Copper-Catalyzed Regioselective C-H Sulfonyloxylation of Electron-Rich Arenes with p-Toluenesulfonic Acid and Sulfonyloxylation of Aryl(mesityl)iodonium Sulfonates

Article abstract of DOI:10.1021/acs.joc.7b00081

Copper-catalyzed regioselective C-H sulfonyloxylation of electron-rich arenes with p-toluenesulfonic acid has been developed. Electron-rich benzene derivatives and heteroarenes can undergo this C-H sulfonyloxylation reaction to generate aryl tosylates. Furthermore, sulfonyloxylation of aryl(mesityl)iodonium sulfonates has also been investigated. Both aryl(mesityl)iodonium tosylates and triflates can react smoothly to get aryl sulfonates. The formed aryl sulfonates can be converted to phenols, as well as used as good partners of cross-coupling reactions.

Full text of DOI:10.1021/acs.joc.7b00081

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Article
Copper Catalyzed Regioselective C-H Sulfonyloxylation
of Electron-Rich Arenes with p-Toluenesulfonic Acid and
Sulfonyloxylation of Aryl(mesityl)iodonium Sulfonates
He Huang, Yang Wu, Wen Zhang, Chun Feng, Bi-Qin Wang,
Wan-Fei Cai, Ping Hu, Ke-Qing Zhao, and Shi-Kai Xiang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b00081 • Publication Date (Web): 23 Feb 2017
Downloaded from http://pubs.acs.org on February 24, 2017
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Copper Catalyzed Regioselective C-H Sulfonyloxylation of
Electron-Rich Arenes with p-Toluenesulfonic Acid and
Sulfonyloxylation of Aryl(mesityl)iodonium Sulfonates
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He Huang,† Yang Wu,† Wen Zhang, Chun Feng, BiꢀQin Wang,* WanꢀFei Cai, Ping Hu, KeꢀQing
Zhao and ShiꢀKai Xiang*
College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610068,
People’s Republic of China
Eꢀmail: xiangsk@hotmail.com; wangbiqin1964@126.com
Graphical Abstract
Cu(OTf)2 (cat.)
R2
R1
OTs
R2
H
MesI(OAc)2
TsOH—H2O
+
DCE, 50ꢀ90 °C
R1
benzene derivatives: R1 = alkyl, alkoxy; R2 = H, alkyl, halogeno
heteroarenes: indole, pyrrole, thiophene
Mes
R2
OSO2R
R2
R1
I
Cu(OTf)2 (cat.)
OSO2R
DCE, 90ꢀ110 °C
R1
R1 and R2 = H, alkyl, alkoxy, halogeno; R = pꢀtolyl, CF3
Abstract: Copper catalyzed regioselective CꢀH sulfonyloxylation of electronꢀrich
arenes with pꢀtoluenesulfonic acid has been developed. Electronꢀrich benzene
derivatives and heteroarenes can undergo this CꢀH sulfonyloxylation reaction to
generate aryl tosylates. Furthermore, sulfonyloxylation of aryl(mesityl)iodonium
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sulfonates has also been investigated. Both aryl(mesityl)iodonium tosylates and
triflates can react smoothly to get aryl sulfonates. The formed aryl sulfonates can be
converted to phenols, as well as used as good partners of crossꢀcoupling reactions.
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INTRODUCTION
The ubiquitous presence of oxygenated aromatic compounds in bioactive
molecules and functional materials makes them valuable synthetic targets.1 In recent
years, synthesis of these compounds by atomꢀeconomic CꢀH oxygenation of arenes
aroused great interest from researchers in the area of synthetic chemistry.2 One of the
biggest challenges in this area is regioselective control of CꢀH oxygenation. After
years of effort, a variety of metalꢀcatalyzed chelateꢀassisted regioselective CꢀH
oxygenation of arenes have been developed greatly, including ortho CꢀH oxygenation
(Scheme 1, (1a)),3 meta CꢀH oxygenation (Scheme 1, (1b))4 and para CꢀH
oxygenation (Scheme 1, (1c)).5 Despite the tremendous advance, nonꢀchelateꢀassisted
regioselective CꢀH oxygenation remains a challenge.6 Recently, iodine(III)ꢀmediated
paraꢀselective CꢀH oxygenation of amides, sulfonamides or phenols was achieved by
Liégault and Taillefer,7a Gu,7b Pan,7c Prakash,7d and Kikugawa7e et al. (Scheme 1,
(2a)). However, this strategy can only be applicable to the specific substrates, such as
amides, phenols and their analogues. In 2011, a gold catalyzed CꢀH acetoxylation of
electronꢀrich arenes was developed by the groups of Wang8a and Michelet8b
independently. Next year, Lei’s group reported a copper catalyzed CꢀH hydroxylation
of electronꢀdeficient arenes and heteroarenes.8c In 2013, Sanford’s group successfully
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achieved the steric control of regioselective CꢀH acetoxylation of simple arenes by
use of MesI(OAc)2 as an oxidant in combination with acridine as a ligand of
palladium catalyst (Scheme 1, (2b)).9 In 2015, the copper catalyzed paraꢀselective
CꢀH amidation and amination of electronꢀrich arenes have been developed by our and
Suna’s groups respectively.10 Just recently, Suna and coꢀworkers achieved a copper
catalyzed paraꢀselective CꢀH aryloxylation of electronꢀrich arenes (Scheme 1, (2c)).11
Various of diaryl ethers can be synthetized by their method. Herein, we report the
copper catalyzed regioselective CꢀH sulfonyloxylation of electronꢀrich arenes with
pꢀtoluenesulfonic acid and sulfonyloxylation of aryl(mesityl)iodonium sulfonates
(Scheme 1, (2d)). The formed aryl sulfonates can be converted to phenols, as well as
used as good partners of crossꢀcoupling reactions.12 Although the iodine(III) sulfonate
mediated CꢀH sulfonyloxylation of arenes was reported by Koser’s group as early as
2006, the substrate scope was limited to electronꢀrich polycyclic aromatic
hydrocarbons.13
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Scheme 1. Regioselective C-H Oxygenation of Arenes.
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(1) Chelate-assisted regioselective C-H oxygenation
3
DG
DG
4
5
6
7
8
9
OY
(a) ortho CꢀH
DG
OY
DG
H
H
(c) para CꢀH
(b) meta CꢀH
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H
OY
OY
(2) Non-chelate-assisted regioselective C-H oxygenation
(a) Paraꢀselective CꢀH oxygenation of amides and phenols
O
O
R
R
PhI(TFA)2
PhI(TFA)2
HOY
HOY
+
+
HN
H
H
HN
HO
HO
OY
(b) Steric control of regioselective CꢀH acetoxylation of arenes
Pd(OAc)2
N
NO2
NO2
NO2
Pd(OAc)2
PhI(OAc)2
MesI(OAc)2
OAc
major isomer
OAc
major isomer
(c) Paraꢀselective CꢀH aryloxylation of electronꢀrich arenes
R2
Mes
OTs
H
I
HO
R2
O
MesI(OH)OTs
Cu(MeCN)4BF4
iꢀPr2NEt
CH2Cl2, rt
(CF3CO)2O
CH2Cl2, rt
R1
R1
R1
(d) Regioselective CꢀH sulfonyloxylation of electronꢀrich arenes with
TsOH—H2O and sulfonyloxylation of aryl(mesityl)iodonium sulfonate
Cu(OTf)2 (cat.)
R2
OTs
R2
H
MesI(OAc)2
TsOH—H2O
+
DCE, 50ꢀ90 °C
R1
R1
benzene derivatives: R1 = alkyl, alkoxy; R2 = H, alkyl, halogeno
heteroarenes: indole, pyrrole, thiophene
Mes
R2
OSO2R
R2
R1
I
Cu(OTf)2 (cat.)
