Flow Synthesis of Iodonium Trifluoroacetates through Direct Oxidation of Iodoarenes by Oxone

Article abstract of DOI:10.1002/ejoc.201900220

Flow chemistry is considered to be a versatile and complementary methodology for the preparation of valuable organic compounds. We describe a straightforward approach for the synthesis of iodonium trifluoroacetates through the direct oxidation of iodoarenes in a simple flow reactor using an Oxone-filled cartridge. Optimization has been carried out using the Nelder–Mead algorithm. The procedure allows a wide range of iodonium salts to be prepared from simple starting materials.

Full text of DOI:10.1002/ejoc.201900220

A Journal of
Accepted Article
Title: Flow Synthesis of Iodonium Trifluoroacetates through Direct
Oxidation of Iodoarenes by Oxone®
Authors: Natalia S Soldatova, Pavel S Postnikov, Mekhman S
Yusubov, and Thomas Wirth
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: Eur. J. Org. Chem. 10.1002/ejoc.201900220
Link to VoR: http://dx.doi.org/10.1002/ejoc.201900220
Supported by

10.1002/ejoc.201900220
European Journal of Organic Chemistry
FULL PAPER
Flow Synthesis of Iodonium Trifluoroacetates through Direct
Oxidation of Iodoarenes by Oxone®
Natalia S. Soldatova,[a,b] Pavel S. Postnikov,[b,c] Mekhman S. Yusubov,*[a,b] and Thomas Wirth*[a]
Abstract: Flow chemistry is considered to be a versatile and
complementary methodology for the preparation of valuable organic
compounds. We describe a straightforward approach for the synthesis
of iodonium trifluoroacetates through the direct oxidation of
iodoarenes in a simple flow reactor using an Oxone-filled cartridge.
Optimization has been carried out using the Nelder-Mead algorithm.
The procedure allows a wide range of iodonium salts to be prepared
from simple starting materials.
preparation of iodonium trifluoroacetates through oxidation with
Oxone is accompanied by a long reaction time.[9b] Therefore, the
development of novel approaches for the preparation of iodonium
salts is required for further simplification of the synthetic protocols.
Flow chemistry is considered to be a straightforward method for
the synthesis of various organic compounds and intermediates.
Flow methodology provides a range of advantages over batch
protocols, such as easy scale-up and optimization, effective
mass- and energy transfer, reduction of waste and reaction time,
safe in situ generation of toxic or hazardous compounds.[11 ]
Moreover, flow methodology allows an easy use of optimization
algorithms in manual or automatic mode, which improve the fast
search for optimal reaction conditions.[12] The flow synthesis of
hypervalent iodine compounds is little explored and only a few
contributions can be found in the literature. Noël and coauthors
developed a synthesis of diaryliodonium salts in flow with mCPBA
as oxidant[13] while we reported the use of electricity as a reagent
for the synthesis of iodine(III) reagents.[ 14 ] Nevertheless, the
method proposed by Noël uses mCPBA with the aforementioned
disadvantages. The electrochemical synthesis is free from
reagent waste but allows the synthesis of diaryliodonium salts
only from electron-rich substrates (Scheme 1).
