One-Pot Synthesis of Unsymmetric Diaryliodonium Salts from Iodine and Arenes

Article abstract of DOI:10.1021/acs.joc.7b01652

The first synthesis of unsymmetric diaryliodonium salts directly from iodine and arenes is presented. The methodology provides diaryliodonium salts with the trimethoxyphenyl (TMP) moiety as dummy group. The protocol avoids the customary use of iodoarenes,

Full text of DOI:10.1021/acs.joc.7b01652

Subscriber access provided by UNIVERSITY OF ADELAIDE LIBRARIES
Note
One-Pot Synthesis of Unsymmetric
Diaryliodonium Salts from Iodine and Arenes
Erik Lindstedt, Marcus Reitti, and Berit Olofsson
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b01652 • Publication Date (Web): 15 Aug 2017
Downloaded from http://pubs.acs.org on August 18, 2017
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
The Journal of Organic Chemistry is published by the American Chemical Society.
1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 14
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
One-Pot Synthesis of Unsymmetric Diaryliodonium Salts from Iodine and Arenes
Erik Lindstedt, Marcus Reitti and Berit Olofsson*
Berit.Olofsson@su.se
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SEꢀ106 91 Stockholm (Sweden)
ABSTRACT
The first synthesis of unsymmetric diaryliodonium salts directly from iodine and arenes is presented. The methodology
provides diaryliodonium salts with the trimethoxyphenyl (TMP) moiety as dummy group. The protocol avoids the
customary use of iodoarenes, which can be both expensive and toxic. Excess reagents are not required, and the reactions
are performed under mild conditions. OꢀArylations with these TMP salts were demonstrated to be highly
chemoselective.
OMe
mCPBA
R
✓
✓
✓
efficient
avoids iodoarenes
no excess reagents
TsOH— H O
I
OTs
+
I
2
+
2
R
CH Cl , rt, 90 min
2
2
TMP
MeO
OMe
3
Diaryliodonium salts (diarylꢀλ ꢀiodanes) have become exceedingly popular electrophilic arylating reagents for a wide
1
range of nucleophiles under both metalꢀfree and metalꢀcatalyzed conditions in the last decade. The interest in
applications with these hypervalent iodine reagents was accelerated by the development of novel synthetic routes to
diaryliodonium salts, making these easily available at low cost. Our first contribution to this field was the development
of a general oneꢀpot route to diaryliodonium salts from iodoarenes using the reagent system mCPBA/triflic acid (TfOH)
2
in dichloromethane, which delivered diaryliodonium triflates in high yields within short reaction times. The reaction
was extended to the direct synthesis of symmetric diaryliodonium salts from arenes and iodine, a cascade reaction
involving iodination, oxidation and electrophilic aromatic substitution between the arene and the formed iodine(III)
2
intermediate.
The triflic acid system proved to be too reactive for the synthesis of iodonium salts with both aryl moieties substituted
with electronꢀdonating groups. Such diaryliodonium salts have previously been synthesized from
3
[
hydroxy(tosyloxy)iodo]benzene (HTIB, Koser’s reagent) derivatives. HTIB can be synthesized from the
4
corresponding iodoarene using mCPBA/tosic acid, and we recently improved the synthesis of HTIB derivatives 1 by
two interconnected routes. They can either be obtained by mCPBAꢀoxidation of iodoarenes (Scheme 1a) or from iodine
5
and arenes by initial oxidative iodination, followed by oxidation to yield 1 (Scheme 1b). The iodination was found to
1
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 14
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
be the most difficult step in this sequence, limiting the substrate scope to arenes with electronꢀdonating (EDG)
6
substituents, and trifluoroethanol (TFE) was employed as coꢀsolvent to increase the reaction rates.
5
Scheme 1. Synthesis of [hydroxy(tosyloxy)iodo]arenes 1.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
To overcome the scope limitations in our mCPBA/triflic acid system, we developed a oneꢀpot synthesis of electronꢀrich
diaryliodonium salts 2 from iodoarenes, which likely proceeds via in situ formation of iodine(III) compounds 1
(Scheme 2a). That transformation could also be extended to the use of iodine and arenes as starting materials (Scheme
7
2
b). The latter route tolerated only arenes with EDG substituents, and the synthesis of unsymmetric diaryliodonium
1
2
8
salts (R ≠ R ) was unsuccessful due to product mixtures, further limiting the scope.
7
, 9
Scheme 2. One-Pot Syntheses of Diaryliodonium Salts with mCPBA/TsOH
Stuart and coworkers later modified our mCPBA/TsOH conditions into a sequential oneꢀpot reaction with iodoarenes
and trimethoxybenzene (TMPꢀH) to obtain unsymmetric aryl(trimethoxyphenyl)iodonium salts 3 with a large scope
9
(Scheme 2c). Other oxidant systems have also been reported for oneꢀpot syntheses, including K S O /TFA,
2
2
8
TM
10
Selectfluor /TMSOTf and Oxone/TfOH.
Arylations with symmetric diaryliodonium salts are straightforward, as only one aryl group can be transferred to the
1
nucleophile. Symmetric salts can, however, be difficult to prepare and sometimes require expensive boronic acids.
2
ACS Paragon Plus Environment

Page 3 of 14
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
Furthermore, a potentially valuable iodoarene is wasted in the arylations. To avoid these drawbacks, we have
1
1
thoroughly investigated the chemoselectivities in metalꢀfree arylations with unsymmetric diaryliodonium salts. While
1
, 11ꢀ12
the anisyl dummy group was found to be sufficient in many applications,
the use of the trimethoxyphenyl (TMP)
9, 11ꢀ12, 13
dummy can sometimes increase the chemoselectivity further.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
DiMagno and Stuart have recently described oneꢀpot protocols focused at the synthesis of unsymmetric diaryliodonium
9
, 10b, 14
salts with anisyl and TMP dummies, respectively,
but the synthesis of unsymmetric diaryliodonium salts from
iodine and arenes has not been reported to date. We hence set out to develop such a oneꢀpot synthesis of aryl(TMP)ꢀ
iodonium salts, to circumvent the need for sometimes expensive and harmful iodoarenes.