OSO2R
DCE, 90ꢀ110 °C
R1
R1 and R2 = H, alkyl, alkoxy, halogeno; R = pꢀtolyl, CF3
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RESULTS AND DISCUSSION
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Initially, the sulfonyloxylation reaction of anisole 1a with 1.5 equivalents of
pꢀtoluenesulfonic acid monohydrate was carried out using Cu(OTf)2 as a catalyst,
MesI(OAc)2 as an oxidant and DCE as solvent. It was pleased that we isolated the
target product 4a in 52% yield (Table 1, entry 1). When the amount of
pꢀtoluenesulfonic acid monohydrate was increased to 2.0 equivalents, the yield was
raised to 77% (Table 1, entry 2). Nevertheless, the further increase of
pꢀtoluenesulfonic acid monohydrate can not improve the yield of 4a (Table 1, entry 3).
The results of screening of solvents indicated that DCE was the best solvent (Table 1,
entries 2 and 4ꢀ9). Strong polar solvents such as DMF, DMSO were used to result in
the failure of the reaction with 39%, 24% recovery of anisole 1a respectively (Table 1,
entries 6 and 7). Reducing the catalyst loading to 5 % resulted in a slightly decreased
yield of 4a (Table 1, entry 10). No desired product was observed in the absence of a
copper catalyst (Table 1, entry 11). While the temperature was lowered to 80 °C, the
yield of 4a decreased markedly to 60% (Table 1, entry 12).
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Table 1. Optimization of Reaction Conditions for C-H Sulfonyloxylation of
Arenes.a
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OMe
OMe
Cu(OTf)2, MesI(OAc)2
+ TsOH•H2O
sovlent, 90 °C, 24 h
7
8
OTs
9
1a
4a
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entry TsOH•H2O (equiv.)
yield(%)
sovlent
1
2
3
4
5
6
7
1.5
2.0
2.4
2.0
2.0
2.0
2.0
2.0
DCE
DCE
52
77
75
26
62
0
DCE
1,4ꢀdioxane
PhCl
DMF
0
DMSO
CH2Cl2
8b
trace
9c
CHCl3
DCE
DCE
DCE
2.0
2.0
2.0
2.0
57
65
0
10d
11e
12f
60
a
Reaction Conditions: anisole 1a (0.3 mmol), TsOH·H2O, Cu(OTf)2 (10% mmol),
MesI(OAc)2 (0.36 mmol), solvent (2.0 mL), 90 °C, 24 h, under argon. The yields were
isolated yields. The isomers and their ratio were determined by GCꢀMS and 1H NMR.
p:(o+m) > 99:1.
b The reaction was carried out at 50 °C.
c The reaction was carried out at 70 °C.
d 5% mmol of Cu(OTf)2 was used.
e Without Cu(OTf)2.
f The reaction was carried out at 80 °C.
With the optimized reaction condition in hand, we next investigated the substrate
scope of arenes 1. Electronꢀrich benzene derivatives and heteroarenes can undergo
this CꢀH sulfonyloxylation reaction to get corresponding aryl tosylates in moderate to
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good yields with excellent regioselectivities. When monosubstituted benzenes were
employed as substrates, the sulfonyloxylation reactions occurred primarily at the para
position to the activating orthoꢀ/paraꢀdirectors. (Table 2, 4aꢀ4e). When disubstituted
benzenes with two different substituents were used as the substrates, stronger
orthoꢀ/paraꢀdirectors dominated the regioselectivities. The sulfonyloxylation
reactions occurred primarily at the para position to the stronger orthoꢀ/paraꢀdirectors
(Table 2, 4hꢀ4m). 1, 2, 3, 4ꢀtetrahydronaphthalene 1n, indane 1o could react smoothly
to generate the desired paraꢀselective products 4n, 4o in yields of 48%, 58%
respectively (Table 2, 4n and 4o). It is noteworthy that substituted benzenes with
strong electronꢀdonating groups, such as alkoxybenzenes and aryloxybenzenes,
showed very high regioselectivities. In this reaction condition, nearly only
paraꢀselective sulfonyloxylation products were acquired (Table 2, 4a, 4b, 4h, 4i, 4j,
4k, 4l and 4m). Furthermore, some substituted heteroarenes containing indole, pyrrole
or thiophene motif can undergo successfully this reaction to get the anticipated
products despite low yields (Table 2, 4p, 4q and 4r). In addition, naphthalene 1s was
used as the substrate to produce the naphthyl tosylate 4s in 35% yield with the
moderate regioselectivitie (1’:2’ = 75:25) (Table 2, 4s). However, we didn’t observe
the formation of intermediate diaryliodonium tosylate 2s by TLC during reaction
process. Therefore, we anticipated that the sulfonyloxylation of naphthalene maybe
proceed via the arene radical cation mechanism similar to Koser’s work.13 As
expected, the sulfonyloxylation of naphthalene can undergo smoothly in the absence
of a copper catalyst with the similar yield and regioselectivitie. PhI(OH)OTs was used
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instead of MesI(OAc)2 to result in a slightly higher yield with poor selectivity.
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Table 2. Substrate Scope for C-H Sulfonyloxylation of Arenes.a
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Cu(OTf)2
MesI(OAc)2
R2
R1
OTs
OTs
R2
R1
+ HOTs•H2O
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DCE, 90 °C
1
4
OTs
PhO
OTs
MeO
Me
4c 72%b,c
4a 77%
4b 68%
p:(o+m) > 99:1
p:(o+m) > 99:1
p:(o+m) = 91:9
3'
4'
OTs
OTs Me
OTs
Pri
But
Me
4d 68%b,c
4e 51%b,c
p:(o+m) = 90:10
4f 72%
4':3' = 98:2
p:(o+m) = 91:9
6'
5'
3'
5'
4' OTs Me
4' OTs
F
OTs
4'
5'
Me
Me MeO
MeO
2'
3'
4i 45%
4':(3'+5'+6') > 99:1 5':(3'+4'+6') > 99:1
6'
4g 65%
4h 64%
4':(2'+5') > 99:1
6'
6'
6'
5'
Cl
OTs Br
OTs
I
OTs
5'
5'
4'
4'
4'
MeO
MeO
MeO
3'
4j 50%
3'
3'
4k 60%
4l 34%
5':(3'+4'+6') > 99:1
5':(3'+4'+6') > 99:1 5':(3'+4'+6') > 99:1
4'
5'
4'
OTs
5'
6' OTs
OTs
5'
6'
O
7'
4m 55%d,e
5':(4'+6'+7') > 99:1
4n 48%b
6':5' = 98:2
4o 58%b,d
5':4' = 95:5
OTs
Br
COOEt
MeOOC
OTs
N
N
Et
Et
4p 33%f
4q 23%g
OTs
1'
35%, 1':2' = 75:25g
40%, 1':2' = 77:23g,i
56%, 1':2' = 50:50g,i,j
45%, 1':2' = 64:36g,i,j,k
2'
Br
OTs
S
4r 22%h
4s
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a
Reaction Conditions: arenes 1 (0.3 mmol), TsOH·H2O (0.6 mmol), Cu(OTf)2 (10%
5
6
7
8
9
mmol), MesI(OAc)2 (0.36 mmol), DCE (2.0 mL), 90 °C, 24 h, under argon. The
yields were isolated yields. The isomers and their ratio were determined by GCꢀMS
and 1H NMR.
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b CF3COOH (0.6 mmol) was used as an additive. Cu(OTf)2 was added after 18 h. The
total reaction time was prolonged to 42 h.
c The reaction was carried out at 80 °C.
d The reaction was carried out at 70 °C.
e The reaction was carried out for 7 h.
f The reaction was carried out at 50 °C for 60 h.
g The reaction was carried out for 12 h.
h The reaction was carried out at 80 °C for 8 h.
i Without Cu(OTf)2.
j PhI(OH)OTs was used instead of MesI(OAc)2.
k The reaction was carried out at 60 °C.