Introduction
In last decades, hypervalent iodine compounds have found wide
application as mild, efficient and environmentally friendly reagents
in the modern toolbox of synthesis.[1] In particular, diaryliodonium
salts have become essential instruments for arylation of different
2
]
nucleophiles with or without metal catalysts.[
Moreover,
iodonium salts are found as reagents for the surface modification
of carbon materials and noble metals.[3]
Traditional procedures for the preparation of iodonium salts
include the reaction of electrophilic iodine(III) species with
electron-rich arenes.[4] Nowadays, the preliminary stage of the
preparation of iodanes can be excluded and reactive iodine(III)
species can be generated in situ. Such procedures have been
investigated by Olofsson and co-workers[ 5 ] and successfully
applied for the preparation of diaryliodonium tosylates, triflates
and tetrafluoroborates.[6] Common oxidants for this reaction are
K2S2O8, NaBO3, AcOOH and H2O2•urea.[7] Nevertheless, one of
the most used oxidants for the preparation of iodonium salts is
meta-chloroperbenzoic acid (mCPBA).[8] Recently, we reported
other methods for the preparation of iodonium salts utilizing
Oxone® as a cheap and alternative oxidant to mCPBA.[9]
A Electrochemical synthesis of diaryliodonium salts in flow
I
I–
–
HSO4
electrolysis
H2SO4, MeCN
I
I
KI, H2O
R2
R2
R1
R1
R2
R1
up to 72%
Wirth et al. 2011
B Synthesis of diaryliodonium triflates in flow with mCPBA
I
TfO–
mCPBA, TfOH
flow synthesis
I
R2
R2
Noël et al. 2011
R1
R1
up to 92%
However, the known approaches for the preparation of iodonium
salts do not align with the modern requirements on industrial
processes. For instance, mCPBA is considered to be a hazardous
reagent requiring specific operation and storage conditions[10] as
well as the disposal of mCPBA-containing by-products. The
C This work: Synthesis of diaryliodonium trifluoroacetates in flow with Oxone
I
®
Oxone®
CF3COO–
I
R1
R2
R1
up to 96%
[a]
[b]
[c]
Prof. Dr. T. Wirth
R2
School of Chemistry, Cardiff University
Park Place, Main Building, Cardiff CF10 3AT, United Kingdom
E-mail: wirth@cf.ac.uk
Scheme 1. Flow synthesis of diaryliodonium salts.
Homepage: http://blogs.cardiff.ac.uk/wirth/
N. S. Soldatova, P. S. Postnikov, M. S. Yusubov
Research School of Chemistry and Applied Biomedical Sciences,
Tomsk Polytechnic University,
634034 Tomsk, Russian Federation
Email: yusubov@tpu.ru
Herein we report on the development of a flow synthesis of
diaryliodonium trifluoroacetates using the Oxone® as the oxidant.
Reaction conditions have been optimized using the Nelder-Mead
algorithm for the synthesis of [bis(trifluoroacetoxy)iodo]benzene
in flow and the subsequent reaction with arenes and arylboronic
acids for the preparation of diaryliodonium salts.
Department of Solid State Engineering, Institute of Chemical
Technology, 16628 Prague, Czech Republic
Supporting information for this article is given via a link at the end of
the document.
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10.1002/ejoc.201900220
European Journal of Organic Chemistry
FULL PAPER
Results and Discussion
Preliminary studies began with the preparation of
[bis(trifluoroacetoxy)iodo]benzene under flow conditions based
on our previous findings.[15] As reported earlier, Oxone® can be
used as an effective oxidant for the preparation of iodine(III)
derivatives and appropriate diaryliodonium trifluoroacetates. We
proposed that a simple cartridge filled by powdered Oxone® can
be the key part of the flow setup for the synthesis of iodine(III)
derivatives. The flow setup is shown in Scheme 2 and proceeds
by pumping
a
0.1
M
solution of iodobenzene 1a in
dichloromethane containing 10% trifluoroacetic acid (TFA)
through the Oxone® cartridge.
O
O
I
CF3
CF3
Ph-I 1a
F3CCO2H
CH2Cl2
Figure 1. Graphic representation of the optimization of the synthesis of 2a.
®
Oxone®
Ph
O
O
Best results were obtained in reactions 5 and 9 where 2a has
been isolated in 90% yield but reactions 5 required an increased
amount of CF3COOH without any influence on the yield of the
desired product. The conditions of reaction 5 (0.09 M PhI, 13.9
vol% TFA, 20 min) have then also been used to successfully
prepare [bis(trifluoroacetoxy)iodo]toluene 2b in 86% yield and
[bis(trifluoroacetoxy)iodo]-3-trifluoromethylbenzene 2c (59%
yield).
