at room temperature. 13C NMR spectra were obtained by using
the same NMR spectrometers and were calibrated with CDCl3 (δ = 77.00
ppm). High-resolution mass spectra (HRMS) were equipped with an ESI
source and a TOF detector. Column chromatography was performed on
silica gel (70−230 mesh ASTM) using the reported eluents. Thin-layer
chromatography (TLC) was carried out on 4×15 cm plates with a layer
thickness of 0.2 mm (silica gel 60 F254).
Scheme 7. Plausible mechanism for the iridium-catalyzed direct ortho-C–H
amidation reaction.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201701028
Chemistry - An Asian Journal
FULL PAPER
Diaryl ether compounds 1a-q[17] and sulfonyl azides 2a-j[18] were
prepared according to the known procedures.
column chromatography on silica gel (PE/EtOAc/DCM: 40:1:1 → 20:1:1)
to afford the desired product 3da (214 mg, 92%) as a white solid. M. p. =
156−157 °C. 1H-NMR (400 MHz, CDCl3): δ = 11.84 (br s, 1H), 8.32 (dd, J
= 5.0, 1.2 Hz, 1H), 7.94 (ddd, J = 7.9, 7.9, 1.4 Hz, 1H), 7.78−7.71 (m, 2H),
7.50 (dd, J = 7.9, 1.3 Hz, 1H), 7.42 (d, J = 8.4 Hz, 2H), 7.40−7.36 (m, 1H),
7.23 (d, J = 8.4 Hz, 2H), 6.67 (dd, J = 7.9, 7.9 Hz, 1H), 2.44 (s, 3H). 13C-
NMR (100 MHz, CDCl3): δ = 155.1 (Cq), 153.5 (Cq), 147.1 (CH), 144.4
(Cq), 140.6 (CH), 140.2 (CH), 135.5 (Cq), 133.5 (CH), 129.5 (CH), 128.0
(CH), 125.4 (Cq), 125.2 (CH), 124.0 (CH), 121.3 (CH), 87.1 (Cq), 21.7
(CH3). HRMS (ESI) m/z calcd for C18H16IN2O3S [M + H]+: 466.9926,
Found 466.9926
The Representative procedure for the synthesis of compounds 3: A
flame-dried sealed tube was cooled to ambient temperature and filled
with N2. To this flask were added 2-(2-fluorophenoxy)pyridine (1a) (94.5
mg, 0.5 mmol), para-toluenesulfonyl azide (2a) (98.5 mg, 0.5 mmol),
[Cp*IrCl2]2 (2.0 mg, 0.0025 mmol), AgSbF6 (3.5 mg, 0.01 mmol) and 1,2-
DCE (2.0 mL). Then the sealed tube was heated at 80 °C. After 12 h, the
reaction mixture was cooled to ambient temperature, filtered through a
pad of celite and silica gel, and washed with EtOAc (3 x 10 mL). The
solvents were removed under reduced pressure. The residue was
purified by silica gel column chromatography (PE/EtOAc = 5:1→2:1) to
afford the desired product 3aa (165 mg, 92%) as a white solid.
4-Methyl-N-{3-nitro-2-(pyridin-2-yloxy)phenyl}benzenesulfonamide
(3ea): The representative procedure was followed using 2-(2-
nitrophenoxy)pyridine (1e) (108.0 mg, 0.5 mmol) and para-
toluenesulfonyl azide (2a) (98.5 mg, 0.5 mmol). After 12 h, purification by
column chromatography on silica gel (PE/EtOAc/DCM: 20:1:1 → 5:1:1) to
afford the desired product 3ea (181 mg, 94%) as a yellow solid. M. p. =
158−159 °C. 1H-NMR (400 MHz, CDCl3): δ = 11.11 (br s, 1H), 8.29 (dd, J
= 5.0, 2.0 Hz, 1H), 8.19 (dd, J = 8.6, 1.6 Hz, 1H), 7.86 (d, J = 8.4 Hz, 2H),
7.82 (dd, J = 7.8, 1.7 Hz, 1H), 7.67 (ddd, J = 7.8, 7.8, 2.0 Hz, 1H), 7.31 (d,
J = 8.4 Hz, 2H), 7.27 (d, J = 8.4 Hz, 1H), 7.13−7.06 (m, 2H), 2.45 (s, 3H).
13C-NMR (100 MHz, CDCl3): δ = 153.2 (Cq), 153.1 (Cq), 148.0 (CH),
144.3 (Cq), 140.7 (CH), 138.4 (CH), 137.0 (Cq), 135.5 (Cq), 129.4 (CH),
129.2 (Cq), 128.5 (CH), 126.0 (CH), 120.7 (CH), 119.3 (CH), 117.4 (CH),
21.7 (CH3). HRMS (ESI) m/z calcd for C18H16N3O5S [M + H]+: 386.0811,
Found 386.0812.
N-{3-fluoro-2-(pyridin-2-yloxy)phenyl}-4-methylbenzenesulfonamide
(3aa): M. p. = 139−140 °C. 1H-NMR (400 MHz, CDCl3): δ = 11.13 (br s,
1H), 8.32 (d, J = 5.3 Hz, 1H), 7.94 (ddd, J = 7.6, 7.6, 0.7 Hz, 1H), 7.74 (d,
J = 3.9 Hz, 1H), 7.48 (d, J = 4.2 Hz, 2H), 7.41−7.36 (m, 1H), 7.33−7.27
(m, 1H), 7.23 (d, J = 4.2 Hz, 2H), 6.87−6.79 (m, 1H), 7.09 (dd, J = 9.8,
8.4 Hz, 1H), 2.42 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ = 153.6 (Cq),
1
153.3 (d, JC–F = 242 Hz, Cq), 147.2 (CH), 144.5 (Cq), 144.4 (Cq), 140.4
4
(CH), 135.9 (Cq), 129.6 (CH), 128.1 (d, JC–F = 3 Hz, CH), 128.0 (CH),
3
125.1 (CH), 124.0 (CH), 118.8 (d, JC–F = 8 Hz, CH), 128.6 (d, 2JC–F = 18
Hz, CH), 21.7 (CH3) (One Cq is invisible). 19F-NMR (376 MHz, CDCl3): δ
= −113.5 (s). HRMS (ESI) m/z calcd for C18H16FN2O3S [M + H]+:
359.0866, Found 359.0867.
4-Methyl-N-{2-(pyridin-2-yloxy)-[1,1'-biphenyl]-3-yl}benzenesulfon-
amide (3fa): The representative procedure was followed using 2-([1,1'-
biphenyl]-2-yloxy)pyridine (1f) (123.0 mg, 0.5 mmol) and para-
toluenesulfonyl azide (2a) (98.5 mg, 0.5 mmol). After 12 h, purification by
column chromatography on silica gel (PE/EtOAc/DCM: 40:1:1 → 20:1:1)
to afford the desired product 3fa (136 mg, 65%) as a white solid. M. p. =
162−163 °C. 1H-NMR (400 MHz, CDCl3): δ = 10.85 (br s, 1H), 8.28 (dd, J
= 5.0, 1.1 Hz, 1H), 7.92 (ddd, J = 7.8, 7.8, 2.0 Hz, 1H), 7.74 (d, J = 8.1
Hz, 1H), 7.55 (d, J = 8.3 Hz, 2H), 7.51 (dd, J = 7.9, 1.5 Hz, 1H),
7.44−7.31 (m, 7H), 7.26 (d, J = 8.3 Hz, 2H), 6.99 (dd, J = 7.7, 7.7 Hz, 1H),
2.47 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ = 153.9 (Cq), 152.7 (Cq),
147.3 (CH), 144.1 (Cq), 139.9 (CH), 138.2 (Cq), 136.0 (Cq), 132.1 (CH),
132.0 (CH), 132.0 (Cq), 129.4 (CH), 129.2 (CH), 128.3 (CH), 128.0 (CH),
127.1 (CH), 126.4 (Cq), 124.9 (CH), 123.7 (CH), 119.9 (CH), 21.7 (CH3).
HRMS (ESI) m/z calcd for C24H21N2O3S [M + H]+: 417.1273, Found
417.1275.