Unfortunately, the electronꢀdeficient arenes could not undergo this CꢀH
sulfonyloxylation reaction to generate the corresponding aryl tosylates, such as
chlorobenzene, nitrobenzene and pyridine. In order to remedy this situation, some
unsymmetrical diaryliodonium tosylates with a mesityl and an electronꢀdeficient
phenyl ligand were employed to react in DCE, using Cu(OTf)2 as a catalyst. To our
delight, the anticipated aryl tosylates were successfully obtained in moderate to
excellent yields (Table 3). The phenyl(mesityl)iodonium tosylates bearing halogen
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substituents on the benzene ring can undergo smoothly the sulfonyloxylation reaction
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to get the desired products 4t, 4u, 4v in yields of 76%, 72%, 83% respectively (Table
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3, 4t, 4u, 4v). Use of diaryliodonium tosylate 2w bearing
a
strong
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electronꢀwithdrawing nitro substituent as a substrate afforded the product 4w in a
good yield of 83% (Table 3, 4w). Two other diaryliodonium tosylates 2x, 2y
containing cyano, trifluoromethyl group were deployed in the reaction to give the
corresponding products 4x, 4y in moderate yields of 62%, 51% respectively (Table 3,
4x, 4y). In addition, several unsymmetrical diaryliodonium tosylates with a mesityl
and an electronꢀrich phenyl ligand were also tested. The diaryliodonium tosylates 2a,
2c, 2k were applied to the reaction condition to afford the corresponding aryl tosylates
4a, 4c, 4k in good yields of 93%, 91%, 63% respectively (Table 3, 4a, 4c, 4k).
Table 3. Sulfonyloxylation of Different Aryl(mesityl)iodonium Tosylates.a
Mes
OTs
Cu(OTf)2
I
R
OTs
R
DCE, 90°C
2
4
OTs
OTs
OTs
OTs
Cl
Br
F
4t 76%
4u 72%
4x 62%
4v 83%
4y 51%
OTs
OTs
OTs
OTs
O2N
F3C
NC
4w 83%
OTs
Br
MeO
MeO
Me
4a 93%
4c 91%
4k 63%
a Reaction Conditions: aryl(mesityl)iodonium tosylates 2 (0.3 mmol), Cu(OTf)2 (10%
mmol), DCE (2.0 mL), 90 °C, 12 h, under argon. The yields were isolated yields.
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In 2012, a metalꢀfree reaction of symmetrical diaryliodonium tosylates in toluene
to produce aryl tosylates was reported by Olofsson’s group.14 According to their
reaction condition, we tested the reaction of unsymmetrical diaryliodonium tosylate 2t,
resulting in only 5% yield of 4ꢀchlorophenyl tosylate 4t, as well as 94% yield of
mesityl tosylate 4z (eq 1). When the reaction of unsymmetrical diaryliodonium
tosylate 2t was carried out according to our reaction condition in the absence of a
copper catalyst, 4ꢀchlorophenyl tosylate 4t and mesityl tosylate 4z were obtained in
yields of 26%, 21% respectively (eq 2). The two reactions in equations 1 and 2 are in
marked contrast to the reaction of 2t in table 3. All of the results indicated that the
copper catalyst played a key role in the regioselective control of the reaction of
unsymmetrical diaryliodonium tosylates.
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OTs
OTs
+
OTs
toluene (2 mL)
reflux, 24h
I
(1)
Cl
Cl
2t (0.3 mmol)
4t 5%
4z 94%
OTs
I
OTs
+
OTs
DCE (2 mL)
90 °C, 24h
(2)
(3)
Cl
Cl
2t (0.3 mmol)
4t 21%
4z 26%
Cu(OTf)2 (10%),
MesI(OAc)2 (1.2 eq.)
+
TfOH
MeO
OTf
MeO
DCE, 90 °C, 60 h
5a 6%
1a (0.3 mmol) (0.6 mmol)
In order to further expand the scope of CꢀH sulfonyloxylation reaction of arenes,
trifluoromethanesulfonic acid was used to react with anisole 1a. It is regrettable that
the target product 4ꢀmethoxyphenyl triflate 5a was obtained in a very low yield of 6%
(eq 3). However, use of diaryliodonium triflates as substrates afforded successfully
the corresponding aryl triflates in satisfactory yields (Table 4). The diaryliodonium
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triflates with electronꢀdonating groups on the benzene ring 3a, 3b, 3c underwent
smoothly the sulfonyloxylation reaction to generate the desired products 5a, 5b, 5c in
yields of 57%, 55%, 38% respectively (Table 4, 5a, 5b, 5c). The diaryliodonium
triflates bearing halogen substituents on the benzene ring 3d, 3e produced the
corresponding aryl triflates in good yields of 55%, 61% respectively (Table 4, 5d, 5e).
The diaryliodonium triflate with a strong electronꢀwithdrawing nitro substituent 3f
afforded the product 5f in a low yield of 26% (Table 4, 5f).
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Table 4. Sulfonyloxylation of Different Aryl(mesityl)iodonium Triflates.a
Mes
OTf
Cu(OTf)2
I
OTf
R
R
DCE, 90°C
3
5
OTf
OTf Me
Me
OTf
MeO
Me
Br
5a 57%
OTf
5b 55%
5c 38%
OTf
OTf
Cl
O2N
5d 55%b
5e 61%b
5f 26%c
a
Reaction Conditions: aryl(mesityl)iodonium triflates 3 (0.3 mmol), Cu(OTf)2 (10%
mmol), DCE (2.0 mL), 90 °C, 60 h, under argon. The yields were isolated yields.
b The reaction was carried out at 110 °C.
c The reaction was carried out for 12 h.
To explore the application of these transformations, 4ꢀmethoxyphenyl tosylate 4a
was hydrolyzed using KOH as a base to get 4ꢀmethoxyphenol 6 in a high yield of
96% (eq 4).12a The compound 4a can also undergo a nickelꢀcatalyzed Suzukiꢀtype
coupling to give 4ꢀmethoxybiphenyl 7 in a good yield of 82% (eq 5).12b
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KOH (20 eq.)
(4)
(5)
MeO
MeO
OH
Ph
MeO
OTs
OTs
EtOH (2 mL), reflux, 2 h
6 96%
4a (0.3 mmol)
NiCl2(PCy3)2 (5%)
K3PO4 (2 eq.)
+ PhB(OH)
MeO
4a (0.3 mmol)
2
dioxane (2 mL)
130 °C, 60 h
(0.45 mmol)
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7 82%
A
possible mechanism for CꢀH sulfonyloxylation of arenes with
pꢀtoluenesulfonic acid is proposed as shown in Scheme 2.10a,15 Initially, arenes 1
undergo a TsOHꢀmediated electrophilic aromatic substitution with MesI(OAc)2 to get
aryl(mesityl)iodonium tosylates 2 with the release of mesityl iodide. Next, the
generated aryl(mesityl)iodonium tosylates 2 oxidize the active copper catalyst A
formed by disproportionation or reduction15 of Cu(OTf)2 to intermediates B. Finally,
the intermediates B generate final products 4 by reductive elimination and release the
active copper catalyst A to complete the catalytic cycle.
Scheme 2. Proposed Reaction Mechanism.
R2
MesI(OAc)2
+
R1
TsOH•H2O
Mes
1
R2
R1
I
OTs
2
MesI
OTf
Cu
R2
R1
Cu(OTf)2
CuOTf
OTs
A
B
R2
R1
OTs
4
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CONCLUSIONS
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In summary, we developed the copper catalyzed regioselective CꢀH
sulfonyloxylation reaction of electronꢀrich arenes with pꢀtoluenesulfonic acid and
sulfonyloxylation reaction of aryl(mesityl)iodonium sulfonates. Electronꢀrich benzene
derivatives and heteroarenes underwent this CꢀH sulfonyloxylation reaction to
generate the corresponding aryl tosylates. Both aryl(mesityl)iodonium tosylates and
triflates reacted smoothly to get the corresponding aryl sulfonates. The
diaryliodonium sulfonates with both electronꢀdonating and electronꢀwithdrawing
groups in the benzene ring could afford the corresponding aryl sulfonates in
satisfactory yields. The formed aryl sulfonates could be converted to phenols, as well
as used as good partners of crossꢀcoupling reactions. Further studies on regioselective
CꢀH functionalization of arenes and the applications are now ongoing in our
laboratory.