During the optimization we found that the amount of TFA is crucial
for obtaining good yields of [bis(trifluoroacetoxy)iodo]benzene 2a.
From the point of view of reducing the amount of trifluoroacetic
acid, best results were obtained in the run 8. However, the
residence time there increased significantly leading to a potential
clogging of the Oxone cartridge, which was also observed when
the cartridge was washed at the high flow rates. The reaction is
most likely to proceed at the border between the liquid and solid
phase. The interaction between Oxone® and TFA leads to the
generation of peroxosulfuric acids and the amount of TFA
determines the effective concentration of oxidant and increases
its solubility.
The optimization study has been carried out using a freshly filled
Oxone® column for each experiment. One advantage of a
reagent-filled column is the possibility for a repeated use. We
therefore determined the number of runs for the one loading of
Oxone® using the preparation of 2a as an example. The yield of
2a did not changed during the first 3 runs (Figure 2). Clogging
issues after the 3rd run was overcome by re-loading the column
with the same Oxone® after drying and crushing allowing to retain
the same efficiency (Figure 2). Re-loading after every 3rd run kept
the efficiency to 11 runs, which corresponds to 1.4 equivalents of
Oxone® for the oxidation of iodobenzene. As reloading is not ideal,
we applied ultrasonication to the Oxone®-filled column after the
3rd run which regenerates the column with same efficiency as the
reloading procedure (Figure S2, supporting information). The
dramatic decrease of yields after run 12 is associated with the
depletion of potassium peroxymonosulfate in the solid phase.
2a
Scheme 2. Flow synthesis of [bis(trifluoroacetoxy)iodo]benzene 2a.
Different factors affect the yield of product and the reaction rate.[16]
For the proposed setup, the concentration of reagents, the
residence time and flow rate are the most important for the flow
process. Even the optimization of a synthetic procedure with few
variables can be performed by the Nelder-Mead Simplex method,
its efficiency for flow protocols has been demonstrated
17
]
previously.[
We investigated the residence time, the
concentration of iodobenzene, and the concentration of TFA. The
results of the optimization are graphically shown in Figure 1,
details are in Table S1 (supporting information). The amount of
Oxone has been constant for the all experiments, the reaction
time varied between 15 and 28.3 minutes, the amount of TFA
between 7.7 and 17.4 vol% and the concentration of iodobenzene
from 0.082 to 0.12 mmol mL–1. After the end of each reaction, the
syringe with the mixture of reagents was replaced by a syringe
with dichloromethane and the Oxone column was washed. Based
on the selected parameters to optimize the yield of the product,
we built the first simplex and run the reaction (reactions 1-4). After
the new simplex has been generated, the reactions have been
carried out under the new conditions until the termination criterion
was reached (reactions 5-10).
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10.1002/ejoc.201900220
European Journal of Organic Chemistry
FULL PAPER
in the tubing reactor and clogging issues. Therefore, mesitylene
was added in the same TFA-dichloromethane mixture, which
allowed the isolation of mesityl(phenyl)iodonium trifluoroacetate
6a in 90% yield. An increase of the reactor volume from 0.5 mL to
1 mL did not change the yield of product 6a.
The flow setup shown in Scheme 3 has then been applied to
different arenes and iodoarenes leading to iodonium salts
displayed in Figure 3.
CF3COO-
CF3COO-
CF3COO-
CF3COO-
OMe
I+
I+
I+
I+
S
OMe
MeO
OMe
6a
90%
6b
67%
6c
64%
6dc
77%
CF3COO-
OMe
CF3COO-
CF3COO-
CF3COO-
Figure 2. Repeated synthesis of 2a using the same Oxone cartridge.
I+
I+
I+
I+
OCF3
MeO
OMe
6hc
72%
6ed
74%
6fd
76%
6g
94%
The optimized procedure for the preparation of iodine(III)
derivatives was then extended to the synthesis of diaryliodonium
salts by adding an arene as the second substrate. The
intramolecular version of the process leads to dibenziodolium
trifluoroacetate as an example for a cyclic iodonium salt[18] in
almost quantitative yields as shown in Scheme 3.