2a, 7
To prevent the previous problems of product mixtures when using two different arenes,
our strategy involved careful
control the stoichiometry of the reaction according to Scheme 1b, with sequential addition of the second arene.
Furthermore, we wanted to avoid the coꢀsolvent TFE to retard the final step in the sequence, when the arene reacts with
iodine(III) intermediate 1, although this would also slow down the formation of intermediate 1. In this fashion, the
reactive trimethoxybenzene (TMPꢀH) was expected to outperform the other arene (or iodoarene) as nucleophile in the
last step.
The reaction was investigated with mesitylene, and the formation of MesI(OH)OTs 1a with mCPBA and tosic acid was
5
performed using our previously reported conditions but without TFE. The iodination and oxidation to 1a was allowed
to proceed for one hour, after which TMPꢀH was added. Under those conditions, mesityl(TMP)iodonium tosylate (3a)
was isolated in 70% yield within 90 min at room temperature (Scheme 3). This should be compared to the symmetric
dimesityliodonium tosylate (2a), which was obtained in 59% yield after 20 h reaction time using our previously
7
reported method in Scheme 2b. The difference in reaction times in the synthesis of 3a and 2a was reassuring and
strengthened our hypothesis that product mixtures could be avoided in this fashion.
The substrate scope of the oneꢀpot synthesis was subsequently investigated. The methodology proved compatible with a
range of alkylꢀsubstituted arenes, providing iodonium salts 3bꢀ3g in yields ranging from 50% to 70% (Scheme 3a). The
reactions were all performed on a 2 mmol scale to demonstrate the ease of synthesis. The products were easily isolated
by concentration and precipitation with diethyl ether.
Salts 3aꢀ3e have all four ortho positions substituted, which makes them of special interest in reactions where aryne
1
3b
formation poses a problem. Gratifyingly, the use of alkylꢀsubstituted arenes that could be iodinated in different
positions furnished products 3c and 3g with complete regioselectivity, both with the bulky tertꢀbutyl group in the para
3
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 14
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
position. The synthesis of 3eꢀ3g benefitted from using TFE as coꢀsolvent, as the purple iodine color remained in its
absence. Despite our previous concerns, product mixtures were not obtained in TFE, illustrating the fine balance
between the rates of the three reaction steps in this sequence.
Scheme 3. Scope of diaryliodonium salts from arenes and iodine
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
a
b
7 c
CH
2
Cl
2
:TFE 1:1 was used. 20 h reaction time using the conditions in Scheme 2b.
Anisole (2.0 equiv) and
additional TsOH (0.5 equiv) were added in the second step instead of TMPꢀH.
A series of disubstituted arenes was investigated next, to understand the regioselectivity of the reaction. The arenes
were all decorated with one methoxy group to facilitate iodination, and a range of other substituents. Reactions with
1,2ꢀdisubstituted arenes proved completely regioselective, and provided pꢀmethoxy iodonium salts 3hꢀ3k in moderate
4
ACS Paragon Plus Environment

Page 5 of 14
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
yields (Scheme 3b). Ester, carboxylic acid and halide substituents were all tolerated, providing suitable handles for
further transformation after arylations with these salts.
1,3ꢀDisubstituted arenes proved more difficult, as exemplified with 3ꢀbromoanisole (Scheme 3c). This reaction resulted
in a mixture of salts 3l and 3m in a 5:1 ratio favoring the paraꢀmethoxy isomer. The third possible isomer, with both
substituents ortho, was not observed. Finally, the corresponding 1,4ꢀdisubstituted arenes were investigated (Scheme
3d). As expected, these substrates reacted with complete regioselectivity, albeit salts 3n and 3o were formed in modest
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
9
yields. The synthesis of 3o was thus examined in acetonitrile at 77 °C (cf Scheme 2c), but 3o was not formed.
Some arenes were incompatible with the reaction, including benzene, fluorobenzene, acetanilide and 1,2ꢀ
dimethoxybenzene. While no attempts were made to individually optimize the conditions for each arene, the
1
5
methodology seems most suitable for arenes with moderately EDG substituents. This can be explained by iodination
of the arene being the most difficult step in this cascade reaction, resulting in retarded iodination of less reactive arenes.
This conclusion is supported by the solution remaining purple, the negative result in acetonitrile, as well as the success
7
in formation of Ph
2
IOTs from iodobenzene but not from benzene in our previous report. Reactions with highly reactive
arenes, on the other hand, resulted in black reaction mixtures from which no iodonium salt could be precipitated.
As stated previously, iodonium salts with the anisyl dummy group give high chemoselectivity in many arylations. As
the electronꢀrich TMP moiety is not tolerated in all arylations, we briefly investigated the use of anisole in the second
step of the reaction with mesitylene and iodine. As expected, the lower nucleophilicity of anisole compared to TMPꢀH
resulted in decreased reaction rate, which could be compensated by adding 2 equiv. anisole and more tosic acid to yield
mesityl salt 2b in 65% (Scheme 3, box).
The efficiency of the oneꢀpot synthesis of salt 3c was compared with the stepꢀwise synthesis with isolated 1c (Scheme
4). The product was obtained in 62% overall yield, compared to 68% obtained with the oneꢀpot reaction, further
illustrating that the iodination is the most difficult step in the sequence, and that the TMPꢀH reaction is facile. With
individual fineꢀtuning of the first part of the reaction, the yields can probably be considerably increased for some of
salts 3. Such optimization would include temperature, stoichiometry and using TFE as coꢀsolvent. The use of TFE in the
synthesis of 3b, 3n or 3o, however, resulted in black reaction mixtures upon addition of TMPꢀH. The oneꢀpot reaction
is superior to the stepꢀwise reaction both by avoiding problems associated with isolation of reagents 1, such as
instability and lack of crystallinity, and by giving higher yields of salts 3.