N-{3-chloro-2-(pyridin-2-yloxy)phenyl}-4-methylbenzenesulfonamide
(3ba): The representative procedure was followed using 2-(2-
chlorophenoxy)pyridine (1b) (103.0 mg, 0.5 mmol) and para-
toluenesulfonyl azide (2a) (98.5 mg, 0.5 mmol). After 12 h, purification by
column chromatography on silica gel (PE/EtOAc/DCM: 40:1:1 → 30:1:1)
to afford the desired product 3ba (159 mg, 85%) as a white solid. M. p. =
155−156 °C. 1H-NMR (400 MHz, CDCl3): δ = 11.52 (br s, 1H), 8.33 (d, J
= 4.9 Hz, 1H), 7.94 (ddd, J = 7.8, 7.7, 1.8 Hz, 1H), 7.74 (d, J = 7.8 Hz,
1H), 7.46 (d, J = 8.4 Hz, 2H), 7.44−7.42 (m, 1H), 7.41−7.34 (m, 2H), 7.23
(d, J = 8.4 Hz, 2H), 6.85 (dd, J = 8.0, 8.0 Hz, 1H), 2.43 (s, 3H). 13C-NMR
(100 MHz, CDCl3): δ = 153.5 (Cq), 152.0 (Cq), 147.2 (CH), 144.4 (Cq),
140.2 (CH), 135.7 (Cq), 131.6 (CH), 131.5 (CH), 129.5 (CH), 128.0 (CH),
127.3 (Cq), 125.1 (CH), 124.0 (CH), 123.6 (Cq), 119.7 (CH), 21.7 (CH3).
HRMS (ESI) m/z calcd for C18H16ClN2O3S [M + H]+: 375.0570, Found
375.0572.
N-{3-bromo-2-(pyridin-2-yloxy)phenyl}-4-methylbenzenesulfonamide
(3ca): The representative procedure was followed using 2-(2-
bromophenoxy)pyridine (1a) (125.0 mg, 0.5 mmol) and para-
toluenesulfonyl azide (2c) (98.5 mg, 0.5 mmol). After 12 h, purification by
column chromatography on silica gel (PE/EtOAc/DCM: 40:1:1 → 20:1:1)
to afford the desired product 3ca (127 mg, 60%) as a white solid. M. p. =
145−146 °C. 1H-NMR (400 MHz, CDCl3): δ = 11.64 (br s, 1H), 8.33 (d, J
= 5.3 Hz, 1H), 7.94 (ddd, J = 7.7, 7.6, 1.6 Hz, 1H), 7.74 (d, J = 8.0 Hz,
1H), 7.53 (dd, J = 8.0, 1.4 Hz, 1H), 7.48 (dd, J = 8.0, 1.4 Hz, 1H), 7.45 (d,
J = 8.2 Hz, 2H), 7.39 (dd, J = 7.5, 5.7 Hz, 1H), 7.23 (d, J = 8.2 Hz, 2H),
6.80 (dd, J = 8.0, 8.0 Hz, 1H), 2.43 (s, 3H). 13C-NMR (100 MHz, CDCl3):
δ = 153.5 (Cq), 152.9 (Cq), 147.2 (CH), 144.4 (Cq), 140.2 (CH), 135.7 (Cq),
134.5 (CH), 132.4 (CH), 129.5 (CH), 128.0 (CH), 126.9 (Cq), 125.1 (CH),
124.0 (CH), 120.4 (CH), 112.8 (Cq), 21.7 (s, CH3). HRMS (ESI) m/z calcd
for C18H16BrN2O3S [M + H]+: 419.0065, Found 419.0057.
4-Methyl-N-{3-methyl-2-(pyridin-2-yloxy)phenyl}benzenesulfon-
amide (3ga): The representative procedure was followed using 2-(o-
tolyloxy)pyridine (1g) (92.5 mg, 0.5 mmol) and para-toluenesulfonyl azide
(2a) (98.5 mg, 0.5 mmol). After 12 h, purification by column
chromatography on silica gel (PE/EtOAc/DCM: 40:1:1 → 20:1:1) to afford
the desired product 3ga (98 mg, 55%) as a white solid. M. p. =
109−111 °C. 1H-NMR (400 MHz, CDCl3): δ = 10.26 (br s, 1H), 8.34 (dd, J
= 5.0, 2.0 Hz, 1H), 7.87 (ddd, J = 7.8, 7.8, 2.0 Hz, 1H), 7.65 (d, J = 7.8
Hz, 1H), 7.53 (d, J = 8.3 Hz, 2H), 7.32 (ddd, J = 7.5, 7.5, 1.0 Hz, 1H),
7.28 (dd, J = 7.8, 1.0 Hz, 1H), 7.23 (d, J = 8.3 Hz, 2H), 7.14 (d, J = 7.5
Hz, 1H), 6.80 (dd, J = 7.8, 7.6 Hz, 1H), 2.43 (s, 3H), 2.18 (s, 3H). 13C-
NMR (100 MHz, CDCl3): δ = 154.0 (Cq), 153.5 (Cq), 147.5 (CH), 144.0
(Cq), 139.8 (CH), 136.2 (Cq), 132.0 (CH), 129.9 (CH), 129.3 (CH), 128.2
(CH), 128.0 (Cq), 125.7 (Cq), 124.5 (CH), 123.6 (CH), 119.4 (CH), 21.7
(CH3), 16.4 (CH3). HRMS (ESI) m/z calcd for C19H19N2O3S [M + H]+:
355.1116, Found 355.1113.
N-{3-iodo-2-(pyridin-2-yloxy)phenyl}-4-methylbenzenesulfonamide
(3da): The representative procedure was followed using 2-(2-
iodophenoxy)pyridine (1d) (145.5 mg, 0.5 mmol) and para-
toluenesulfonyl azide (2a) (98.5 mg, 0.5 mmol). After 12 h, purification by
N-{3-(tert-butyl)-2-(pyridin-2-yloxy)phenyl}-4-methylbenzenesulfon-
amide (3ha): The representative procedure was followed using 2-{2-(tert-
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201701028
Chemistry - An Asian Journal
FULL PAPER
butyl)phenoxy}pyridine (1h) (113.5 mg, 0.5 mmol) and para-
toluenesulfonyl azide (2a) (98.5 mg, 0.5 mmol). After 12 h, purification by
column chromatography on silica gel (PE/EtOAc/DCM: 20:0:1 → 10:1:1)
to afford the desired product 3ha (131 mg, 66%) as a white solid. M. p. =
131−132 °C. 1H-NMR (400 MHz, CDCl3): δ = 10.47 (br s, 1H), 8.35 (d, J
= 4.9 Hz, 1H), 7.90 (ddd, J = 7.8, 7.8, 1.7 Hz, 1H), 7.69 (d, J = 8.0 Hz,
1H), 7.49 (d, J = 8.4 Hz, 2H), 7.39−7.32 (m, 2H), 7.29−7.25 (m, 1H), 7.20
(d, J = 8.4 Hz, 2H), 6.84 (dd, J = 7.9, 7.9 Hz, 1H), 2.41 (s, 3H), 1.29 (s,
9H). 13C-NMR (100 MHz, CDCl3): δ = 154.4 (Cq), 154.1 (Cq), 147.3 (CH),
143.9 (Cq), 139.7 (CH), 139.3 (Cq), 136.2 (Cq), 130.4 (CH), 129.3 (CH),
128.2 (CH), 128.1 (CH), 126.5 (Cq), 124.8 (CH), 123.6 (CH), 119.0 (CH),
34.9 (Cq), 29.3 (CH3), 21.6 (CH3). HRMS (ESI) m/z calcd for
C22H25N2O3S [M + H]+: 397.1586, Found 397.1587.
N-{5-formyl-2-[(3-methylpyridin-2-yl)oxy]phenyl}-4-methylbenzene-
sulfonamide (3la): The representative procedure was followed using 4-
{(3-methylpyridin-2-yl)oxy}benzaldehyde (1l) (159.8 mg, 0.75 mmol),
para-toluenesulfonyl azide (2a) (98.5 mg, 0.5 mmol) , [Cp*IrCl2]2 (4.0 mg,
0.005 mmol) and AgSbF6 (6.9 mg, 0.02 mmol). After 12 h, purification by
column chromatography on silica gel (PE/EtOAc/DCM: 20:1:1 → 10:1:1)
to afford the desired product 3la (153 mg, 80%) as a white solid. M. p. =
196−197 °C. 1H-NMR (400 MHz, CDCl3): δ = 12.02 (br s, 1H), 9.91 (br s,
1H), 8.24 (dd, J = 5.0, 1.3 Hz, 1H), 8.12 (d, J = 2.0 Hz, 1H), 7.86 (d, J =
7.6 Hz, 1H), 7.80 (dd, J = 8.6, 2.0 Hz, 1H), 7.46 (d, J = 8.4 Hz, 2H), 7.39
(dd, J = 7.6, 7.6 Hz, 1H), 7.25 (d, J = 8.4 Hz, 2H), 6.91 (d, J = 8.6 Hz, 1H),
2.75 (s, 3H), 2.45 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ = 189.9 (Cq),
161.7 (Cq), 151.8 (Cq), 144.7 (CH), 144.4 (Cq), 142.2 (CH), 136.5 (CH),
136.2 (Cq), 136.0 (Cq), 131.7 (CH), 129.5 (CH), 129.5 (Cq), 128.2 (CH),
125.1 (Cq), 125.1 (CH), 119.7 (CH), 21.7 (CH3), 18.3 (CH3). HRMS (ESI)
m/z calcd for C20H19N2O4S [M + H]+: 383.1066, Found 383.1063.