CF3COO-
CF3COO-
CF3COO-
CF3COO-
I+
I+
I+
I+
S
OMe
OMe
6k
93%
6l
88%
6i
96%
6j
83%
CF3COO-
CF3COO-
CF3COO-
CF3COO-
OMe
OMe
I+
I+
I+
I+
MeO
OMe F3CO
F3CO
MeO
OMe
Cl
OMe
6oc
66%
6p
56%
–
6mc
50%
6n
78%
CF3CO2
I
I
®
Oxone®
CF3COO-
CF3COO-
CF3COO-
CF3COO-
C
OMe
OMe
I+
I+
I+
F3
OMe
I+
S
Cl
MeO
OMe
F
F
MeO
3
4 96%
6sc
60%
6t
60%
6qc
59%
6r
78%
F3CCO2H
CH2Cl2
CF3COO-
C
OMe
F3
I+
Scheme 3. Synthesis of dibenziodolium trifluoroacetate 4.
MeO
OMe
6uc
18%
Initial efforts to prepare acyclic diaryliodonium trifluoroacetates in
flow were less successful when a mixture of mesitylene and
iodobenzene were pumped through the Oxone cartridge. We
observed the overoxidation of the mesitylene and the desired
mesityl(phenyl)iodonium trifluoroacetate was obtained in only
68% yield. Addition of the arene to the flow stream after the
iodine(III) formation as shown in Scheme 4 is leading to higher
yields.
Figure 3. Synthesis of iodonium salts. aReaction conditions: 10 mL reagent
mixture 1: 1 (0.9 mmol) and TFA (1.39 mL) in CH2Cl2, flow rate: 0.11 mL/min;
11 ml reagent mixture 2: 5 (1.09 mmol), flow rate: 0.11 mL/min; Oxone-filled
cartidge (5 g), room temperature; c1.04 mmol of arene was used;
dPhenylboronic acid was used instead arene; e4-Trifluoromethoxyboronic acid
was used instead of arene.
Iodobenzene 1a smoothly reacted with electron-rich arenes 5a-d
with the formation of desired iodonium salts 6a-d in good yields.
Similar reactivities have been found in the reaction of methyl-
substituted iodoarenes 1b,1d, 1e and 1f with arenes 5a-d. The
corresponding iodonium salts have been isolated in excellent
yields. Only (3,5-dimethylphenyl)(2,4,6-trimethoxyphenyl) iodo-
nium trifluoroacetate 6m was accessible in only 50% yield,
probably due to steric hindrance. We successfully applied the
method to the preparation of iodonium salts from electron-poor
iodoarenes 1c, 1g and 1h. In these cases, the yields of target
compounds 6p-u have been slightly lower than for electron-rich
arenes. This fact can be explained by the lower reactivity of
appropriate iodoarenes in the oxidation process.[9b] Nevertheless,
the flow approach provides a much shorter reaction time in
comparison with batch procedures.[9a] We successfully prepared
a range of 1,3,5-trimethoxyphenyl-substituted iodonium salts,
Ph-I 1a
F3CCO2H
CH2Cl2
®
Oxone®
–
CF3CO2
I
Ph
0.5 mL
6a 90%
5a
F3CCO2H
CH2Cl2
Scheme 4. Synthesis of iodonium salt 6a.
Initial experiments have been carried out using mesitylene 5a as
an arene and iodobenzene 1a. The addition of mesitylene in pure
dichloromethane has been unsuccessful due to sedimentation of
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10.1002/ejoc.201900220
European Journal of Organic Chemistry
FULL PAPER
pump at a flow rate of 0.11 mL/min. After the end of the reagent
addition, the syringe with the mixture of reagents was immediately
replaced with a syringe containing CH2Cl2 (10 mL) and CH2Cl2
was pumped with 0.11 mL/min flow rate for 30 min after which the
flow rate was increased to 0.5 mL/min. The solvent was removed
from the reaction mixture in vacuo and the residue was dried in
vacuo (7 mbar) for 30 min. The crude mixture was dissolved in
CH2Cl2 (5 mL) and any precipitate was removed through filtration.