Scheme 4. Step-wise synthesis of 3c.
5
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 14
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
The nature of the counterion has shown to play an important role in many reactions employing diaryliodonium salts.
We therefore investigated the possibility of a oneꢀpot anion exchange to the triflate counterion using our previously
7
developed methodology (Scheme 5). To our delight, addition of one equivalent of TfOH to the reaction mixture
allowed the facile isolation of 3p in 60% yield.
Scheme 5. In situ anion exchange from tosylate to triflate.
As described above, iodonium salts with a TMP dummy have resulted in highly chemoselective arylations with several
9
, 11ꢀ12, 13
nucleophiles, including enolates, phenols, hydroxyamides, alcohols, anilines, amines and azide.
The majority of
the salts employed in those studies have had electronꢀwithdrawing substituents, making the differences in electronic
properties between the aryl groups wide. To the contrary, the aryl(TMP)iodonium salts synthesized with the present
methodology have aryl groups with electronꢀdonating substituents. To investigate the utility of these salts, a phenol was
arylated with salt 3a (Scheme 5a). The reaction indeed proved to be completely chemoselective, with diaryl ether 4 as
the only observed product. Furthermore, we have recently demonstrated that salt 3a gives excellent chemoselectivity in
13b
arylations of aliphatic alcohols, as exemplified by the synthesis of aryl ether 5 (Scheme 5b).
Scheme 5. Chemoselective arylations
6
ACS Paragon Plus Environment

Page 7 of 14
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
To conclude, we have developed an efficient oneꢀpot synthesis of unsymmetric diaryliodonium salts carrying the
trimethoxyphenyl dummy group. The methodology employs iodine and arenes, hence avoiding the need for expensive
and toxic iodoarenes. The conditions are mild, and the scope includes a variety of arenes with at least one electronꢀ
donating substituent, to ensure efficient iodination and oxidation to iodine(III) under the presented conditions. The
efficacy in arylations with electron rich aryl(TMP) salts 3 has been demonstrated by chemoselective Oꢀarylations of a
phenol and an aliphatic alcohol.
EXPERIMENTAL SECTION
General Methods
2 2 ,
Commercial CH Cl (stabilized with ethanol) 2,2,2ꢀtrifluoroethanol and diethyl ether were used as received. Toluene
was dried using a VAC purification system and stored over 4Å MS. Iodine, 2,4ꢀdimethylphenol, tBuOK, pꢀ
toluenesulfonic acid monohydrate and all arenes were commercially available and used as received. mCPBA was
purchased from commercial suppliers, then dried under vacuum at rt for 2ꢀ6 h and subsequently the percentage of active
16
oxidizing reagent was determined by iodometric titration. The aryl ether products were purified by flash column
chromatography using automated flash system Teledyne ISCO CombiFlash Rf 200 with RediSep Rf columns. Melting
points were measured using a STUART SMP3 and are reported uncorrected. All NMR spectra were recorded using a
400 MHz Bruker AVANCE II with a BBO probe at 298 K using CDCl , CD OD or DMSO
d as solvents. Chemical
3
3
6
1
13
shifts are given in ppm relative to the residual solvent peak ( H NMR: CDCl δ 7.26; CD OD 3.31; DMSO
d 2.50;
C
3
3
6
NMR: CDCl δ 77.16; CD OD 49.00 DMSO
d 39.52) with multiplicity (br = broad, s = singlet, d = doublet, dd =
3
3
6
doublet of doublets, q = quartet, m = multiplet), coupling constants (in Hz) and integration. High‐resolution mass
analyses were obtained using a Bruker microTOF ESI.
General experimental procedure for synthesis of unsymmetric diaryliodonium salts 3. Iodine (0.5 equiv) was
weighed into a roundꢀbottomed flask or suitable vial to which CH Cl (0.05 M) was added. mCPBA (1.5 equiv), arene
2
2
7
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 14
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(1.0 equiv) and tosic acid (TsOH⋅H
2
O 1.0 equiv) were added sequentially and the reaction mixture was stirred at
ambient temperature for 1 h. The mixture gradually changed color from purple to yellow/clear solution or white
precipitate, indicating formation of intermediate 1. 1,3,5ꢀTrimethoxybenzene (TMPꢀH, 1.0 equiv) was added in one
portion and the resulting reaction mixture was stirred for additionally 30 min, after which the solvent was concentrated
until signs of precipitation were seen. Diethyl ether (0.025 M) was added, the mixture was stirred at rt for 15 min and
then kept in the freezer for 30 min. The resulting solid was filtered off, washed three times with diethyl ether, dried
under water suction and further dried under high vacuum to afford the desired diaryliodonium tosylate.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Mesityl(4-methoxyphenyl)iodonium tosylate (2b). Synthesized according to general procedure using I (587 mg, 2.3
2
2 2
mmol), mesitylene (0.64 mL, 4.6 mmol) and tosic acid (880 mg, 4.6 mmol) in CH Cl (46 mL). Anisole (1.00 mL, 9.25
mmol) was added as the second arene, and after 15 min additional tosic acid ((440 mg, 2.3 mmol) was added. After the
reaction the solvent was concentrated, still maintaining a homogenous solution, to which ether was added causing a
precipitation of the desired compound. Note: The solution needs to be homogenous before addition of ether to ensure
that the tosic acid remains in solution. 2b was isolated as a white powder in 65% yield (1.57 g, 2.99 mmol). Spectral
1
7
data matches literature.