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EXPERIMENTAL SECTION
General Information. Unless otherwise noted, all commercial reagents and solvents
16a
were used without further purification. MesI(OAc)2 and diaryliodonium salts16b
were synthesized according to literature’s methods. DCE, PhCl, DMF, DMSO,
1
CH2Cl2, CHCl3 and 1, 4ꢀdioxane were freshly distilled over CaH2. H NMR spectra
were recorded on the Varian 400 MHz WB spectrometers. Chemical shifts (in ppm)
were referenced to tetramethylsilane (δ = 0.00 ppm) as an internal standard in CDCl3.
13C NMR spectra were recorded on the same NMR spectrometers. Chemical shifts (in
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ppm) were calibrated with CDCl3 (δ = 77.0 ppm). 19F NMR spectra were recorded on
5
6
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1
the same NMR spectrometers under H decoupling conditions. Chemical shifts (in
8
9
ppm) were referenced to PhCF3 (δ = 62.28 ppm) as an internal standard in CDCl3.
Mass spectra were obtained using electrospray ionization (ESI) or electron impact (EI)
mass spectrometer. Highꢀresolution mass spectra (HRMS) were obtained using a
microTOFꢀQ II mass spectrometer (ESI). Melting points were determined with a
melting point apparatus.
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Synthesis of Heteroarenes 1p and 1q. The heteroarenes 1p16c and 1q16d were
synthesized according to literature’s methods.
Ethyl 5-bromo-1-ethyl-1H-indole-2-carboxylate (1p). 1p was synthesized from ethyl
5ꢀbromoꢀ1Hꢀindoleꢀ2ꢀcarboxylate and bromoethane. Yellow solid, mp 58ꢀ59 °C; IR
(KBr, cmꢀ1) νmax 2984, 1707, 1515, 1248, 1210, 825, 762; 1H NMR (400 MHz, CDCl3,
ppm) δ 7.79 (d, J = 1.6 Hz, 1H), 7.39 (dd, J1 = 8.8 Hz, J2 = 2.0 Hz, 1H), 7.26 (d, J =
8.8 Hz, 1H), 7.21 (s, 1H), 4.58 (q, J = 7.2 Hz, 2H), 4.37 (q, J = 7.2 Hz, 2H), 1.43ꢀ1.35
(m, 6H); 13C NMR (100 MHz, CDCl3, ppm) δ 161.5, 137.0, 128.1, 127.7, 127.4,
124.8, 113.5, 111.7, 109.4, 60.7, 39.8, 15.6, 14.3; HRMS (ESI) calcd for
C13H14BrNNaO2 [M+Na]+ 318.0106, Found 318.0102.
Methyl 1-ethyl-1H-pyrrole-2-carboxylate (1q).17 1q was synthesized from methyl
1Hꢀpyrroleꢀ2ꢀcarboxylate and bromoethane. Colourless liquid; IR (KBr, cmꢀ1) νmax
1
2962, 1709, 1530, 1261, 1102, 802, 738; H NMR (400 MHz, CDCl3, ppm) δ
6.95ꢀ6.93 (m, 1H), 6.86ꢀ6.84 (m, 1H), 6.12ꢀ6.10 (m, 1H), 4.35 (q, J = 7.2 Hz, 2H),
3.80 (s, 3H), 1.38 (t, J = 7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ 161.3,
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127.8, 121.2, 118.0, 107.9, 50.8, 43.9, 16.9; MS (EI) m/z 153 (M+).
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General Procedure for C-H Sulfonyloxylation of Arenes with p-Toluenesulfonic
Acid. Procedure A: Cu(OTf)2 (10.8 mg, 0.03 mmol), TsOH·H2O (114.1 mg, 0.6 mmol)
were placed into a 25 mL Schlenk tube equipped with a magnetic stir bar. To this
mixture was added in sequence DCE (1.0 mL), arenes 1 (0.3 mmol), MesI(OAc)2
(131.1 mg, 0.36 mmol, dissolved in 1.0 mL of DCE, dropwise) with an injection
syringe under stirring and an argon atmosphere. The solution was stirred for the
appointed time at the appointed temperature. The mixture was cooled to room
temperature and purified by column chromatography on silica gel (eluent: petroleum
ether / ethyl acetate = 10 : 1) to afford the products 4. Procedure B: TsOH·H2O
(114.1 mg, 0.6 mmol) were placed into a 25 mL Schlenk tube equipped with a
magnetic stir bar. To this tube was added in sequence DCE (1.0 mL), arenes 1 (0.3
mmol), CF3COOH (0.6 mmol), MesI(OAc)2 (131.1 mg, 0.36 mmol, dissolved in 1.0
mL of DCE, dropwise) with an injection syringe under stirring and an argon
atmosphere. After the reaction solution was stirred for 18 h at the appointed
temperature, Cu(OTf)2 (10.8 mg, 0.03 mmol) were added under an argon atmosphere.
The solution was stirred again for 24 h at same temperature. The mixture was cooled
to room temperature and purified by column chromatography on silica gel (eluent:
petroleum ether / ethyl acetate = 10 : 1) to afford the products 4.
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4-Methoxyphenyl tosylate (4a).12b 4a was synthesized from anisole 1a and TsOH·H2O
according to the procedure A. White solid, 64.3 mg, 77% yield; mp 71ꢀ72 °C; IR
(KBr, cmꢀ1) νmax 2935, 2840, 1594, 1498, 1346, 1173, 1147, 843, 679; 1H NMR (400
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MHz, CDCl3, ppm) δ 7.69 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 8.4 Hz, 2H), 6.88 (d, J =
8.8 Hz, 2H), 6.77 (d, J = 9.2 Hz, 2H), 3.76 (s, 3H), 2.45 (s, 3H); 13C NMR (100 MHz,
CDCl3, ppm) δ 158.1, 145.2, 143.0, 132.2, 129.7, 128.5, 123.3, 114.4, 55.5, 21.7; MS
(ESI) m/z 301.0 [M+Na]+.
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4-Phenoxyphenyl tosylate (4b).18 4b was synthesized from diphenyl ether 1b and
TsOH·H2O according to the procedure A. White solid, 69.4 mg, 68% yield; mp
1
109ꢀ110 °C; IR (KBr, cmꢀ1) νmax 3062, 2362, 1892, 1591, 1493, 1091, 867, 550; H
NMR (400 MHz, CDCl3, ppm) δ 7.72 (d, J = 8.0 Hz, 2H), 7.37ꢀ7.30 (m, 4H), 7.13 (t,
13
J = 7.6 Hz, 1H), 6.98 (d, J = 8.4 Hz, 2H), 6.93ꢀ6.86 (m, 4H), 2.45 (s, 3H); C NMR
(100 MHz, CDCl3, ppm) δ 156.5, 156.0, 145.4, 144.6, 132.1, 129.8, 129.7, 128.5,
123.8, 123.6, 119.1, 109.9, 21.7; MS (ESI) m/z 363.0 [M+Na]+.
p-Tolyl tosylate (4c).12b 4c was synthesized from toluene 1c and TsOH·H2O according
to the procedure B. White solid, 56.6 mg, 72% yield; mp 71ꢀ72 °C; IR (KBr, cmꢀ1)
1
νmax 3038, 1927, 1658, 1376, 1093, 865, 832, 652; H NMR (400 MHz, CDCl3, ppm)
δ 7.70 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 8.4 Hz, 2H), 7.07 (d, J = 8.2 Hz, 2H), 6.85 (d,
J = 8.4 Hz, 2H), 2.45 (s, 3H), 2.30 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ 147.4,
145.2, 136.9, 132.4, 130.0, 129.7, 128.5, 122.0, 21.7, 20.9; MS (ESI) m/z 285.0
[M+Na]+.