4-Methyl-N-{2-(pyridin-2-yloxy)phenyl}benzenesulfonamide
(3ia):
The representative procedure was followed using 2-phenoxypyridine (1i)
(128.2 mg, 0.75 mmol) and para-toluenesulfonyl azide (2a) (98.5 mg, 0.5
mmol). After 12 h, purification by column chromatography on silica gel
(PE/EtOAc/DCM: 20:0:1 → 10:1:1) to afford the desired product 3ia (100
mg, 59%) as a white solid. M. p. = 166−167 °C. 1H-NMR (400 MHz,
CDCl3): δ = 10.38 (br s, 1H), 8.33 (dd, J = 5.1, 1.8 Hz, 1H), 7.89 (ddd, J =
7.8, 7.7, 2.0 Hz, 1H), 7.69 (d, J = 8.0 Hz, 1H), 7.49 (d, J = 8.4 Hz, 2H),
7.45 (dd, J = 8.2, 1.7 Hz, 1H), 7.34 (ddd, J = 7.6, 5.0, 1.0 Hz, 1H), 7.25 (d,
J = 7.9 Hz), 7.21 (d, J = 8.4 Hz, 2H), 6.91−6.86 (m, 2H), 2.42 (s, 3H).
13C-NMR (100 MHz, CDCl3): δ = 152.2 (CH), 154.0 (Cq), 147.4 (CH),
144.1 (Cq), 139.8 (CH), 136.2 (Cq), 132.8 (Cq), 131.0 (CH), 129.4 (CH),
128.1 (CH), 126.1 (Cq), 124.9 (CH), 123.7 (CH), 120.2 (CH), 119.1 (CH),
21.7 (CH3). HRMS (ESI) m/z calcd for C18H17N2O3S [M + H]+: 341.0960,
Found 341.0959.
N-{5-acetyl-2-[(3-methylpyridin-2-yl)oxy]phenyl}-4-methylbenzene-
sulfonamide (3ma): The representative procedure was followed using 1-
{4-[(3-methylpyridin-2-yl)oxy]phenyl}ethanone (1m) (170.2 mg, 0.75
mmol), para-toluenesulfonyl azide (2a) (98.5 mg, 0.5 mmol), [Cp*IrCl2]2
(4.0 mg, 0.005 mmol) and AgSbF6 (6.9 mg, 0.02 mmol). After 12 h,
purification by column chromatography on silica gel (PE/EtOAc/DCM:
20:1:1 → 10:1:1) to afford the desired product 3ma (99 mg, 50%) as a
white solid. M. p. = 167−168 °C. 1H-NMR (400 MHz, CDCl3): δ = 11.76
(br s, 1H), 8.23 (d, J = 5.0 Hz, 1H), 8.21 (d, J = 1.8 Hz, 1H), 7.88 (dd, J =
8.4, 1.8 Hz, 1H), 7.84 (d, J = 7.6 Hz, 1H), 7.46 (d, J = 8.1 Hz, 2H), 7.37
(dd, J = 7.6, 7.6 Hz, 1H), 7.24 (d, J = 8.1 Hz, 2H), 6.84 (d, J = 8.6 Hz, 1H),
2.74 (s, 3H), 2.59 (s, 3H), 2.45 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ =
195.9 (Cq), 160.4 (Cq), 152.0 (Cq), 144.7 (CH), 144.3 (Cq), 142.1 (CH),
136.1 (Cq), 136.1 (Cq), 134.4 (CH), 131.3 (CH), 129.9 (Cq), 129.4 (CH),
128.2 (CH), 125.0 (CH), 124.5 (Cq), 118.9 (CH), 26.3 (CH3), 21.7 (CH3),
18.4 (CH3). HRMS (ESI) m/z calcd for C21H21N2O4S [M + H]+: 397.1222,
Found 397.1225.
N-{5-bromo-2-(pyridin-2-yloxy)phenyl}-4-methylbenzenesulfonamide
(3ja): The representative procedure was followed using 2-(4-
bromophenoxy)pyridine (1j) (187.5 mg, 0.75 mmol) and para-
toluenesulfonyl azide (2a) (98.5 mg, 0.5 mmol). After 12 h, purification by
column chromatography on silica gel (PE/EtOAc/DCM: 40:1:1 → 20:1:1)
to afford the desired product 3ja (108 mg, 51%) as a white solid. M. p. =
156−157 °C. 1H-NMR (400 MHz, CDCl3): δ = 10.72 (br s, 1H), 8.33 (dd, J
= 4.7, 1.6 Hz, 1H), 7.94 (ddd, J = 7.8, 7.8, 1.6 Hz, 1H), 7.71 (d, J = 7.8
Hz, 1H), 7.62 (d, J = 2.3 Hz, 1H), 7.49 (d, J = 8.2 Hz, 2H), 7.39 (dd, J =
7.3, 7.3 Hz, 1H), 7.34 (dd, J = 8.7, 2.3 Hz, 1H), 7.24 (d, J = 8.2 Hz, 2H),
6.79 (d, J = 8.7 Hz, 1H), 2.44 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ =
154.7 (Cq), 153.5 (Cq), 147.4 (CH), 144.4 (Cq), 140.1 (CH), 135.9 (Cq),
135.3 (CH), 133.9 (CH), 129.5 (CH), 128.1 (CH), 127.2 (Cq), 125.2 (CH),
124.1 (CH), 120.6 (CH), 111.0 (Cq), 21.7 (CH3). HRMS (ESI) m/z calcd
for C18H16BrN2O3S [M + H]+: 419.0065, Found 419.0065.
Methyl
3-(4-methylphenylsulfonamido)-4-{(3-methylpyridin-2-
yl)oxy}benzoate (3na): The representative procedure was followed
using methyl 4-{(3-methylpyridin-2-yl)oxy}benzoate (1n) (182.2 mg, 0.75
mmol), para-toluenesulfonyl azide (2a) (98.5 mg, 0.5 mmol), [Cp*IrCl2]2
(4.0 mg, 0.005 mmol) and AgSbF6 (6.9 mg, 0.02 mmol). After 12 h,
purification by column chromatography on silica gel (PE/EtOAc/DCM:
20:1:1 → 10:1:1) to afford the desired product 3na (126 mg, 61%) as a
white solid. M. p. = 157−158 °C. 1H-NMR (400 MHz, CDCl3): δ = 11.68
(br s, 1H), 8.30 (d, J = 2.0 Hz, 1H), 8.23 (d, J = 4.0 Hz, 1H), 7.93 (dd, J =
8.6, 2.0 Hz, 1H), 7.84 (d, J = 7.6 Hz, 1H), 7.47 (d, J = 8.2 Hz, 2H), 7.36
(dd, J = 7.6, 7.6 Hz, 1H), 7.24 (d, J = 8.2 Hz, 2H), 6.82 (d, J = 8.6 Hz, 1H),
3.92 (s, 3H), 2.75 (s, 3H), 2.45 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ =
156.2 (Cq), 160.2 (Cq), 152.1 (Cq), 144.7 (CH), 144.2 (Cq), 142.0 (CH),
136.2 (Cq), 136.2 (Cq), 135.2 (CH), 132.6 (CH), 129.4 (CH), 128.2 (CH),
124.9 (CH), 124.5 (Cq), 122.1 (Cq), 118.8 (CH), 52.0 (CH3), 21.7 (CH3),
18.4 (CH3). HRMS (ESI) m/z calcd for C21H21N2O5S [M + H]+: 413.1171,
Found 413.1171.