Mesityl(2,4,6-trimethoxyphenyl)iodonium tosylate (3a). Synthesized according to general procedure using using I
511 mg, 2.0 mmol), mesitylene (0.56 mL, 4.0 mmol), tosic acid (766 mg, 4.0 mmol) and TMPꢀH (677 mg, 4.0 mmol)
in CH Cl (40 mL). The crude residue was precipitated from CH Cl after initial trituration with ether. 3a was isolated
as a white powder in 70% yield (1.64 g, 2.81 mmol). Spectral data matches literature.
2
(
2
2
2
2
18
(2,4,6-triethylphenyl)(2,4,6-trimethoxyphenyl)iodonium tosylate (3b). Synthesized according to general procedure
using I (761 mg, 3.0 mmol), 1,3,5ꢀtriethylbenzene (1.13 mL, 6.0 mmol), tosic acid (1.14 g, 6.0 mmol) and TMPꢀH
2
(1.01 g, 6.0 mmol) in CH
2
Cl
2
(60 mL). The crude residue was filtered through a basic alumina pad using 10% MeOH in
1
acetone as eluent. 3b was isolated as a white powder in 63% yield (2.36 g, 3.77 mmol). mp: 120ꢀ122 °C; H NMR
(
CDCl , 400 MHz) δ 7.56 (d, J = 8.1 Hz, 2H), 7.00 (d, J = 7.9 Hz, 2H), 6.92 (s, 2H), 6.11 (s, 2H), 3.79 (s, 3H), 3.78 (s,
3
1
3
1
3
6H), 2.94 (q, J = 7.5 Hz, 4H), 2.58 (q, J = 7.6 Hz, 2H), 2.27 (s, 3H), 1.24ꢀ1.07 (m, 6H); C{ H} NMR (CDCl , 100
MHz) δ 166.5, 160.3, 149.0, 147.5, 143.6, 138.8, 128.3, 127.0, 126.0, 122.5, 91.8, 82.3, 56.8, 56.1, 33.1, 28.5, 21.3,
+
15.2, 14.9; HRMS (ESI): calcd for C21
H28IO
3
[M  OTs] : 455.1078; found 455.1081.
(4-(tert-butyl)-2,6-dimethylphenyl)(2,4,6-trimethoxyphenyl)iodonium tosylate (3c). Synthesized according to
general procedure using I
2
(508 mg, 2.0 mmol), 1ꢀ(tertꢀbutyl)ꢀ3,5ꢀdimethylbenzene (0.75 mL, 4.0 mmol), tosic acid
8
ACS Paragon Plus Environment

Page 9 of 14
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
(761 mg, 4.0 mmol) and TMPꢀH (673 mg, 4.0 mmol) in CH
2
Cl
2
(40 mL). 3c was isolated as yellow powder in 68%
1
yield (1.71 g, 2.72 mmol). mp: 175ꢀ177 °C; H NMR (CDCl
3
, 400 MHz) δ 7.61 (d, J = 8.2 Hz, 2H), 7.09 (s, 2H), 7.05
1
3
1
(d, J = 8.2 Hz, 2H), 6.13 (s, 2H), 3.83 (s, 9H) (Overlapping peaks), 2.64 (s, 6H), 2.25 (s, 3H), 1.25 (s, 9H); C{ H}
NMR (CDCl
3
, 100 MHz) δ 166.4, 160.6, 155.5, 143.2, 142.3, 139.2, 128.5, 126.2, 126.2, 122.3, 91.8, 82.6, 56.7, 56.0,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
+
3
4.8, 31.2, 27.1, 21.4; HRMS (ESI): calcd for C21
H
28IO
3
[M  OTs] : 455.1078; found 455.1080.
(
2,3,5,6-tetramethylphenyl)(2,4,6-trimethoxyphenyl)iodonium tosylate (3d). Synthesized according to general
(270 mg, 1.1 mmol), 1,2,4,5ꢀtetramethylbenzene (286 mg, 2.1 mmol), tosic acid (405 mg, 2.1
procedure using using I
2
mmol) and TMPꢀH (358 mg, 2.1 mmol) in CH
2
Cl
2
(20 mL). 3d was isolated as slightly purple powder in 54% yield
, 400 MHz) δ 7.46 (d, J = 7.8 Hz, 2H), 7.18 (s, 1H),
1
(686 mg, 1.15 mmol). mp: 156 °C (decomp); H NMR (DMSOꢀd
6
1
3
1
7
.10 (d, J = 7.8 Hz, 2H), 6.43 (s, 2H), 3.89 (s, 6H), 3.84 (s, 3H), 2.54 (s, 6H), 2.28 (s, 3H), 2.29 (s, 6H); C{ H} NMR
(DMSOꢀd
6
, 100 MHz) δ 165.8, 159.6, 145.8, 137.5, 137.4, 135..7, 134.8, 128.9, 128.0, 125.5, 92.2, 84.6, 57.0, 56.1,
+
23.9, 21.0, 20.8; HRMS (ESI): calcd for C19
H
24IO
3
[M  OTs] : 427.0765; found 427.0758.
(
3-bromo-2,4,6-trimethylphenyl)(2,4,6-trimethoxyphenyl)iodonium tosylate (3e). Synthesized according to general
procedure using I (520 mg, 2.0 mmol), 2ꢀbromomesitylene (0.63 mL, 4.1 mmol), tosic acid (779 mg, 4.1 mmol) and
TMPꢀH (689 mg, 4.1 mmol) in CH Cl (20 mL) and TFE (20 mL). The crude residue was precipitated with ether after
dissolved in CH Cl /MeOH after initial trituration with ether. 3e was isolated as a white powder in 70% yield (1.9 g,
.86 mmol). Spectral data matches literature.