4-Isopropylphenyl tosylate (4d).19 4d was synthesized from cumene 1d and
TsOH·H2O according to the procedure B. Colourless liquid, 59.2 mg, 68% yield; IR
1
(KBr, cmꢀ1) νmax 2962, 1598, 1501, 1373, 1179, 866, 767, 552; H NMR (400 MHz,
CDCl3, ppm) δ 7.70 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 8.4 Hz,
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2H), 6.88 (d, J = 8.4 Hz, 2H), 2.86 (hept, J = 6.8 Hz, 1H), 2.44 (s, 3H), 1.19 (d, J =
7.2 Hz, 6H); 13C NMR (100 MHz, CDCl3, ppm) δ 147.7, 147.5, 145.2, 132.5, 129.7,
128.5, 127.4, 122.0, 33.5, 23.9, 21.7; MS (EI) m/z 290 (M+).
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4-Tert-butylphenyl tosylate (4e).12b 4e was synthesized from tertꢀbutyl benzene 1e and
TsOH·H2O according to the procedure B. White solid, 46.5 mg, 51% yield; mp
1
114ꢀ115 °C; IR (KBr, cmꢀ1) νmax 2963, 1596, 1366, 1181, 870, 759, 647, 585; H
NMR (400 MHz, CDCl3, ppm) δ 7.73 (d, J = 8.0 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H),
7.28 (d, J = 8.8 Hz, 2H), 6.89 (d, J = 8.8 Hz, 2H), 2.46 (s, 3H), 1.28 (s, 9H); 13C NMR
(100 MHz, CDCl3, ppm) δ 150.0, 147.2, 145.1, 132.6, 129.7, 128.4, 126.4, 121.6,
34.5, 31.3, 21.7; MS (ESI) m/z 327.0 [M+Na]+.
3,4-Dimethylphenyl tosylate (4f).20 4f was synthesized from oꢀxylene 1f and
TsOH·H2O according to the procedure A. White solid, 59.7 mg, 72% yield; mp
124ꢀ125 °C; IR (KBr, cmꢀ1) νmax 3053, 2925, 1596, 1494, 1360, 1174, 941, 829, 718,
1
652, 552; H NMR (400 MHz, CDCl3, ppm) δ 7.71 (d, J = 8.4 Hz, 2H), 7.31 (d, J =
8.0 Hz, 2H), 6.99 (d, J = 8.0 Hz, 1H), 6.82 (d, J = 2.4 Hz, 1H), 6.62 (dd, J1 = 8.4 Hz,
J2 = 2.4 Hz, 1H), 2.45 (s, 3H), 2.20 (s, 3H), 2.18 (s, 3H); 13C NMR (100 MHz, CDCl3,
ppm) δ 147.5, 145.1, 138.2, 135.5, 132.6, 130.3, 129.6, 128.5, 123.2, 119.2, 21.7, 19.8,
19.2; MS (EI) m/z 276 (M+).
2,4-Dimethylphenyl tosylate (4g).20,21 4g was synthesized from mꢀxylene 1g and
TsOH·H2O according to the procedure A. White solid, 53.8 mg, 65% yield; mp
72ꢀ73 °C; IR (KBr, cmꢀ1) νmax 3045, 2920, 1926, 1595, 1494, 1369, 1175, 1087, 839,
1
691, 542; H NMR (400 MHz, CDCl3, ppm) δ 7.73 (d, J = 8.0 Hz, 2H), 7.31 (d, J =
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8.0 Hz, 2H), 6.95 (s, 1H), 6.90 (d, J = 8.4 Hz, 1H), 6.84 (d, J = 8.4 Hz, 1H), 2.45 (s,
3H), 2.27 (s, 3H), 2.03 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ 146.1, 145.2,
136.7, 133.1, 132.1, 131.1, 129.7, 128.3, 127.3, 121.9, 21.7, 20.8, 16.2; MS (ESI) m/z
299.0 [M+Na]+.
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4-Methoxy-3-methylphenyl tosylate (4h). 4h was synthesized from 2ꢀmethylanisole 1h
and TsOH·H2O according to the procedure A. White solid, 56.1 mg, 64% yield; mp
84ꢀ85 °C; IR (KBr, cmꢀ1) νmax 3008, 2973, 2843, 1597, 1496, 1365, 1175, 1089, 1027,
874, 699, 548; 1H NMR (400 MHz, CDCl3, ppm) δ 7.70 (d, J = 8.0, 2H), 7.30 (d, J =
8.0, 2H), 6.78 (d, J = 2.4, 1H), 6.70 (dd, J1 = 8.8 Hz, J2 = 2.4 Hz, 1H), 6.64 (d, J = 8.8,
1H), 3.78 (s, 3H), 2.45 (s, 3H), 2.12 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ
156.2, 145.1, 142.4, 132.3, 129.6, 128.5, 127.9, 124.4, 120.0, 109.8, 55.5, 21.7, 16.2;
HRMS (ESI) calcd for C15H16NaO4S [M+Na]+ 315.0667, Found 315.0666.
3-Fluoro-4-methoxyphenyl tosylate (4i). 4i was synthesized from 2ꢀfluoroanisole 1i
and TsOH·H2O according to the procedure A. White solid, 39.9 mg, 45% yield; mp
75ꢀ76 °C; IR (KBr, cmꢀ1) νmax 1508, 1347, 1214, 1020, 814, 685; 1H NMR (400 MHz,
CDCl3, ppm) δ 7.70 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 6.87ꢀ6.81 (m, 1H),
6.77ꢀ6.71 (m, 2H), 3.86 (s, 3H), 2.46 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ
151.5 (d, J = 247.8 Hz), 146.7, 145.6, 142.1 (d, J = 9.3 Hz), 131.8, 129.8, 128.5,
118.2 (d, J = 3.9 Hz), 112.9 (d, J = 2.5 Hz), 111.2 (d, J = 21.2 Hz), 56.3, 21.7; HRMS
(ESI) calcd for C14H13FNaO4S [M+Na]+ 319.0416, Found 319.0412.
3-Chloro-4-methoxyphenyl tosylate (4j).22 4j was synthesized from 2ꢀchloroanisole 1j
and TsOH·H2O according to the procedure A. White solid, 46.8 mg, 50% yield; mp
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97ꢀ98 °C; IR (KBr, cmꢀ1) νmax 1595, 1492, 1168, 891, 815, 790, 649, 545; H NMR
(400 MHz, CDCl3, ppm) δ 7.69 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 7.00 (d,
J = 2.8 Hz, 1H), 6.87 (dd, J1 = 8.8 Hz, J2 = 2.8 Hz, 1H), 6.80 (d, J = 9.2 Hz, 1H), 3.86
(s, 3H), 2.46 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ 153.9, 145.6, 142.4,
131.7, 129.8, 128.5, 124.4, 122.5, 121.6, 111.7, 56.3, 21.7; MS (EI) m/z 312 (M+).
3-Bromo-4-methoxyphenyl tosylate (4k).23 4k was synthesized from 2ꢀbromoanisole
1k and TsOH·H2O according to the procedure A. White solid, 64.3 mg, 60% yield; mp
98ꢀ99 °C; IR (KBr, cmꢀ1) νmax 3018, 2844, 2558, 1589, 1487, 1386, 1163, 897, 810,
725, 671, 554; 1H NMR (400 MHz, CDCl3, ppm) δ 7.70 (d, J = 8.0 Hz, 2H), 7.33 (d, J
= 8.0 Hz, 2H), 7.16 (d, J = 2.8 Hz, 1H), 6.93 (dd, J1 = 8.8 Hz, J2 = 2.8 Hz, 1H), 6.77
(d, J = 8.8 Hz, 1H), 3.86 (s, 3H ), 2.46 (s, 3H ); 13C NMR (100 MHz, CDCl3, ppm) δ
154.8, 145.6, 142.7, 131.8, 129.8, 128.5, 127.3, 122.3, 111.5, 111.3, 56.5, 21.7; MS
(ESI) m/z 381.0 [M+Na]+.