4-Methyl-N-{2-((3-methylpyridin-2-yl)oxy)-5-nitrophenyl}benzene-
sulfonamide (3ka): The representative procedure was followed using 3-
methyl-2-(4-nitrophenoxy)pyridine (1k) (172.5 mg, 0.75 mmol), para-
toluenesulfonyl azide (2a) (98.5 mg, 0.5 mmol), [Cp*IrCl2]2 (4.0 mg, 0.005
mmol) and AgSbF6 (6.9 mg, 0.02 mmol). After 12 h, purification by
column chromatography on silica gel (PE/EtOAc/DCM: 40:1:1 → 20:1:1)
to afford the desired product 3ka (126 mg, 63%) as a white solid. M. p. =
194−195 °C. 1H-NMR (400 MHz, CDCl3): δ = 12.41 (br s, 1H), 8.52 (d, J
= 2.5 Hz, 1H), 8.24 (d, J = 4.4 Hz, 1H), 8.14 (dd, J = 8.8, 2.5 Hz, 1H),
7.89 (d, J = 7.7 Hz, 1H), 7.45 (d, J = 8.6 Hz, 2H), 7.44‒ 7.39 (m, 1H),
7.26 (d, J = 8.6 Hz, 2H), 6.86 (d, J = 9.0 Hz, 1H), 2.75 (s, 3H), 2.46 (s,
3H). 13C-NMR (100 MHz, CDCl3): δ = 162.2 (Cq), 151.4 (Cq), 144.7 (Cq),
144.6 (CH), 142.5 (CH), 140.3 (Cq), 136.4 (Cq), 135.7 (Cq), 129.7 (CH),
129.6 (CH), 128.2 (CH), 126.7 (CH), 125.3 (CH), 124.6 (Cq), 119.1 (CH),
21.7 (CH3), 18.4 (CH3). HRMS (ESI) m/z calcd for C19H18N3O5S [M + H]+:
400.0967, Found 400.0967.
4-Methyl-N-{4-methyl-2-(pyridin-2-yloxy)phenyl}benzenesulfon-
amide (3oa): The representative procedure was followed using 2-(m-
tolyloxy)pyridine (1o) (92.5 mg, 0.5 mmol) and para-toluenesulfonyl azide
(2a) (98.5 mg, 0.5 mmol). After 12 h, purification by column
chromatography on silica gel (PE/EtOAc/DCM: 40:1:1 → 20:1:1) to afford
the desired product 3oa (124 mg, 70%) as a white solid. M. p. =
123−124 °C. 1H-NMR (400 MHz, CDCl3): δ = 10.24 (br s, 1H), 8.33 (d, J
= 4.9 Hz, 1H), 7.89 (ddd, J = 7.8, 7.8, 1.8 Hz, 1H), 7.68 (d, J = 7.8 Hz,
1H), 7.52 (d, J = 8.2 Hz, 2H), 7.37‒ 7.31 (m, 2H), 7.24 (d, J = 8.2 Hz, 2H),
6.73 (s, 1H), 6.72 (d, J = 8.2 Hz, 1 H), 2.43 (s, 3H), 2.30 (s, 3H). 13C-
NMR (100 MHz, CDCl3): δ = 154.7 (Cq), 154.1 (Cq), 147.4 (CH), 144.0
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201701028
Chemistry - An Asian Journal
FULL PAPER
1
(Cq), 141.5 (Cq), 139.8 (CH), 136.3 (Cq), 132.4 (CH), 129.4 (CH), 128.1
(CH), 124.8 (CH), 123.6 (CH), 123.5 (Cq), 121.2 (CH), 119.5 (CH), 21.7
(CH3), 21.3 (CH3). HRMS (ESI) m/z calcd for C19H19N2O3S [M + H]+:
355.1116, Found 355.1117.
(100 MHz, CDCl3): δ = 165.6 (d, JC‒ F = 256 Hz, Cq), 153.1 (Cq), 148.0
4
(CH), 140.7 (CH), 138.5 (CH), 136.1 (d, JC‒ F = 3 Hz, Cq), 135.5 (Cq),
3
131.6 (d, JC‒ F = 9 Hz, CH), 128.8 (Cq), 126.3 (CH), 120.8 (CH), 119.5
(CH), 116.8 (CH), 115.9 (d, 2JC‒ F = 22 Hz, CH) (One Cq is invisible). 19F-
NMR (376 MHz, CDCl3) δ = −(104.0−104.2) (m). HRMS (ESI) m/z calcd
for C17H13FN3O5S [M + H]+: 390.0560, Found 390.0557.
N-{3,5-dichloro-2-(pyridin-2-yloxy)phenyl}-4-methylbenzenesulfon-
amide (3pa): The representative procedure was followed using 2-(2,4-
dichlorophenoxy)pyridine (1p) (120.0 mg, 0.50 mmol), TsN3 (2a) (127.8
mg, 0.6 mmol). After 12 h, purification by column chromatography on
silica gel (PE/EtOAc/DCM: 40:1:1 → 20:1:1) yielded 3pa (116 mg, 56%)
as a white solid. M. p. = 153−154 °C. 1H-NMR (400 MHz, CDCl3): δ =
11.77 (br s, 1H), 8.32 (d, J = 5.0 Hz, 1H), 7.97 (ddd, J = 7.8, 7.8, 1.8 Hz,
1H), 7.74 (d, J = 7.8 Hz, 1H), 7.53‒ 7.40 (m, 4H), 7.37 (d, J = 2.7 Hz, 1H),
7.24 (d, J = 8.2 Hz, 2H), 2.44 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ =
153.1 (Cq), 151.1 (Cq), 147.2 (CH), 144.7 (Cq), 140.4 (CH), 135.5 (Cq),
131.4 (CH), 131.2 (CH), 129.6 (CH), 128.0 (CH), 127.6 (Cq), 125.3 (CH),
124.3 (CH), 123.6 (Cq), 21.7 (CH3). HRMS (ESI) m/z calcd for
C18H15Cl2N2O3S [M + H]+: 409.0180, Found 409.0171.
4-Chloro-N-{3-nitro-2-(pyridin-2-yloxy)phenyl}benzenesulfonamide
(3ee): The representative procedure was followed using 2-(2-
nitrophenoxy)pyridine
(1e)
(108.0
mg,
0.5
mmol),
4-
chlorobenzenesulfonyl azide (2e) (130.6 mg, 0.6 mmol), [Cp*IrCl2]2 (4.0
mg, 0.005 mmol) and AgSbF6 (6.9 mg, 0.02 mmol). After 12 h,
purification by column chromatography on silica gel (PE/EtOAc/DCM:
20:1:1 → 10:1:1) to afford the desired product 3ee (166 mg, 82%) as a
1
yellow solid. M. p. = 153−154 °C. H-NMR (400 MHz, CDCl3): δ = 11.04
(br s, 1H), 8.31 (d, J = 5.0 Hz, 1H), 8.22 (dd, J = 8.6, 1.2 Hz, 1H), 7.98 (d,
J = 8.6 Hz, 2H), 7.82 (dd, J = 7.8, 1.2 Hz, 1H), 7.65 (ddd, J = 7.8, 7.8, 1.7
Hz, 1H), 7.49 (d, J = 8.6 Hz, 2H), 7.09‒ 7.01 (m, 3H). 13C-NMR (100 MHz,
CDCl3): δ = 153.1 (Cq), 153.0 (Cq), 148.0 (CH), 140.7 (CH), 139.8 (Cq),
138.7 (Cq), 138.5 (CH), 135.4 (Cq), 130.2 (CH), 129.0 (CH), 128.8 (Cq),
126.3 (CH), 120.8 (CH), 119.5 (CH), 116.7 (CH). HRMS (ESI) m/z calcd
for C17H13ClN3O5S [M + H]+: 406.0264, Found 406.0264.