2
2
2
2
2
1
3b
2
(
2,5-dimethylphenyl)(2,4,6-trimethoxyphenyl)iodonium tosylate (3f). Synthesized according to general procedure I
508 mg, 2.0 mmol), 1,3ꢀdimethylbenzene (0.49 mL, 4.0 mmol), tosic acid (761 mg, 4.0 mmol) and TMPꢀH (673 mg,
Cl (20 mL) and TFE (20 mL).. The crude residue was precipitated with ether after dissolved in
2
(
4.0 mmol) in CH
2
2
CH
2
Cl
2
/MeOH after initial trituration with ether. 3f was isolated as a grey powder in 50% yield (1.15 g, 2.02 mmol).
1
mp: 146ꢀ148 °C; H NMR (DMSOꢀd
6
, 400 MHz) δ 7.87 (s, 1H), 7.46 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 7.8 Hz, 1H),
7
.33 (d, J = 7.8 Hz, 1H), 7.10 (d, J = 7.8 Hz, 2H), 6.44 (s, 2H), 3.95 (s, 6H), 3.85 (s, 3H), 2.54 (s, 3H), 2.28 (s, 6H);
13
1
C{ H} NMR (DMSOꢀd
6
, 100 MHz) δ 165.9, 159.4, 145.8, 138.5, 137.5, 137.3, 137.1, 132.9, 130.7, 128.0, 125.5,
+
1
21.1, 92.1, 86.5, 57.1, 56.1, 24.2, 20.8, 20.0; HRMS (ESI): calcd for C17
99.0440.
H20IO
3
[M  OTs] : 399.0452; found
3
(4-(tert-butyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium tosylate (3g). Synthesized according to general procedure
using I
2
(566 mg, 2.2 mmol), tertꢀbutylbenzene (0.69 mL, 4.5 mmol), tosic acid (848 mg, 4.5 mmol) and TMPꢀH (750
9
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 14
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
mg, 4.5 mmol) in CH
2
Cl
2
(20 mL) and TFE (20 mL).. The crude residue was precipitated with ether after dissolved in
CH
2
Cl
2
/MeOH after initial trituration with ether. 3g was isolated as a grey powder in 59% yield (1.57 g, 2.62 mmol).
9
Spectral data matches literature.
4-methoxy-3-methoxycarbonylphenyl(2,4,6-trimethoxyphenyl)iodonium tosylate (3h). Synthesized according to
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
general procedure using I (139 mg, 0.55 mmol), methyl 2ꢀmethoxybenzoate (0.15 mL, 1.1 mmol), tosic acid (208 mg,
2
1.1 mmol) and TMPꢀH (184 mg, 1.1 mmol) in CH
2
Cl
2
(11 mL). 3h was isolated as a white powder in 61% yield (418
1
mg, 0.66 mmol). mp: 186ꢀ189 °C; H NMR (CDCl
3
, 400 MHz) δ 8.20 (d, J = 2.3 Hz, 1H), 8.10 (dd, J = 9.0, 2.3 Hz,
1
3
1
H), 7.63 (d, J = 7.8 Hz, 2H), 7.06 (d, J = 7.8 Hz, 2H), 6.90 (d, J = 9.1 Hz, 1H), 6.13 (s, 2H), 3.87 (s, 6H), 3.86 (s, 3H),
13
1
.84 (s, 3H), 3.83 (s, 3H) Overlapping peaks!, 2.30 (s, 3H); C{ H} NMR (CDCl , 100 MHz) δ 167.0, 164.6, 161.5,
3
1
60.5, 143.2, 140.4, 139.3, 138.0, 128.5, 126.1, 122.6, 115.0, 104.0, 91.7, 84.8, 57.0, 56.5, 56.1, 52.6, 21.4; H NMR
(
DMSOꢀd
6
, 400 MHz) δ 8.17 (d, J = 2.4 Hz, 1H), 8.03 (dd, J = 9.0, 2.4 Hz, 1H), 7.46 (d, J = 8.0 Hz, 2H), 7.22 (d, J =
9.0 Hz, 1H), 7.10 (d, J = 7.9 Hz, 2H), 6.46 (s, 2H), 3.95 (s, 6H), 3.86 (s, 3H), 3.85 (s, 3H), 3.81 (s, 3H), 2.28 (s, 3H);
13
1
C{ H} NMR (DMSOꢀd
6
, 100 MHz) δ 166.1, 164.3, 160.2, 159.2, 145.8, 139.7, 137.5, 136.9, 128.0, 125.5, 122.3,
+
115.8, 104.5, 92.1, 87.6, 57.3, 56.4, 56.2, 52.5, 20.8; HRMS (ESI): calcd for C18
H20IO
6
[M  OTs] : 459.0299; found
459.0288.
3
-carboxy-4-methoxyphenyl(2,4,6-trimethoxyphenyl)iodonium tosylate (3i). Synthesized according to general
procedure using I (139 mg, 0.55 mmol), 2ꢀmethoxybenzoic acid (167 mg, 1.1 mmol), tosic acid (208 mg, 1.1 mmol)
and TMPꢀH (184 mg, 1.1 mmol) in CH Cl (11 mL). The crude residue was precipitated with ether after dissolved in
CH Cl /MeOH after initial trituration with ether. 3i was isolated as a pale yellow powder in 35% yield (236 mg, 0.38
mmol). mp: 181ꢀ182 °C (decomp); H NMR (DMSOꢀd
dd, J = 9.0, 2.4 Hz, 1H), 7.47 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 9.0 Hz, 1H), 7.1 (d, J = 8.0 Hz, 2H), 6.46 (s, 2H), 3.95
2
2
2
2
2
1
6
, 400 MHz) δ 13.17 (br s, 1H), 8.12 (d, J = 2.4 Hz, 1H), 8.00
(
1
3
1
(s, 6H), 3.86 (s, 3H), 3.84 (s, 3H), 2.28 (s, 3H); C{ H} NMR (DMSO-d , 100 MHz) δ 166.1, 165.4, 160.2, 159.2,
6
145.8, 139.3, 137.5, 136.7, 128.0, 125.5, 123.8, 115.7, 104.4, 92.1, 87.6, 57.3, 56.3, 56.2, 20.8; HRMS (ESI): calcd for
+
C
17
H18IO
6
[M  OTs] : 445.0143; found 445.0134.