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3-Iodo-4-methoxyphenyl tosylate (4l).24 4l was synthesized from 2ꢀiodoanisole 1l and
TsOH·H2O according to the procedure A. Yellow solid, 41.1 mg, 34% yield; mp
1
84ꢀ85 °C; IR (KBr, cmꢀ1) νmax 1593, 1481, 1369, 1159, 811, 792, 669, 553; H NMR
(400 MHz, CDCl3, ppm) δ 7.69 (d, J = 8.0 Hz, 2H), 7.34ꢀ7.32 (m, 3H), 6.95 (dd, J1 =
8.8 Hz, J2 = 2.8 Hz, 1H), 6.68 (d, J = 8.8 Hz, 1H), 3.84 (s, 3H), 2.46 (s, 3H); 13C
NMR (100 MHz, CDCl3, ppm) δ 156.9, 145.6, 142.9, 133.1, 131.8, 129.8, 128.5,
123.2, 110.3, 85.0, 56.6, 21.7; MS (EI) m/z 404 (M+).
2,3-Dihydrobenzofuran-5-yl tosylate (4m). 4m was synthesized from
2,3ꢀdihydrobenzofuran 1m and TsOH·H2O according to the procedure A. White solid,
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47.8 mg, 55% yield; mp 100ꢀ101 °C; IR (KBr, cmꢀ1) νmax 3053, 2925, 1596, 1494,
1360, 1174, 941, 829, 718, 652, 552; 1H NMR (400 MHz, CDCl3, ppm) δ 7.70 (d, J =
8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 6.92 (s, 1H), 6.58 (d, J = 8.8 Hz, 1H), 6.54 (d, J
= 8.8 Hz, 1H), 4.57 (t, J = 8.8 Hz, 2H), 3.17 (t, J = 8.8 Hz, 2H), 2.45 (s, 3H) ; 13C
NMR (100 MHz, CDCl3, ppm) δ 158.7, 145.2, 143.0, 132.3, 129.6, 128.5, 128.3,
121.6, 119.5, 109.1, 71.8, 29.7, 21.7; HRMS (ESI) calcd for C15H14NaO4S [M+Na]+
313.0510, Found 313.0516.
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5,6,7,8-Tetrahydronaphthalen-2-yl tosylate (4n).25 4n was synthesized from
tetrahydronaphthalene 1n and TsOH·H2O according to the procedure B. Yellow liquid,
43.5 mg, 48% yield; IR (KBr, cmꢀ1) νmax 2947, 1598, 1372, 1173, 926, 871, 811, 565,
553; 1H NMR (400 MHz, CDCl3, ppm) δ 7.71 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.0 Hz,
2H), 6.92 (d, J = 8.4 Hz, 1H), 6.71 (d, J = 2.0 Hz, 1H), 6.61 (dd, J1 = 8.4 Hz, J2 = 2.4
Hz, 1H), 2.69ꢀ2.66 (m, 4H), 2.44 (s, 3H), 1.76ꢀ1.66 (m, 4H); 13C NMR (100 MHz,
CDCl3, ppm) δ 147.1, 145.1, 138.6, 136.0, 132.6, 129.9, 129.6, 128.4, 122.4, 119.0,
29.2, 28.8, 22.8, 22.6, 21.6; MS (ESI) m/z 325.0 [M+Na]+.
2,3-Dihydro-1H-inden-5-yl tosylate (4o). 4o was synthesized from indane 1o and
TsOH·H2O according to the procedure B. White solid, 50.1 mg, 58% yield; mp
105ꢀ106 °C; IR (KBr, cmꢀ1) νmax 3087, 2962, 1595, 1484, 1370, 1169, 870, 842, 725,
655, 546; 1H NMR (400 MHz, CDCl3, ppm) δ 7.72 (d, J = 8.4 Hz, 2H) , 7.31 (d, J =
8.0 Hz, 2H), 7.06 (d, J = 8.0 Hz, 1H), 6.89 (s, 1H), 6.63 (dd, J1 = 8.0 Hz, J2 = 2.0 Hz,
1H), 2.86ꢀ2.82 (m, 4H), 2.45 (s, 3H), 2.09ꢀ2.04 (m, 2H); 13C NMR (100 MHz, CDCl3,
ppm) δ 148.1, 146.0, 145.1, 143.1, 132.6, 129.6, 128.5, 124.7, 119.7, 118.4, 32.8, 32.2,
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25.6, 21.7; HRMS (ESI) calcd for C16H16NaO3S [M+Na]+ 311.0718, Found 311.0710.
Ethyl 5-bromo-1-ethyl-3-(tosyloxy)-1H-indole-2-carboxylate (4p). 4p was synthesized
from Ethyl 5ꢀbromoꢀ1ꢀethylꢀ1Hꢀindoleꢀ2ꢀcarboxylate 1p and TsOH·H2O according to
the procedure A. White solid, 46.1 mg, 33% yield; mp 117ꢀ118 °C; IR (KBr, cmꢀ1)
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νmax 2985, 1709, 1378, 1231, 1192, 802, 751, 554; H NMR (400 MHz, CDCl3, ppm)
δ 7.73 (d, J = 8.4 Hz, 2H), 7.34ꢀ7.29 (m, 3H), 7.21 (d, J = 8.8 Hz, 1H), 6.66 (d, J =
1.2 Hz, 1H), 4.52 (q, J = 7.2 Hz, 2H), 4.36 (q, J = 7.2 Hz, 2H), 2.50 (s, 3H), 1.45 (t, J
13
= 7.2 Hz, 3H), 1.37 (t, J = 7.2 Hz, 3H); C NMR (100 MHz, CDCl3, ppm) δ 160.4,
145.9, 133.2, 132.9, 130.6, 129.8, 128.7, 128.5, 121.9, 120.5, 120.3, 114.1, 111.7,
61.4, 40.1, 21.8, 15.6, 14.1; HRMS (ESI) calcd for C20H20BrNNaO5S [M+Na]+
488.0143, Found 488.0128.
Methyl 1-ethyl-5-(tosyloxy)-1H-pyrrole-2-carboxylate (4q). 4q was synthesized from
methyl 1ꢀethylꢀ1Hꢀpyrroleꢀ2ꢀcarboxylate 1q and TsOH·H2O according to the
procedure A. Yellow solid, 22.3 mg, 23% yield; mp 62ꢀ63 °C; IR (KBr, cmꢀ1) νmax
1
1712, 1596, 1368, 1240, 1178, 840, 788, 522; H NMR (400 MHz, CDCl3, ppm) δ
7.72 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 8.4 Hz, 2H), 6.61 (d, J = 2.0 Hz, 1H), 6.53 (d, J
= 2.4 Hz, 1H), 4.26 (q, J = 7.2 Hz, 2H), 3.77 (s, 3H), 2.45 (s, 3H), 1.32 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3, ppm) δ 160.8, 145.3, 133.9, 131.8, 129.6, 128.5,
119.1, 118.8, 110.1, 51.2, 44.3, 21.7, 16.7; HRMS (ESI) calcd for C15H17NNaO5S
[M+Na]+ 346.0725, Found 346.0722.
5-bromothiophen-2-yl tosylate (4r). 4r was synthesized from 2ꢀbromothiophene 1r
and TsOH·H2O according to the procedure A. Tawny liquid, 22.0 mg, 22% yield; IR
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(KBr, cmꢀ1) νmax 2963, 1630, 1261, 1091, 802, 690, 565; 1H NMR (400 MHz, CDCl3,
ppm) δ 7.76 (d, J = 8.0 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 6.74 (d, J = 4.0 Hz, 1H),
6.30 (d, J = 4.4 Hz, 1H), 2.48 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ 149.9,
146.3, 130.5, 130.0, 128.9, 126.9, 118.5, 106.8, 21.8; HRMS (ESI) calcd for
C11H9BrNaO3S2 [M+Na]+ 354.9074, Found 354.9071.