N-{3-nitro-2-(pyridin-2-yloxy)phenyl}benzenesulfonamide (3eb): The
representative procedure was followed using 2-(2-nitrophenoxy)pyridine
(1e) (108.0 mg, 0.5 mmol), benzenesulfonyl azide (2b) (109.8 mg, 0.6
mmol), [Cp*IrCl2]2 (4.0 mg, 0.005 mmol) and AgSbF6 (6.9 mg, 0.02
mmol). After 12 h, purification by column chromatography on silica gel
(PE/EtOAc/DCM: 40:1:1 → 20:1:1) to afford the desired product 3eb (184
mg, 99%) as a yellow solid. M. p. = 159−160 °C. 1H-NMR (400 MHz,
CDCl3): δ = 11.09 (br s, 1H), 8.29 (dd, J = 4.9, 1.2 Hz, 1H), 8.19 (dd, J =
8.6, 1.5 Hz, 1H), 7.99 (d, J = 7.8 Hz, 2H), 7.82 (dd, J = 7.8, 1.5 Hz, 1H),
7.67 (ddd, J = 7.8, 7.8, 2.0 Hz, 1H), 7.63 (dd, J = 7.5, 7.5 Hz, 1H), 7.52
(dd, J = 7.8, 7.5 Hz, 2H), 7.26 (dd, J = 8.6, 8.6 Hz, 1H), 7.16‒ 7.05 (m,
2H). 13C-NMR (100 MHz, CDCl3): δ = 153.1 (Cq), 153.1 (Cq), 148.0 (CH),
140.7 (CH), 140.0 (Cq), 138.4 (CH), 135.5 (Cq), 133.3 (CH), 129.0 (Cq),
128.8 (CH), 128.5 (CH), 126.1 (CH), 120.8 (CH), 119.3 (CH), 117.4 (CH).
HRMS (ESI) m/z calcd for C17H14N3O5S [M + H]+: 372.0654, Found
372.0653.
3-Methyl-N-{3-nitro-2-(pyridin-2-yloxy)phenyl}benzenesulfonamide
(3ef): The representative procedure was followed using 2-(2-
nitrophenoxy)pyridine
(1e)
(108.0
mg,
0.5
mmol),
3-
methylbenzenesulfonyl azide (2f) (118.2 mg, 0.6 mmol), [Cp*IrCl2]2 (4.0
mg, 0.005 mmol) and AgSbF6 (6.9 mg, 0.02 mmol). After 12 h,
purification by column chromatography on silica gel (PE/EtOAc/DCM:
20:1:1 → 10:1:1) to afford the desired product 3ef (148 mg, 77%) as a
1
yellow solid. M. p. = 143−144 °C. H-NMR (400 MHz, CDCl3): δ = 11.14
(br s, 1H), 8.29 (d, J = 5.0 Hz, 1H), 8.19 (d, J = 8.6 Hz, 1H), 7.81 (d, J =
7.8 Hz, 1H), 7.77 (s, 1H), 7.76 (d, J = 8.6 Hz, 1H), 7.69 (ddd, J = 7.8, 7.8,
1.2 Hz, 1H), 7.46‒ 7.37 (m, 2H), 7.30 (d, J = 8.4 Hz, 1H), 7.14‒ 7.06 (m,
2H), 2.43 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ = 153.1 (Cq), 148.0
(CH), 140.6 (CH), 139.8 (Cq), 139.0 (Cq), 138.4 (CH), 135.6 (Cq), 134.2
(CH), 129.1 (Cq), 128.7 (CH), 128.7 (CH), 126.1 (CH), 125.5 (CH), 120.9
(CH), 119.3 (CH), 117.6 (CH), 21.4 (CH3) (One Cq is invisible). HRMS
(ESI) m/z calcd for C18H16N3O5S [M + H]+: 386.0811, Found 386.0808.
4-Methoxy-N-{3-nitro-2-(pyridin-2-yloxy)phenyl}benzenesulfonamide
(3ec): The representative procedure was followed using 2-(2-
nitrophenoxy)pyridine
(1e)
(108.0
mg,
0.5
mmol),
4-
methoxybenzenesulfonyl azide (2c) (127.8 mg, 0.6 mmol), [Cp*IrCl2]2
(4.0 mg, 0.005 mmol) and AgSbF6 (6.9 mg, 0.02 mmol). After 12 h,
purification by column chromatography on silica gel (PE/EtOAc/DCM:
20:1:1 → 10:1:1) to afford the desired product 3ec (192 mg, 96%) as a
3-Fluoro-N-{3-nitro-2-(pyridin-2-yloxy)phenyl}benzenesulfonamide
(3eg): The representative procedure was followed using 2-(2-
nitrophenoxy)pyridine
(1e)
(108.0
mg,
0.5
mmol),
3-
1
yellow solid. M. p. = 144−145 °C. H-NMR (400 MHz, CDCl3): δ = 11.13
fluorobenzenesulfonyl azide (2g) (120.6 mg, 0.6 mmol), [Cp*IrCl2]2 (4.0
mg, 0.005 mmol) and AgSbF6 (6.9 mg, 0.02 mmol). After 12 h,
purification by column chromatography on silica gel (PE/EtOAc/DCM:
20:1:1 → 8:1:1) to afford the desired product 3eg (136 mg, 70%) as a
(br s, 1H), 8.29 (d, J = 5.0 Hz, 1H), 8.18 (d, J = 8.6 Hz, 1H), 7.92 (d, J =
8.8 Hz, 2H), 7.81 (d, J = 7.8 Hz, 1H), 7.66 (dd, J = 8.0, 7.8 Hz, 1H), 7.24
(d, J = 8.2 Hz, 1H), 7.12‒ 7.04 (m, 2H), 6.97 (d, J = 8.8 Hz, 2H), 3.89 (s,
3H). 13C-NMR (100 MHz, CDCl3): δ = 163.5 (Cq), 153.2 (Cq), 153.1 (Cq),
147.9 (CH), 140.7 (CH), 138.4 (CH), 135.6 (Cq), 131.4 (Cq), 130.8 (CH),
129.2 (Cq), 126.0 (CH), 120.6 (CH), 119.3 (CH), 117.2 (CH), 113.9 (CH),
55.6 (CH3). HRMS (ESI) m/z calcd for C18H16N3O6S [M + H]+: 402.0760,
Found 402.0761.
1
yellow solid. M. p. = 140−141 °C. H-NMR (400 MHz, CDCl3): δ = 11.07
(br s, 1H), 8.32 (d, J = 4.1 Hz, 1H), 8.23 (dd, J = 8.6, 1.6 Hz, 1H),
7.88‒ 7.73 (m, 3H), 7.67 (ddd, J = 8.0, 7.6, 1.8 Hz, 1H), 7.55‒ 7.48 (m,
1H), 7.33 (d, J = 8.2, 8.2, 1.5 Hz, 1H), 7.17‒ 7.07 (m, 3H). 13C-NMR (100
1
MHz, CDCl3): δ = 162.2 (d, JC‒ F = 251 Hz, Cq), 153.0 (Cq), 152.9 (Cq),
148.1 (CH), 142.1 (3JC‒ F = 7 Hz, Cq), 140.7 (CH), 138.5 (CH), 135.5 (Cq),
3
4
130.4 (d, JC‒ F = 7 Hz, CH), 128.7 (Cq), 126.3 (CH), 124.3 (d, JC‒ F = 3
4-Fluoro-N-{3-nitro-2-(pyridin-2-yloxy)phenyl}benzenesulfonamide
(3ed): The representative procedure was followed using 2-(2-
2
Hz, CH), 121.0 (CH), 120.5 (d, JC‒ F = 24 Hz, CH), 119.5 (CH), 117.0
(CH), 116.1 (d, JC‒ F = 24 Hz, CH). 19F-NMR (376 MHz, CDCl3) δ =
2
nitrophenoxy)pyridine
(1e)
(108.0
mg,
0.5
mmol),
4-
‒ (109.9‒ 110.0) (m). HRMS (ESI) m/z calcd for C17H13FN3O5S [M + H]+:
fluorobenzenesulfonyl azide (2d) (120.6 mg, 0.6 mmol), [Cp*IrCl2]2 (4.0
mg, 0.005 mmol) and AgSbF6 (6.9 mg, 0.02 mmol). After 12 h,
purification by column chromatography on silica gel (PE/EtOAc/DCM:
20:1:1 → 10:1:1) to afford the desired product 3ed (190 mg, 98%) as a
390.0560, Found 390.0561.