3
-chloro-4-methoxyphenyl(2,4,6-trimethoxyphenyl)iodonium tosylate (3j). Synthesized according to general
procedure using I (136 mg, 0.54 mmol), 2ꢀchloroanisole (0.14 mL, 1.1 mmol), tosic acid (203 mg, 1.1 mmol) and
TMPꢀH (180 mg, 1.1 mmol) in CH Cl (11 mL). The crude residue was precipitated with ether after dissolved in
CH Cl /MeOH after initial trituration with ether. 3j was isolated as a white powder in 40% yield (259 mg, 0.43 mmol).
mp: 196ꢀ197 °C; H NMR (DMSOꢀd
2
2
2
2
2
1
6
, 400 MHz)         d, J = 2.2 Hz, 1H), 7.84 (dd, J = 8.9, 2.3 Hz, 1H), 7.46
10
ACS Paragon Plus Environment

Page 11 of 14
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
(d, J = 8.0, 2H), 7.21 (d, J = 8.9 Hz, 1H), 7.10 (d, J = 8.0 Hz, 2H), 6.46 (s, 2H), 3.95 (s, 6H), 3.88 (s, 3H), 3.86 (s, 3H),
1
3
1
2
.28 (s, 3H); C{ H} NMR (DMSO-d
6
, 100 MHz)  δ 166.6, 159.7, 157.6, 146.3, 138.0, 135.7, 135.6, 128.5, 126.0,
+
123.3, 116.0, 105.1, 92.5, 88.1, 57.8, 57.1, 56.6, 21.2; HRMS (ESI): calcd for C16
H17ClIO
4
[M  OTs] : 434.9855;
found 434.9850.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3
-bromo-4-methoxyphenyl(2,4,6-trimethoxyphenyl)iodonium tosylate (3k). Synthesized according to general
procedure using. I (136 mg, 0.54 mmol), 2ꢀbromoanisole (0.14 mL, 1.1 mmol), tosic acid (204 mg, 1.1 mmol) and
2
TMPꢀH (180 mg, 1.1 mmol) in CH
2
Cl
2
(11 mL). 3k was isolated as a white powder in 44% yield (308 mg, 0.47 mmol).
1
mp: 188ꢀ191 °C; H NMR (DMSOꢀd
6
, 400 MHz) δ 8.12 (d, J = 2.2 Hz, 1H), 7.87 (dd, J = 8.8, 2.2 Hz, 1H), 7.46 (d, J =
8.1 Hz, 2H), 7.17 (d, J = 8.9 Hz, 1H), 7.10 (d, J = 8.1 Hz, 2H), 6.46 (s, 2H), 3.95 (s, 6H), 3.85 (s, 3H), 3.85 (s, 3H),
1
3
1
2.28 (s, 3H); C{ H} NMR (DMSOꢀd
6
, 100 MHz) δ 166.1, 159.2, 158.0, 145.8, 138.0, 137.5, 135.7, 128.0, 125.5,
+
115.4, 112.3, 105.1, 92.1, 87.7, 57.3, 56.8, 56.2, 20.8; HRMS (ESI): calcd for C H BrIO [M  OTs] : 478.9349;
1
6
17
4
found 478.9340.
2-bromo-4-methoxyphenyl(2,4,6-trimethoxyphenyl)iodonium tosylate (3l) and 4-bromo-2-methoxyphenyl(2,4,6-
trimethoxyphenyl)iodonium tosylate (3m). Synthesized according to general procedure using I (140 mg, 0.55 mmol),
ꢀbromoanisole (0.14 mL, 1.1 mmol), tosic acid (212 mg, 1.1 mmol) and TMPꢀH (186 mg, 1.1 mmol) in CH Cl (10
2
3
2
2
mL). 3l and 3m were isolated as a 5:1 mixture as a yellow powder in 40% yield (288 mg, 0.44 mmol). NMR Data for
1
major isomer: H NMR (DMSOꢀd
6
, 400 MHz) δ 8.05 (d, J = 8.9 Hz, 1H), 7.49ꢀ7.42 (m, 3H), 7.10 (d, J = 7.8 Hz, 2H),
13
1
6
.98 (dd, J = 8.0, 2.8 Hz, 1H), 6.43 (s, 2H), 3.93 (s, 6H), 3.85 (s, 3H), 3.80 (s, 3H), 2.28 (s, 3H); C{ H} NMR
DMSOꢀd , 100 MHz) δ 166.1, 162.5, 159.4, 145.9, 140.1, 137.5, 128.0, 127.9, 125.5, 118.7, 116.3, 111.3, 91.9, 57.1,
6.1, 56.1, 20.8.
(
6
5
(5-chloro-2-methoxyphenyl)(2,4,6-trimethoxyphenyl)iodonium tosylate (3n). Synthesized according to general
procedure using I (126 mg, 0.50 mmol), 4ꢀchloroanisole (0.12 mL, 1.0 mmol), tosic acid (189 mg, 1.0 mmol) and
2
TMPꢀH (167 mg, 1.0 mmol) in CH
2
2
Cl (10 mL). 3n was isolated as a grey powder in 14% yield (86 mg, 0.14 mmol).