The solvent was removed in vacuo, the residue was washed with
hexane (3 x 2 mL) and dried in vacuo.
which are considered to be most valuable compounds for further
substitution.[8a,19]
Finally, we investigated to obtain the iodonium salts from electron-
poor arenes such as benzene and toluene. The application of flow
method did not change the reactivity of hypervalent iodine(III)
species, and our efforts to involve benzene were unsuccessful.
But the desired iodonium salts 6e and 6f could be obtained in the
same setup using appropriate boronic acids as reagents in high
yields. To the best our knowledge, these is the first example of
the preparation of iodonium salts from boronic acids in a flow
approach.
[Bis(trifluoroacetoxy)iodo]benzene (2a) [15]
The reaction of iodobenzene 1a (0.898 mmol, 183 mg, 100 µL) and TFA
(1.39 mL) according to the general procedure afforded 344-363mg (89-
94%) of [bis(trifluoroacetoxy)iodo]benzene 2a as a white crystalline solid;
mp: 119-121 ºC (lit 118-120 ºC [15]). 1H NMR (400 MHz, CDCl3:CF3COOH
25:1): δ 8.21 (d, J = 8.4 Hz, 2H), 7.76 (t, J = 7.6 Hz, 1H), 7.63 (t, J = 7.6
Hz, 2H) ppm.
Conclusions
In conclusion, the synthesis of diaryliodonium trifluoroacetates in
flow was demonstrated using an Oxone®-packed reactor. The
Nelder-Mead algorithm for the optimization of the synthesis of
bis(trifluoroacetoxy)iodobenzene enabled an increase of
efficiency and speeded up the optimization process. Under
optimized flow conditions a wide range of diaryliodonium
1-Bis(trifluoroacetoxy)iodo-4-methylbenzene (2b) [20]
The reaction of 4-iodotoluene 1b (0.898 mmol, 196 mg) and TFA (1.39 mL)
according to the general procedure afforded 343 mg (86%) of 1-
[bis(trifluoroacetoxy)iodo]-4-methylbenzene 2b as a pale yellow crystalline
solid; mp: 114-116 ºC (lit 113-115 ºC [20]). 1H NMR (400 MHz,
CDCl3:CF3COOH 25:1): δ 8.10 (d, J = 8.4 Hz, 2H), 7.41 (d, J = 8.4 Hz, 2H),
2.51 (s, 3H) ppm.
trifluoroacetates including
a
cyclic derivative and some
derivatives of [bis(trifluoroacetoxy)iodo]benzene with yields up to
96% were accessible. The flow approach to the synthesis of
diaryliodonium trifluoroacetates simplifies their formation with
sensitive to strong oxidants electron-rich arenes with good yields.
Successful examples of utilizing arylboronic acids to replace
electron-poor arenes expands the applications of this method.
1-[Bis(trifluoroacetoxy)iodo]-3-(trifluoromethyl)benzene (2c) [21]
The reaction of 3-iodobenzotrifluoride 1c (0.898 mmol, 244 mg) and TFA
(1.39 mL) according to the general procedure afforded 262 mg (59%) of 3-
[bis(trifluoroacetoxy)iodo]-1-(trifluoromethyl)benzene 2c as
a
white
crystalline solid; mp: 96-98 ºC (lit 96-97 ºC [21]). 1H NMR (400 MHz,
CDCl3:CF3COOH 25:1): δ 8.44 (s, 1H), 8.39 (d, J = 8.4 Hz, 1H), 8.00 (d, J
= 7.6 Hz, 1H), 7.79 (t, J = 8.0 Hz, 1H) ppm. 19F NMR (376 MHz,
CDCl3:CF3COOH 25:1): δ -62.98, -75.70 ppm.