2-Fluoro-N-{3-nitro-2-(pyridin-2-yloxy)phenyl}benzenesulfonamide
(3eh): A) The representative procedure was followed using 2-(2-
1
yellow solid. M. p. = 161−162 °C. H-NMR (400 MHz, CDCl3): δ = 11.07
(br s, 1H), 8.31 (dd, J = 5.2, 1.7 Hz, 1H), 8.22 (dd, J = 8.6, 1.1 Hz, 1H),
8.11‒ 8.01 (m, 2H), 7.83 (dd, J = 7.8, 1.1 Hz, 1H), 7.66 (ddd, J = 7.8, 7.8,
1.5 Hz, 1H), 7.19 (dd, J = 8.6, 8.6 Hz, 2H), 7.15‒ 7.07 (m, 3H). 13C-NMR
nitrophenoxy)pyridine
methylbenzenesulfonyl azide (2h) (118.2 mg, 0.6 mmol), [Cp*IrCl2]2 (4.0
mg, 0.005 mmol) and AgSbF6 (6.9 mg, 0.02 mmol). After 12 h,
(1e)
(108.0
mg,
0.5
mmol),
2-
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201701028
Chemistry - An Asian Journal
FULL PAPER
purification by column chromatography on silica gel (PE/EtOAc/DCM:
20:1:1 → 10:1:1) to afford the desired product 3eh (74 mg, 39%) as a
yellow solid. B) The representative procedure was followed using 2-(2-
chromatography (PE/EtOAc/DCM = 20:1:1→10:1:1→6:1:1) to yield 3ea
(5 mg, 2%) as a yellow solid and 3qa (62 mg, 34%) as a white solid.
nitrophenoxy)pyridine
(1e)
(108.0
mg,
0.5
mmol),
2-
Intermolecular competition experiment with azides 2c and 2d
(Scheme 5): The mixture of 2-(2-nitrophenoxy)pyridine (1e) (92.5 mg,
0.5 mmol), 4-methoxybenzenesulfonyl azide (2c) (213.0 mg, 1.0 mmol),
4-fluorobenzenesulfonyl azide (2d) (201.0 mg, 1.0 mmol), [Cp*IrCl2]2 (4.0
mg, 0.005 mmol), AgSbF6 (6.9 mg, 0.02 mmol) and 1,2-DCE (2.0 mL)
was stirred at 80 °C under N2 for 12 h. The reaction mixture was cooled
to ambient temperature, filtered through a pad of celite and silica gel, and
washed with EtOAc (3 x 10 mL). The solvents were removed under
reduced pressure. The residue was purified by silica gel column
chromatography (PE/EtOAc/DCM = 20:1:1→8:1:1) to yield 3ed (66 mg,
34%) as a yellow solid and 3ec (121 mg, 60%) as a yellow solid.
methylbenzenesulfonyl azide (2h) (118.2 mg, 0.6 mmol), [Cp*IrCl2]2 (8.0
mg, 0.01 mmol) and AgSbF6 (13.8 mg, 0.04 mmol). After 12 h,
purification by column chromatography on silica gel (PE/EtOAc/DCM:
20:1:1 → 10:1:1) to afford the desired product 3eh (187 mg, 97%) as a
1
yellow solid. M. p. = 100−101 °C. H-NMR (400 MHz, CDCl3): δ = 11.22
(br s, 1H), 8.30 (d, J = 4.1 Hz, 1H), 8.14 (d, J = 8.5 Hz, 1H), 7.96 (d, J =
8.0 Hz, 1H), 7.81 (d, J = 7.7 Hz, 1H), 7.73 (dd, J = 8.0, 7.5 Hz, 1H), 7.49
(dd, J = 7.7, 7.5 Hz, 1H), 7.45 (d, J = 8.4 Hz, 1H), 7.33 (d, J = 7.5 Hz, 1H),
7.30‒ 7.25 (m, 1H), 7.15 (dd, J = 7.1, 6.8 Hz, 1H), 7.04 (dd, J = 8.0, 8.0
Hz, 1H), 2.56 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ = 153.3 (Cq), 153.0
(Cq), 148.0 (CH), 140.4 (CH), 138.5 (Cq), 138.4 (CH), 138.3 (Cq), 135.6
(Cq), 133.3 (CH), 132.8 (CH), 130.4 (CH), 129.0 (Cq), 126.1 (CH), 125.9
(CH), 121.4 (CH), 119.5 (CH), 119.1 (CH), 20.7 (CH3). HRMS (ESI) m/z
calcd for C18H16N3O5S [M + H]+: 386.0811, Found 386.0809.
Iridium-catalyzed direct ortho-C–H amidation azide 2a with diaryl
ether 1i in 1,2-DCE and [D]4-AcOH (Scheme 6): A mixture of 2-
phenoxypyridine (1i) (342.0 mg, 2.0 mmol), para-toluenesulfonyl azide
(2a) (197.0 mg, 1.0 mmol), [Cp*IrCl2]2 (8.0 mg, 0.01 mmol), AgSbF6 (13.8
mg, 0.04 mmol), 1,2-DCE (2.0 mL) and [D]4-AcOH (112 μL, 2.0 mmol)
was stirred at 80 °C under N2 for 12 h. The reaction mixture was cooled
to ambient temperature, filtered through a pad of celite and silica gel, and
washed with EtOAc (3 x 10 mL). The solvents were removed under
reduced pressure. The residue was purified by silica gel column
chromatography (PE/EtOAc/DCM = 40:1:1→20:1:1) to give [D]n-1i (117
mg, 68%) as a white solid and [D]n-3ia (74 mg, 22%) as a white solid.
The deuterium incorporation was estimated by 1H-NMR spectroscopy.
2-Fluoro-N-{3-nitro-2-(pyridin-2-yloxy)phenyl}benzenesulfonamide
(3ei): The representative procedure was followed using 2-(2-
nitrophenoxy)pyridine
fluorobenzenesulfonyl azide (2i) (120.6 mg, 0.6 mmol), [Cp*IrCl2]2 (4.0
mg, 0.005 mmol) and AgSbF6 (6.9 mg, 0.02 mmol). After 12 h,
purification by column chromatography on silica gel (PE/EtOAc/DCM:
20:1:1 → 10:1:1) to afford the desired product 3ei (186 mg, 96%) as a
(1e)
(108.0
mg,
0.5
mmol),
2-
1
yellow solid. M. p. = 177−178 °C. H-NMR (400 MHz, CDCl3): δ = 11.11
(br s, 1H), 8.26 (dd, J = 5.0, 1.1 Hz, 1H), 8.19 (dd, J = 8.6, 1.5 Hz, 1H),
8.06 (ddd, J = 7.6, 7.4, 1.5 Hz, 1H), 7.91 (dd, J = 7.8, 1.3 Hz, 1H), 7.68
(ddd, J = 7.8, 7.8, 1.8 Hz, 1H), 7.66‒ 7.59 (m, 1H), 7.35‒ 7.23 (m, 2H),
7.20 (dd, J = 9.3, 9.3 Hz, 1H), 7.14‒ 7.07 (m, 2H). 13C-NMR (100 MHz,
Removal of the directing group (Scheme 8): [16k,16n] To a solution of 4-
methyl-N-{2-(pyridin-2-yloxy)phenyl}benzenesulfonamide (3ia) (170.0 mg,
0.5 mmol) in PhMe (10.0 mL) under N2 was added MeOTf (100 μL, 0.88
mmol). The reaction mixture was stirred under N2 at 100 °C for 4 h. The
reaction mixture was allowed to cool to ambient temperature.
Evaporation of the solvent in vacuo yielded a white solid. The solid was
dissolved in dry MeOH (5.0 mL) and was added under N2 to a solution of
Na (276 mg, 12 mmol) in dry MeOH (20.0 mL). The reaction mixture was
heated at 90 °C for 2 h. The reaction mixture was allowed to cool to
ambient temperature and the solvent was evaporated in vacuo. H2O (50
mL) was added, and the resulting mixture was extracted with EtOAc (3 x
50 mL). The combined organic layers were dried over Na2SO4. After
filtration and evaporation of the solvents in vacuo, the residue was
1
CDCl3): δ = 159.2 (d, JC‒ F = 258 Hz, Cq), 153.2 (Cq), 153.1 (Cq), 147.9
4
3
(CH), 140.8 (d, JC‒ F = 2 Hz, CH), 138.4 (CH), 135.7 (d, JC‒ F = 8 Hz,
2
CH), 135.4 (Cq), 131.9 (CH), 128.8 (Cq), 128.4 (d, JC‒ F = 13 Hz, Cq),
3
126.1 (CH), 124.2 (d, JC‒ F = 4 Hz, CH), 121.0 (CH), 119.3 (CH), 117.5
2
(CH), 117.2 (d, JC‒ F = 21 Hz, CH). 19F-NMR (376 MHz, CDCl3) δ =
−(106.9−107.1) (m). HRMS (ESI) m/z calcd for C17H13FN3O5S [M + H]+:
390.0560, Found 390.0560.