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Naphthalen-1-yl tosylate (4s).12b 4s was synthesized from naphthalene 1s and
TsOH·H2O according to the procedure A. White solid, 31.3 mg, 35% yield; mp
93ꢀ94 °C; IR (KBr, cmꢀ1) νmax 2926, 2856, 1598, 1369, 1215, 1178, 890, 768, 711,
661, 554; 1H NMR (400 MHz, CDCl3, ppm) δ 7.90 (d, J = 8.0 Hz, 1H), 7.82ꢀ7.72 (m,
4H), 7.49ꢀ7.40 (m, 2H), 7.38ꢀ7.33 (m, 1H), 7.27 (d, J = 8.4 Hz, 2H), 7.19 (d, J = 7.6
Hz, 1H), 2.41 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ 145.7, 145.4, 134.6, 132.6,
129.7, 128.4, 127.6, 127.2, 127.0, 126.65, 126.63, 125.0, 121.7, 118.3, 21.6; MS (EI)
m/z 298 (M+).
General Procedure for the Synthesis of Aryl Tosylates from
Aryl(mesityl)iodonium Tosylates. Cu(OTf)2 (10.8 mg, 0.03 mmol),
aryl(mesityl)iodonium tosylates 2 (0.3 mmol) were placed into a 25 mL Schlenk tube
equipped with a magnetic stir bar. To this mixture was added DCE (2.0 mL) with an
injection syringe under stirring and an argon atmosphere. The solution was stirred for
12 h at 90 °C. The mixture was cooled to room temperature and purified by column
chromatography on silica gel (eluent: petroleum ether / ethyl acetate = 10 : 1) to
afford the products 4.
4-Chlorophenyl
tosylate
(4t).19
4t
was
synthesized
from
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(4ꢀchlorophenyl)(mesityl)iodonium tosylate 2t according to the general procedure.
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White solid, 64.3 mg, 76% yield; mp 72ꢀ73 °C; IR (KBr, cmꢀ1) νmax 3437, 3095, 1595,
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9
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1378, 1169, 867, 752, 644, 548; H NMR (400 MHz, CDCl3, ppm) δ 7.70 (d, J = 8.4
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Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 7.26ꢀ7.23 (m, 2H), 6.94ꢀ6.90 (m, 2H), 2.46 (s, 3H);
13C NMR (100 MHz, CDCl3, ppm) δ 148.0, 145.6, 132.8, 131.9, 129.8,129.7, 128.5,
123.8, 21.7; MS (EI) m/z 282 (M+).
4-Bromophenyl
tosylate
(4u).12b,19
4u
was
synthesized
from
(4ꢀbromophenyl)(mesityl)iodonium tosylate 2u according to the general procedure.
White solid, 70.2 mg, 72% yield; mp 82ꢀ83 °C; IR (KBr, cmꢀ1) νmax 3092, 1657, 1483,
1
1376, 1166, 866, 744, 664, 561; H NMR (400 MHz, CDCl3, ppm) δ 7.69 (d, J = 8.4
Hz, 2H), 7.42ꢀ7.39 (m, 2H), 7.32 (d, J = 8.4 Hz, 2H), 6.88ꢀ6.84 (m, 2H), 2.46 (s, 3H);
13C NMR (100 MHz, CDCl3, ppm) δ 148.5, 145.6, 132.7, 131.9, 129.8, 128.5, 124.1,
120.6, 21.7; MS (EI) m/z 328 (M+).
4-Fluorophenyl
tosylate
(4v).26
4v
was
synthesized
from
(4ꢀfluorophenyl)(mesityl)iodonium tosylate 2v according to the general procedure.
Colourless liquid, 66.3 mg, 83% yield; IR (KBr, cmꢀ1) νmax 3438, 2925, 1599, 1499,
1
1374, 1193, 847, 656, 551; H NMR (400 MHz, CDCl3, ppm) δ 7.69 (d, J = 8.0 Hz,
2H), 7.32 (d, J = 8.4 Hz, 2H), 6.97ꢀ6.93 (m, 4H), 2.45 (s, 3H); 13C NMR (100 MHz,
CDCl3, ppm) δ 161.0 (d, J = 245.3 Hz), 145.5, 145.4, 132.0, 129.8, 128.5, 124.0 (d, J
= 8.7 Hz), 116.3 (d, J = 23.5 Hz), 21.7; MS (EI) m/z 266 (M+).
4-Nitrophenyl
tosylate
(4w).12b,19
4w
was
synthesized
from
(4ꢀnitrophenyl)(mesityl)iodonium tosylate 2w according to the general procedure.
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White solid, 73.1 mg, 83% yield; mp 103ꢀ104 °C; IR (KBr, cmꢀ1) νmax 3436, 3083,
1589, 1350, 1147, 882, 742, 670, 567; 1H NMR (400 MHz, CDCl3, ppm) δ 8.19 (d, J
= 9.2 Hz, 2H), 7.73 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.18 (d, J = 9.2 Hz,
2H), 2.47 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ 153.9, 146.2, 146.1, 131.6,
130.1, 128.4, 125.4, 123.2, 21.8; MS (EI) m/z 293 (M+).
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4-Cyanophenyl
tosylate
(4x).12b
4x
was
synthesized
from
(4ꢀcyanophenyl)(mesityl)iodonium tosylate 2x according to the general procedure.
White solid, 50.8 mg, 62% yield; mp 95ꢀ96 °C; IR (KBr, cmꢀ1) νmax 3100, 2231, 1594,
1494, 1372, 1153, 885, 769, 647, 545; 1H NMR (400 MHz, CDCl3, ppm) δ 7.71 (d, J
= 8.4 Hz, 2H), 7.62 (d, J = 8.8 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.13 (d, J = 9.2 Hz,
2H), 2.47 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ 152.5, 146.1, 133.8, 131.7,
130.0, 128.4, 123.4, 117.7, 111.1, 21.7; MS (EI) m/z 273 (M+).
4-(Trifluoromethyl)phenyl
tosylate
(4y).27
4y
was
synthesized
from
(4ꢀ(trifluoromethyl)phenyl)(mesityl)iodonium tosylate 2y according to the general
procedure. Colourless liquid, 48.4 mg, 51% yield; IR (KBr, cmꢀ1) νmax 3437, 2926,
1604, 1454, 1167, 864, 745, 664, 556; 1H NMR (400 MHz, CDCl3, ppm) δ 7.72 (d, J
= 8.4 Hz, 2H), 7.57 (d, J = 8.8 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 8.4 Hz,
2H), 2.47 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ 151.8 (q, J = 1.3 Hz), 145.9,
131.8, 129.9, 129.2 (q, J = 32.8 Hz), 128.4, 126.96 (q, J = 3.8 Hz), 123.5 (q, J = 270.8
Hz), 122.8, 21.7; MS (EI) m/z 316 (M+).
Mesityl tosylate (4z).28 White solid; mp 76ꢀ77 °C; IR (KBr, cmꢀ1) νmax 2931, 2855,
1604, 1468, 1178, 891, 778, 729, 670; 1H NMR (400 MHz, CDCl3, ppm) δ 7.84 (d, J
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= 8.4 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H), 6.82 (s, 2H), 2.47 (s, 3H), 2.24 (s, 3H), 2.07
5
6
7
13
(s, 6H); C NMR (100 MHz, CDCl3, ppm) δ 145.3, 145.0, 136.3, 134.4, 131.7,
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9
129.78, 129.77, 128.1, 21.7, 20.7, 17.2; MS (EI) m/z 290 (M+).
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General Procedure for the Synthesis of Aryl Triflates from
Aryl(mesityl)iodonium Triflates.