Experimental Section
General information
All aromatic precursors, and other reagents and solvents were
from commercial sources and used without further purification
from freshly opened containers, NMR spectra were recorded at
300, 400 and 500 MHz (1H NMR), 75, 100 MHz (13C NMR), 376
and 471 MHz (19F NMR). Chemical shifts (δ) are reported in parts
per million. Mass spectrometric measurements were performed
by Laboratory of Physical–Chemical Analytical Methods of Tomsk
State University or the EPSRC Mass Spectrometry Service
Centre, Swansea University and ions were generated by the
atmospheric pressure Electrospray Ionization (ESI).
Synthesis of dibenzo[b,d]iodoniumtrifluoroacetate (4)
2-Iodobiphenyl 3 (0.898 mmol, 251 mg) and TFA (1.39 mL) was dissolved
in CH2Cl2 (5 mL) and the volume of mixture was brought to 10 mL by
adding CH2Cl2. Then the reagent mixture was pumped through Oxone-
filled column with syringe pump. Flow rate was 0.11 mL/min. After the end
of the reagent addition, the syringe with a mixture of reagents was
immediately replaced with a syringe with CH2Cl2 (10 mL) and CH2Cl2 was
pumped with 0.11 mL/min flow rate for 30 min. Then flow rate was
increased to 0.5 mL/min and addition continued until the end of the CH2Cl2
in the syringe. The solvent was removed from the resulting solution in
vacuo and obtained residue was diluted with 5 mL of water. Product was
extracted with CH2Cl2 (3 x 5 mL). The organic layer was dried over Na2SO4
and solvent was removed in vacuo. Then diethyl ether (5 mL) was added
to residue and formation of precipitate was observed. The suspension was
stirred for 10 minutes and product was filtrated and washed with diethyl
ether (5 mL) and hexane (2 x 5 mL). The product was dried in vacuo.
Dibenzo[b,d]iodoniumtrifluoroacetate 4 was obtained in 96% yield (379 mg)
as a beige crystalline solid; mp: 108-110 ºС. 1H NMR (400 MHz, CDCl3): δ
8.46 (d, J = 8.4 Hz, 2H), 8.10 (dd, J = 8.0, 1.2 Hz, 2H), 7.76 (t, J = 8.0 Hz,
2H), 7.61 (t, J = 8.4 Hz, 2H) ppm. 13C NMR (100 MHz, CDCl3): δ 161.3 (q,
J = 38 Hz), 142.1, 131.4, 131.4, 131.0, 126.5, 122.0, 115.7 (q, J = 287 Hz)
ppm. 19F NMR (376 MHz, CDCl3): δ -75.52 ppm. HRMS (ESI): m/z calcd
for C12H8I+: 278.9665; found: 278.9665.
Preparation of the Oxone® cartridge:
An Omnifit column 150 mm (6.6 mm ID) was packed with fine
powdered Oxone (5.0 g, 8.1 mmol) occupying a volume of approx.
2.2 ml, and the column was washed with CH2Cl2 (10 mL) at a flow
rate of 0.5 mL/min.
General Procedure for the synthesis of [bis(trifluoro-
acetoxy)iodo]benzene derivatives 2a-b
Iodoarene (0.898 mmol) and TFA (1.39 mL) were dissolved in
CH2Cl2 to achieve a total volume of 10 mL. The reagent mixture
was pumped through the Oxone-filled cartridge using a syringe
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10.1002/ejoc.201900220
European Journal of Organic Chemistry
FULL PAPER
General Procedure for the synthesis of diaryliodonium
trifluoroacetates 6a-u
8.8 Hz, 2H), 3.81 (s,3H) ppm. 13C NMR (75 MHz, CDCl3): δ 162.9, 161.0
(q, J = 37 Hz), 137.3, 134.3, 132.2, 132.1, 118.0,115.9 (q, J = 290
Hz),115.4, 102.9, 55.8 ppm. 19F NMR (376 MHz, CDCl3): δ -75.32 ppm.