N-{3-nitro-2-(pyridin-2-yloxy)phenyl}methanesulfonamide (3ej): The
representative procedure was followed using 2-(2-nitrophenoxy)pyridine
(1e) (108.0 mg, 0.5 mmol), methanesulfonyl azide (2j) (72.6 mg, 0.6
mmol), [Cp*IrCl2]2 (4.0 mg, 0.005 mmol) and AgSbF6 (6.9 mg, 0.02
mmol). After 12 h, purification by column chromatography on silica gel
(PE/EtOAc/DCM: 20:1:1 → 10:1:1) to afford the desired product 3ej (98
mg, 63%) as a yellow solid. M. p. = 120−121 °C. 1H-NMR (400 MHz,
CDCl3): δ = 11.01 (br s, 1H), 8.44 (d, J = 3.8 Hz, 1H), 8.24 (dd, J = 8.2,
1.1 Hz, 1H), 7.87 (dd, J = 7.8, 1.1 Hz, 1H), 7.62 (dd, J = 7.8, 7.8 Hz, 1H),
7.16 (dd, J = 8.2, 8.2 Hz, 1H), 7.09 (dd, J = 7.8, 7.8 Hz, 1H), 6.75 (d, J =
8.2 Hz, 1H), 3.65 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ = 153.9 (Cq),
152.7 (Cq), 148.1 (CH), 141.6 (CH), 138.5 (CH), 135.1 (Cq), 128.7 (Cq),
126.2 (CH), 119.9 (CH), 119.7 (CH), 113.8 (CH), 42.9 (CH3). HRMS
(ESI) m/z calcd for C12H12N3O5S [M + H]+: 310.0498, Found 310.0498.
purified by silica gel column chromatography (PE/EtOAc/DCM
=
10:1:1→6:1:1) to afford N-(2-hydroxyphenyl)-4-methylbenzenesulfon-
amide (4ia) (97 mg, 73%) as a white solid. M. p. = 142−143 °C. 1H-NMR
(400 MHz, CDCl3): δ = 7.64 (d, J = 8.2 Hz, 2H), 7.23 (d, J = 8.2 Hz, 2H),
7.07 (dd, J = 7.8, 7.8 Hz, 1H), 6.94‒ 6.85 (m, 2H), 6.76 (d, J = 7.8 Hz,
1H), 6.73 (br s, 1H), 6.59 (br s, 1H), 2.40 (s, 3H). 13C-NMR (100 MHz,
CDCl3): δ = 150.2 (Cq), 144.3 (Cq), 135.0 (Cq), 129.6 (CH), 127.9 (CH),
127.5 (CH), 125.2 (CH), 123.0 (Cq), 121.0 (CH), 116.9 (CH), 21.6 (CH3).
HRMS (ESI) m/z calcd for C13H14NO3S [M + H]+: 264.0694, Found
264.0692. The spectral data were in accordance with those reported in
the literature.[19]
Intermolecular competition experiment with diaryl ethers 1q and 1e
(Scheme 4): The mixture of 2-(2-methoxyphenoxy)pyridine (1q) (201.0
mg, 1.0 mmol), 2-(2-nitrophenoxy)pyridine (1e) (216.0 mg, 1.0 mmol),
para-toluenesulfonyl azide (2a) (98.5 mg, 0.5 mmol), [Cp*IrCl2]2 (4.0 mg,
0.005 mmol), AgSbF6 (6.9 mg, 0.02 mmol) and 1,2-DCE (2.0 mL) was
stirred at 80 °C under N2 for 12 h. The reaction mixture was cooled to
ambient temperature, filtered through a pad of celite and silica gel, and
washed with EtOAc (3 x 10 mL). The solvents were removed under
reduced pressure. The residue was purified by silica gel column
Acknowledgements
This research was supported by NSF of China (Nos. 21602064
and 21572072), NSF of Fujian Province (2015J01056, JA15032),
Xiamen Southern Oceanographic Center (15PYY052SF01), and
Huaqiao University (ZQN-PY317).
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201701028
Chemistry - An Asian Journal
FULL PAPER
Ryu, J. Kwak, K. Shin, D. Lee, S. Chang, J. Am. Chem. Soc. 2013, 135,
12861−12868.
Keywords: Amination • azides • hydroxyanilines • iridium •
phenoxypyridines
[12] Selected contributions from other groups, see: a) S. Chen, B. Feng, X.
Zheng, J. Yin, S. Yang, J. You, Org. Lett. 2017, 19, 2502−2505; b) S. Kim,
P. Chakrasali, H. S. Suh, N. K. Mishra, T. Kim, S. H. Han, H. S. Kim, B. M.
Lee, S. B. Han, I. S. Kim, J. Org. Chem. 2017, 82, DOI:
10.1021/acs.joc.7b01280; c) S. H. Han, H. S. Suh, H. Jo, Y. Oh, N. K.
Mishra, S. Han, H. S. Kim, Y. H. Jung, B. M. Lee, I. S. Kim, Bioorg. Med.
Chem. Lett. 2017, 27, 2129−2134; d) X. Xiao, C. Hou, Z. Zhang, Z. Ke, J.
Lan, H. Jiang, W. Zeng, Angew. Chem. Int. Ed. 2016, 55, 11897−11901;
Angew. Chem. 2016, 128, 12076−12080; e) G. N. Hermann, P. Becker, C.
Bolm, Angew. Chem. Int. Ed. 2016, 55, 3781−3784; Angew. Chem. 2016,
128, 3845−3848; f) Z. Song, A. P. Antonchick, Org. Biomol. Chem. 2016,
14, 4804−4808; g) L. Xu, L. Tan, D. Ma, J. Org. Chem. 2016, 81,
10476−10483; h) T. Zhang, X. Hu, Z. Wang, T. Yang, H. Sun, G. Li, H. Lu,
Chem. Eur. J. 2016, 22, 2920−2924; i) M. A. Ali, X. Yao, G. Li, H. Lu, Org.
Lett. 2016, 18, 1386−1389; j) H. Chen, M. P. Huestis, ChemCatChem
2015, 7, 743−746.
[1] a) A. Ricci, Amino Group Chemistry: From Synthesis to the Life Sciences;
Wiley-VCH: Weinheim, 2007; b) R. Hili, A. K. Yudin, Nat. Chem. Biol.
2006, 2, 284−287.
[2] a) Z. Zhang, C. Shao, P. Zou, P. Zhang, M. Zhang, J. Mu, Z. Guo, X. Li, C.
Wang, Y. Liu, Chem. Commun. 2011, 47, 3906−3908; b) D. Jana, A.
Dandapat, G. De, Langmuir 2010, 26, 12177−12184.
[3] S. A. Lawrence, Amines: Synthesis Properties and Applications,
Cambridge University Press, Cambridge, 2004.
[4] S. Enthaler, ChemSusChem 2010, 3, 1024−1029.
[5] J. Bariwal, E. Van der Eycken, Chem. Soc. Rev. 2013, 42, 9283−9303.
[6] a) D. S. Surry, S. L. Buchwald, Angew. Chem. Int. Ed. 2008, 47,
6338−6361; Angew. Chem. 2008, 120, 6438−6461; b) J. F. Hartwig, Acc.
Chem. Res. 2008, 41, 1534−1544.
[7] a) F. Monnier, M. Taillefer, Angew. Chem. Int. Ed. 2009, 48, 6954−6971;
Angew. Chem. 2009, 121, 7088−7105; b) G. Evano, N. Blanchard, M.
Toumi, Chem. Rev. 2008, 108, 3054−3131.
[13] For direct C‒ N amidation with a modifiable directing group, see: a) D. Lee,
S. Chang, Chem. Eur. J. 2015, 21, 5364−5368; b) Y.-F. Zhang, B. Wu, Z.-
J. Shi, Chem. Eur. J. 2016, 22, 17808−17812.
[8] Y. Aubin, C. Fischmeister, C. M. Thomas, J.-L. Renaud, Chem. Soc. Rev.
2010, 39, 4130−4145.
[14] For reviews, see: a) W. Ma, P. Gandeepan, J. Li, L. Ackermann, Org.
Chem. Front. 2017, 4, 1435−1467; b) R. K. Rit, M. R. Yadav, K. Ghosh, A.