1
mp: 158ꢀ159 °C; H NMR (MeOHꢀd
4
, 400 MHz) δ 7.81 (d, J = 2.5 Hz, 1H), 7.69 (d, J = 8.1 Hz, 2H), 7.57 (dd, J =
13
1
8.9, 2.5 Hz, 1H), 7.24ꢀ7.18 (m, 3H), 6.41 (s, 2H), 3.97 (s, 6H), 3.94 (s, 3H), 3.89 (s, 3H), 2.36 (s, 3H); C{ H} NMR
(MeOHꢀd
4
, 100 MHz) δ 168.8, 161.6, 157.4, 143.6, 141.6, 136.2, 135.1, 129.8, 128.0, 126.9, 114.6, 105.6, 92.9, 84.9,
+
57.9, 57.7, 56.7, 21.3; HRMS (ESI): calcd for C H ClIO [M  OTs] : 434.9855; found 434.9839.
1
6
17
4
11
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 14
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(5-bromo-2-methoxyphenyl)(2,4,6-trimethoxyphenyl)iodonium tosylate (3o). Synthesized according to general
2
procedure using I (138 mg, 0.54 mmol), 4ꢀbromoanisole (0.14 mL, 1.1 mmol), tosic acid (207 mg, 1.1 mmol) and
TMPꢀH (183 mg, 1.1 mmol) in CH
2
Cl
2
(10 mL). 3o was isolated as a yellow powder in 23% yield (165 mg, 0.25
, 400 MHz) δ 7.94 (d, J = 2.4 Hz, 1 H), 7.72ꢀ7.66 (m, 3H), 7.21 (d,
1
mmol). mp: 172 °C (decomp); H NMR (MeOHꢀd
4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
13
1
J = 7.9 Hz, 2H), 7.15 (d, J = 8.9 Hz, 1H), 6.41 (s, 2H), 3.96 (s, 6H), 3.93 (s, 3H), 3.89 (s, 3H), 2.36 (s, 3H); C{ H}
NMR (MeOHꢀd
4
, 100 MHz) δ 168.8, 161.6, 157.8, 143.6, 141.6, 139.0, 138.1, 129.8, 126.9, 115.4, 114.6, 106.5, 92.9,
+
84.9, 57.9, 57.7, 57.7, 21.3; HRMS (ESI): calcd for C16
H17BrIO
4
[M  OTs] : 478.9349; found 478.9341.
4-(tert-butyl)-2,6-dimethyl(hydroxy)(tosyloxy)iodobenzene (1c). Synthesized according to the general procedure
except no second arene was added and the reaction time was limited to 1 h at RT, .starting from I (635 mg, 2.5 mmol),
tertꢀbutylbenzene (0.94 mL, 5.0 mmol), and tosic acid (951 mg, 5.0 mmol) in CH Cl (40 mL). The product was
2
2
2
precipitated using a mixture of ether and pentane and was isolated as a white powder in 66% yield (1.56 g, 3.27 mmol).
1
mp: 133 °C (decomp); H NMR (CDCl
3
, 400 MHz) δ 7.39 (d, J = 8.1 Hz, 2H), 7.18 (s, 2H), 7.05 (d, J = 8.1 Hz, 2H),
13
1
4
3
.90 (br s, 1H), 2.68 (br s, 6H), 2.34 (s, 3H), 1.33 (s, 9H); C{ H} NMR (CDCl , 100 MHz) δ 157.5, 141.9, 141.3,
139.3, 129.0, 126.0, 125.7, 35.1, 31.2, 26.9, 21.5 Note: The C-I carbon could not be observed. HRMS (ESI): calcd for
+
C
12
H
18IO [M  OTs] : 305.0397; found 305.0392.
Mesityl(2,4,6-trimethoxyphenyl)iodonium triflate (3p). Synthesized according to general procedure using using I
251 mg, 1.0 mmol), mesitylene (0.28 mL, 2.0 mmol), tosic acid (376 mg, 2.0 mmol) and TMPꢀH (333 mg, 2.0 mmol)
in CH Cl (20 mL). The crude mixture was cooled to 0 °C and triflic acid (0.18 mL, 2.0 mmol) was added dropꢀwise
followed by stirring at RT for 1 h. The crude residue was precipitated from CH
2
(
2
2
2
Cl
2
after initial trituration with ether. 3a
1
was isolated as a white powder in 60% yield (0.66 g, 1.2 mmol). mp: 140ꢀ141 °C (decomp); H NMR (DMSOꢀd
6
, 400
, 100
1
3
1
MHz) δ 7.13 (s, 2H), 6.44 (s, 2H), 3.90 (s, 6H), 3.85 (s, 3H), 2.56 (s, 6H), 2.26 (s, 3H); C{ H} NMR (DMSOꢀd
6
1
9
MHz) δ 165.8, 159.6, 142.2, 141.7, 129.3 121.7, 120.7 (q, J = 321 Hz), 92.2, 84.3, 57.0, 56.1, 25.7, 20.4; F NMR
+
(DMSOꢀd
6
, 337 MHz) ꢀ77.8. HRMS (ESI): calcd for C18
H22IO
3
[M  OTf] : 413.0608; found 413.0612.
19
2
,4-Dimethylphenyl(2,4,6-trimethylphenyl) ether (4). Synthesized according to literature procedure. Isolated as a
20
transparent oil in 91% yield (109 mg, 0.45 mmol). Spectral data matches literature.
AUTHOR INFORMATION
Corresponding Author
*
berit.olofsson@su.se
12
ACS Paragon Plus Environment

Page 13 of 14
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
ORCID
Berit Olofsson: 0000ꢀ0001ꢀ7975ꢀ4582
Notes
The authors declare no competing financial interest.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACKNOWLEDGMENTS
The Swedish Research Council (2015ꢀ04404) is kindly acknowledged for financial support.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/joc.xxxxxx:
1
13
Copies of the H and C NMR spectra of all products (PDF).