Cu(OTf)2
(10.8 mg, 0.03
mmol),
aryl(mesityl)iodonium triflates 3 (0.3 mmol) were placed into a 25 mL Schlenk tube
equipped with a magnetic stir bar. To this mixture was added DCE (2.0 mL) with an
injection syringe under stirring and an argon atmosphere. The solution was stirred for
the appointed time at the appointed temperature. The mixture was cooled to room
temperature and purified by column chromatography on silica gel (eluent: petroleum
ether / ethyl acetate = 10 : 1) to afford the products 5.
4-Methoxyphenyl
triflate
(5a).29
5a
was
synthesized
from
(4ꢀ
methoxyphenyl)(mesityl)iodonium triflate 3a according to the general procedure.
Yellow liquid, 43.7 mg, 57% yield; IR (KBr, cmꢀ1) νmax 3095, 1595, 1378, 1169, 867,
1
752, 644, 548; H NMR (400 MHz, CDCl3, ppm) δ 7.21ꢀ7.18 (m, 2H), 6.94ꢀ6.91 (m,
2H), 3.82 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ 159.0, 143.0, 122.3, 118.7 (q,
19
J = 319.2 Hz), 115.0, 55.7; F NMR (376 MHz, CDCl3, PhCF3, ppm) δ ꢀ72.35; MS
(EI) m/z 256 (M+).
p-Tolyl triflate (5b).30 5b was synthesized from (pꢀtolyl)(mesityl)iodonium triflate 3b
according to the general procedure. Colourless liquid, 39.6 mg, 55% yield; IR (KBr,
cmꢀ1) νmax 2360, 2341, 1502, 1424, 1214, 1142, 891, 611; 1H NMR (400 MHz, CDCl3,
ppm) δ 7.21 (d, J = 8.8 Hz, 2H), 7.13 (d, J = 8.8 Hz, 2H), 2.35 (s, 3H); 13C NMR (100
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MHz, CDCl3, ppm) δ 147.6, 138.5, 130.6, 120.9, 118.8 (q, J = 318.9 Hz), 20.7; 19F
5
6
7
NMR (376 MHz, CDCl3, PhCF3, ppm) δ ꢀ72.57; MS (EI) m/z 240 (M+).
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9
3,4-Dimethylphenyl
triflate
(5c).30
5c
was
synthesized
from
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(3,4ꢀdimethylphenyl)(mesityl)iodonium triflate 3c according to the general procedure.
Colourless liquid, 29.0 mg, 38% yield; IR (KBr, cmꢀ1) νmax 2366, 2344, 1423, 1212,
1
1143, 939, 853, 620; H NMR (400 MHz, CDCl3, ppm) δ 7.15 (d, J = 8.4 Hz, 1H),
7.02 (d, J = 2.4 Hz, 1H), 6.97 (dd, J1 = 8.4 Hz, J2 = 2.4 Hz, 1H), 2.26 (s, 3H), 2.24 (s,
3H); 13C NMR (100 MHz, CDCl3, ppm) δ 147.6, 139.1, 137.1, 130.9, 121.9, 118.8 (q,
J = 318.9 Hz), 118.2, 19.7, 19.1; 19F NMR (376 MHz, CDCl3, PhCF3, ppm) δ ꢀ72.66;
MS (EI) m/z 254 (M+).
4-Chlorophenyl
triflate
(5d).30
5d
was
synthesized
from
(4-chlorophenyl)(mesityl)iodonium triflate 3d according to the general procedure.
Colourless liquid, 42.9 mg, 55% yield; IR (KBr, cmꢀ1) νmax 1485, 1429, 1216, 1141,
888, 835, 610; 1H NMR (400 MHz, CDCl3, ppm) δ 7.42 (d, J = 9.2 Hz, 2H), 7.22 (d, J
= 8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3, ppm) δ 147.9, 134.3, 130.3, 122.7, 118.7
(q, J = 319.1 Hz); 19F NMR (376 MHz, CDCl3, PhCF3, ppm) δ ꢀ72.34; MS (EI) m/z
260 (M+).
4-Bromophenyl
triflate
(5e).30
5e
was
synthesized
from
(4ꢀbromophenyl)(mesityl)iodonium triflate 3e according to the general procedure.
Colourless liquid, 55.8 mg, 61% yield; IR (KBr, cmꢀ1) νmax 1481, 1428, 1215, 1142,
886, 750, 628, 524; 1H NMR (400 MHz, CDCl3, ppm) δ 7.56 (d, J = 8.8 Hz, 2H), 7.16
(d, J = 9.2 Hz, 2H); 13C NMR (100 MHz, CDCl3, ppm) δ 148.4, 133.3, 123.0, 122.0,
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118.6 (q, J = 319.1 Hz); 19F NMR (376 MHz, CDCl3, PhCF3, ppm) δ ꢀ72.40; MS (EI)
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m/z 306 (M+).
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4-Nitrophenyl
triflate
(5f).30
5f
was
synthesized
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(4ꢀnitrophenyl)(mesityl)iodonium triflate 3f according to the general procedure.
White solid, 21.2 mg, 26% yield; mp 56ꢀ57 °C; IR (KBr, cmꢀ1) νmax 3125, 1537, 1350,
1
1213, 1134, 898, 862, 742, 613; H NMR (400 MHz, CDCl3, ppm) δ 8.38 (d, J = 9.2
Hz, 2H), 7.50 (d, J = 9.2 Hz, 2H); 13C NMR (100 MHz, CDCl3, ppm) δ 153.1, 147.1,
126.0, 122.5, 118.6 (q, J = 319.2 Hz); 19F NMR (376 MHz, CDCl3, PhCF3, ppm) δ
ꢀ72.14; MS (EI) m/z 271 (M+).
Synthesis of 4-Methoxyphenol (6).31 4ꢀMethoxyphenol 6 was synthesized by
hydrolysis of 4ꢀmethoxyphenyl tosylate according to the literature method.12a White
solid, 35.7 mg, 96% yield; mp 57ꢀ58 °C; IR (KBr, cmꢀ1) νmax 3402, 2951, 1511, 1232,
1031, 824, 731; 1H NMR (400 MHz, CDCl3, ppm) δ 6.81ꢀ6.75 (m, 4H), 4.65 (s, 1H),
3.77 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ 153.7, 149.4, 115.9, 114.8, 55.8;
MS (EI) m/z 124 (M+).
Synthesis of 4-Methoxybiphenyl (7).32 4ꢀMethoxybiphenyl 7 was synthesized from
4ꢀmethoxyphenyl tosylate and phenylboronic acid according to the literature
method.12b White solid, 45.2 mg, 82% yield; mp 92ꢀ93 °C; IR (KBr, cmꢀ1) νmax 2935,
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1605, 1485, 1280, 1198, 1037, 833, 760; H NMR (400 MHz, CDCl3, ppm) δ
7.60ꢀ75.4 (m, 4H), 7.47ꢀ7.42 (m, 2H), 7.33 (t, J = 7.6 Hz, 1H), 7.03ꢀ6.99 (m, 2H),
13
3.87 (s, 3H); C NMR (100 MHz, CDCl3, ppm) δ 159.1, 140.8, 133.7, 128.7, 128.1,
126.7, 126.6, 114.1, 55.3; MS (EI) m/z 184 (M+).
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ASSOCIATED CONTENT
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Supporting Information
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Copies of 1H, 13C NMR spectra of compounds 1p, 1q, 4aꢀ4z, 5a-5f, 6, 7 and 19F NMR
spectra of compounds 5a-5f. This material is available free of charge via the Internet
at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Eꢀmail: xiangsk@hotmail.com
*Eꢀmail: wangbiqin1964@126.com
Author Contributions
†He Huang and Yang Wu contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We are grateful for the financial supports from National Natural Science Foundation
of China (No. 21202109), Sichuan Provincial Department of Education (No.
14ZB0028), and Sichuan Normal University (Nos.16ZP10, DJ2016ꢀ44 and
xyz2016ꢀ4ꢀ34).
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