K. Sahoo, Tetrahedron 2015, 71, 4450−4459; c) H. Sun, Y. Huang,
Synlett 2015, 26, 2751−2762; d) M. R. Yadav, R. K. Rit, M. Shankar, A. K.
Sahoo, Asian J. Org. Chem. 2015, 4, 846−864; e) F. Zhang, D. R. Spring,
Chem. Soc. Rev. 2014, 43, 6906−6919; f) G. Rousseau, B. Breit, Angew.
Chem. Int. Ed. 2011, 50, 2450−2494; Angew. Chem. 2011, 123,
2498−2543.
[9] C. C. C. Johansson Seechurn, M. O. Kitching, T. J. Colacot, V. Snieckus,
Angew. Chem. Int. Ed. 2012, 51, 5062−5085; Angew. Chem. 2012, 124,
5150−5174.
[10] Selected reviews: a) Q. Wang, Y. Su, L. Li, H. Huang, Chem. Soc. Rev.
2016, 45, 1257−1272; b) J. Jiao, K. Murakami, K. Itami, ACS Catal. 2016,
6, 610−633; c) H. Kim, S. Chang, ACS Catal. 2016, 6, 2341−2351; for
selected examples for C‒ H amidation of arenes with tosyl azides by
Rh(III) catalysis, see: d) S. H. Park, J. Kwak, K. Shin, J. Ryu, Y. Park, S.
Chang, J. Am. Chem. Soc. 2014, 136, 2492−2502; e) K. Shin, Y. Baek, S.
Chang, Angew. Chem. Int. Ed. 2013, 52, 8031−8036; Angew. Chem.
2013, 125, 8189−8194; f) J. Ryu, K. Shin, S. H. Park, J. Y. Kim, S. Chang,
Angew. Chem. Int. Ed. 2012, 51, 9904−9908; Angew. Chem. 2012, 124,
10042−10046; g) J. Y. Kim, S. H. Park, J. Ryu, S. H. Cho, S. H. Kim, S.
Chang, J. Am. Chem. Soc. 2012, 134, 9110−9113; for selected examples
for C‒ H amidation of arenes with tosyl azides by Ru(II) catalysis, see: h)
R. Manoharan, M. Jeganmohan, Eur. J. Org. Chem. 2016, 4013−4019; i)
K. Shin, J. Ryu, S. Chang, Org. Lett. 2014, 16, 2022−2025; j) L.-L. Zhang,
L.-H. Li, Y.-Q. Wang, Y.-F. Yang, X.-Y. Liu, Y.-M. Liang, Organometallics
2014, 33, 1905−1908; k) Y. Shin, S. Han, U. De, J. Park, S. Sharma, N. K.
Mishra, E.-K. Lee, Y. Lee, H. S. Kim, I. S. Kim, J. Org. Chem. 2014, 79,
9262−9271; l) M. R. Yadav, R. K. Rit, A. K. Sahoo, Org. Lett. 2013, 15,
1638−1641; m) J. Kim, J. Kim, S. Chang, Chem. Eur. J. 2013, 19,
[15] a) L. Wang, Y. Yu, M. Yang, C. Kuai, D. Cai, J. Yu, X. Cui, Adv. Synth.
Catal. 2017, DOI: 10.1002/adsc.201700726; b) Y. Li, Y. Feng, L. Xu, L.
Wang, X. Cui, Org. Lett. 2016, 18, 4924−4927; c) C. Kuai, L. Wang, H.
Cui, J. Shen, Y. Feng, X. Cui, ACS Catal. 2016, 6, 186−190; d) B. Zhu, X.
Cui, C. Pi, D. Chen, Y. Wu, Adv. Synth. Catal. 2016, 358, 326−332; e) C.
Pi, X. Cui, Y. Wu, J. Org. Chem. 2015, 80, 7333−7339.
[16] For selected reports on direct C‒ H functionalaizations of 2-
phenoxypyridines, see: a) D. C. McAteer, E. Javed, L. Huo, S. Huo, Org.
Lett. 2017, 19, 1606−1609; b) P. Wang, M. E. Farmer, X. Huo, P. Jain, P.-
X. Shen, M. Ishoey, J. E. Bradner, S. R. Wisniewski, M. D. Eastgate, J.-Q.
Yu, J. Am. Chem. Soc. 2016, 138, 9269−9276; c) K. Raghuvanshi, K.
Rauch, L. Ackermann, Chem. Eur. J. 2015, 21, 1790−1794; d) S.-J. Lou,
Q. Chen, Y.-F. Wang, D.-Q. Xu, X.-H. Du, J.-Q. He, Y.-J. Mao, Z.-Y. Xu,
ACS Catal. 2015, 5, 2846−2849; e) Y. Xu, P. Liu, S.-L. Li, P. Sun, J. Org.
Chem. 2015, 80, 1269−1274; f) C. Zhang, P. P. Sun, J. Org. Chem. 2014,
79, 8457−8461; g) B. Liu, H.-Z. Jiang, B.-F. Shi, J. Org. Chem. 2014, 79,
1521−1526; h) B. Liu, H. Z. Jiang, B. F. Shi, Org. Biomol. Chem. 2014, 12,
2538−2542; i) W. Ma, L. Ackermann, Chem. Eur. J. 2013, 19,
13925−13928; j) J. Yao, R. Feng, Z. Wu, Z. Liu, Y. Zhang, Adv. Synth.
Catal. 2013, 355, 1517−1522; k) L. Ackermann, E. Diers, A. Manvar, Org.
Lett. 2012, 14, 1154−1157; l) S. Guin, S. K. Rout, A. Banerjee, S. Nandi,
B. K. Patel, Org. Lett. 2012, 14, 2618−2621; m) L. Niu, H. Yang, R. Wang,
H. Fu, Org. Lett. 2012, 14, 2618−2621; n) J.-H. Chu, P.-S. Lin, M.-J. Wu,
Organometallics 2010, 29, 4058−4065.
7328−7333;
for
selected
examples
for C‒ H amidation of arenes with tosyl azides by Co(III) catalysis, see: n)
S. Wang, S.-Y. Chen, X.-Q. Yu, Chem. Commun. 2017, 53, 3165−3180;
o) B. Sun, T. Yoshino, S. Matsunaga, M. Kanai, Adv. Synth. Catal. 2014,
356, 1491−1495.
[11] a) K. Shin, H. Kim, S. Chang, Acc. Chem. Res. 2015, 48, 1040−1052; b)
H. Kim, G. Park, J. Park, S. Chang, ACS Catal. 2016, 6, 5922−5929; c) Y.
Kim, J. Park, S. Chang, Org. Lett. 2016, 18, 1892−1895; d) D. Lee, S.
Chang, Chem. Eur. J. 2015, 21, 1132−5368; e) T. Kang, Y. Kim, D. Lee, Z.
Wang, S. Chang, J. Am. Chem. Soc. 2014, 136, 4141−4144; f) H. J. Kim,
M. J. Ajitha, Y. Lee, J. Ryu, J. Kim, Y. Lee, Y. Jung, S. Chang, J. Am.
Chem. Soc. 2014, 136, 1132−1140; g) J. Kim, S. Chang, Angew. Chem.
Int. Ed. 2014, 53, 2203−2207; Angew. Chem. 2014, 126, 2235−2239; h)
D. Lee, Y. Kim, S. Chang, J. Org. Chem. 2013, 78, 11102−11109; i) J.
[17] D. Maiti, S. L. Buchwald, J. Org. Chem. 2010, 75, 1791−1794.
[18] J. Waser, B. Gaspar, H. Nambu, E. M. Carreira, J. Am. Chem. Soc. 2006,
128, 11693−11712.
[19] K. K. Andemen, G. G. Linda Jewell, P. McGraw, B. T. Phillips, J. Org.
Chem. 1982, 47, 1884−1889.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201701028
Chemistry - An Asian Journal
FULL PAPER
FULL PAPER
Lianhui Wang, Zi Yang, Mengqi Yang,
Miaodou Tian, Changsheng Kuai and
Xiuling Cui*
Page No. – Page No.
A
Facile
Access
to
Ortho-
Hydroxyanilnes Based on Ir(III)-
Catalyzed Direct C−H Amidation of 2-
Phenoxypyridines
A highly efficient and regioselective C−H amidation of 2-phenoxypyridines with
sulfonyl azides catalyzed by Ir(III) was developed, offering the synthetically useful
ortho-hydroxyanilnes after removal of the 2-pyridyl moiety.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.