REFERENCES
(1) (a) Olofsson, B. Top. Curr. Chem. 2015, 373, 135ꢀ166. (b) Aradi, K.; Tóth, B. L.; Tolnai, G. L.; Novák, Z. Synlett 2016, 27,
1456ꢀ1485. (c) Merritt, E. A.; Olofsson, B. Angew. Chem. Int. Ed. 2009, 48, 9052ꢀ9070.
(2) (a) Bielawski, M.; Zhu, M.; Olofsson, B. Adv. Synth. Catal. 2007, 349, 2610ꢀ2618. (b) Bielawski, M.; Olofsson, B. Chem.
Commun. 2007, 2521ꢀ2523.
(3) (a) Koser, G. F.; Wettach, R. H.; Smith, C. S. J. Org. Chem. 1980, 45, 1543ꢀ1544. (b) Carroll, M. A.; Pike, V. W.; Widdowson,
D. A. Tetrahedron Lett. 2000, 41, 5393ꢀ5396. (c) Dohi, T.; Ito, M.; Morimoto, K.; Minamitsuji, Y.; Takenaga, N.; Kita, Y. Chem.
Commun. 2007, 4152ꢀ4154. (d) Chun, J.ꢀH.; Pike, V. W. J. Org. Chem. 2012, 77, 1931ꢀ1938. (e) Sokolovs, I.; Suna, E. J. Org.
Chem. 2016, 81, 371ꢀ379.
(4) Yamamoto, Y.; Togo, H. Synlett 2005, 2486ꢀ2488.
(
5) Merritt, E. A.; Carneiro, V. M. T.; Silva, L. F.; Olofsson, B. J. Org. Chem. 2010, 75, 7416ꢀ7419.
6) Dohi, T.; Yamaoka, N.; Kita, Y. Tetrahedron 2010, 66, 5775ꢀ5785.
(
(7) Zhu, M.; Jalalian, N.; Olofsson, B. Synlett 2008, 2008, 592ꢀ596.
8) The synthesis of unsymmetrical salts with mCPBA/TfOH was also unsuccessful, despite several attempts to alter reaction
(
conditions and stoichiometry, as the reaction between the formed iodine(III) intermediate and the arene was faster than the iodination
of the arene (see ref 2).
(9) Seidl, T. L.; Sundalam, S. K.; McCullough, B.; Stuart, D. R. J. Org. Chem. 2016, 81, 1998ꢀ2009.
(10) (a) Hossain, M. D.; Ikegami, Y.; Kitamura, T. J. Org. Chem. 2006, 71, 9903ꢀ9905. (b) Qin, L.; Hu, B.; Neumann, K. D.;
Linstad, E. J.; McCauley, K.; Veness, J.; Kempinger, J. J.; DiMagno, S. G. Eur. J. Org. Chem. 2015, 2015, 5919ꢀ5924. (c) Soldatova,
N.; Postnikov, P.; Kukurina, O.; Zhdankin, V. V.; Yoshimura, A.; Wirth, T.; Yusubov, M. S. ChemistryOpen 2017, 6, 18ꢀ20.
(11) Malmgren, J.; Santoro, S.; Jalalian, N.; Himo, F.; Olofsson, B. Chem. Eur. J. 2013, 19, 10334ꢀ10342.
13
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 14
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(
12) (a) Oh, C. H.; Kim, J. S.; Jung, H. H. J. Org. Chem. 1999, 64, 1338ꢀ1340. For a recent example, see (b) Linstad, E. J.; Vavere,
A. L.; Hu, B.; Kempinger, J. J.; Snyder, S. E.; DiMagno, S. G. Org. Biomol. Chem. 2017, 15, 2246ꢀ2252.
13) (a) Ghosh, R.; Olofsson, B. Org. Lett. 2014, 16, 1830ꢀ1832. (b) Lindstedt, E.; Stridfeldt, E.; Olofsson, B. Org. Lett. 2016, 18,
234ꢀ4237. (c) Sandtorv, A. H.; Stuart, D. R. Angew. Chem. Int. Ed. 2016, 55, 15812ꢀ15815. (d) Dohi, T.; Ueda, S.; Hirai, A.;
Kojima, Y.; Morimoto, K.; Kita, Y. Heterocycles 2017, 95, 1272ꢀ1284.
(
4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(14) Carreras, V.; Sandtorv, A. H.; Stuart, D. R. J. Org. Chem. 2017, 82, 1279ꢀ1284.
(15) The corresponding transformation using triflic acid with less reactive arenes proved unsuccessful, and complex mixtures were
obtained with bromobenzene and trifluoromethylbenzene also when water and TMPꢀH were added in a sequential fashion to decrease
the reactivity in the second step, see Bielawski, M.; Malmgren, J.; Pardo, L. M.; Wikmark, Y.; Olofsson, B. ChemistryOpen 2014, 3,
1
9ꢀ22.
16) Vogel, A. I.; Furniss, B. S.; Hannaford, A. J.; Rogers, V.; Smith, P. W. G.; Tatchell, A. R., Vogel's Textbook of Practical
Organic Chemistry 5th Ed.: Prentice Hall: Harlow, 1996; p 456.
(
(
(
(
(
17) Sundalam, S. K.; Nilova, A.; Seidl, T. L.; Stuart, D. R. Angew. Chem. Int. Ed. 2016, 55, 8431ꢀ8434.
18) Gonda, Z.; Novák, Z. Chem. Eur. J. 2015, 21, 16801ꢀ16806.
19) Jalalian, N.; Petersen, T. B.; Olofsson, B. Chem. Eur. J. 2012, 18, 14140ꢀ14149.
20) Jalalian, N.; Ishikawa, E. E.; Silva, L. F.; Olofsson, B. Org. Lett. 2011, 13, 1552ꢀ1555.
14
ACS Paragon Plus Environment