HRMS (ESI): m/z calcd for C13H12IO+: 310.9933; found: 310.9930.
Reagent mixture 1: Iodoarene 1a-h (0.898 mmol, 183 mg, 100 µL)
and TFA (1.39 mL) were dissolved CH2Cl2 to achieve a total
volume of 10 mL. Reagent mixture 2: Arene 5a-d (1.037-1.087
mmol) or boronic acid 5e, f (1.087 mmol) and TFA (1.53 mL) were
dissolved CH2Cl2 to achieve a total volume of 11 mL.
Phenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate (6d)
The reaction of iodobenzene 1a (0.898 mmol, 183 mg, 100 µL), 1,3,5-
trimethoxybenzene 5d (1.037 mmol, 174 mg) and TFA (2.92 mL)
according to the general procedure afforded 336 mg (77%) of
Reagent mixture 1 was pumped through the Oxone-filled
cartridge using a syringe pump at a flow rate of 0.11 mL/min. After
15.5 minutes, reagent mixture 2 was started to pump with a
second syringe pump with 0.11 mL/min. After the end of the
reagent mixture 1 addition, the syringe with a mixture of reagents
was immediately replaced with a syringe with CH2Cl2 (10 ml) and
DC CH2Cl2 M was pumped with 0.11 ml/min until the end of the
pumping reagent mixture 2. Then flow rate was increased to 0.22
mL/min for 5 min, then and addition continued until the end of the
CH2Cl2 in the syringe with 0.5 mL/min flow rate. Solvent was
removed from the resulting solution in vacuo and the residue was
diluted with water (5 mL). The product was extracted with CH2Cl2
(3 x 5 mL). The organic layer was dried over Na2SO4 and the
solvent was removed in vacuo. Then diethyl ether (5 mL) was
added to the residue and a precipitate was formed, the
suspension was stirred for 10 min, then the product was filtered
off and washed with diethyl ether (5 mL) and hexane (10 mL). The
obtained product was dried in vacuo.
phenyl(2,4,6-trimethoxyphenyl)iodoniumtrifluoroacetate 6d as
a pale
yellow crystalline solid; mp: 153-155 ºС (lit 160-165 ºС [8d]). 1H NMR (400
MHz, CDCl3): δ 7.88 (d, J = 8.0 Hz, 2H), 7.46 (t, J = 7.4 Hz, 1H), 7.32 (t, J
= 8.0 Hz, 2H), 6.16 (s, 2H), 3.86 (s, 6H), 3.85 (s, 3H) ppm. 13C NMR (100
MHz, CDCl3): δ 166.8,161.7 (q, J = 34 Hz), 160.6, 133.9, 131.4, 131.3,
117.0, 116.5 (q, J = 293 Hz), 91.5, 85.8, 56.9, 56.0 ppm. 19F NMR (376
MHz, CDCl3): δ -75.31 ppm. HRMS (ESI): m/z calcd for C15H16IO3
+
:
371.0139; found: 371.0139.
Diphenyliodoniumtrifluoroacetate (6e)
The reaction of iodobenzene 1a (0.898 mmol, 183 mg, 100 µL),
phenylboronic acid 5e (1.087 mmol, 133 mg) and TFA (2.92 mL) according
to
the
general
procedure
afforded
261
mg
(74%)
of
diphenyliodoniumtrifluoroacetate 6e as a white crystalline solid; mp: 202-
1
203 ºС (lit 197-198 ºС [7b]). H NMR (400 MHz, DMSO-d6): δ 8.25 (d, J =
7.2 Hz, 4H), 7.66 (t, J = 7.6 Hz, 2H), 7.52 (t, J = 7.6 Hz, 4H) ppm. 13C NMR
(100 MHz, DMSO-d6): δ 157.9 (q, J = 37 Hz), 135.2, 132.0, 131.7,117.3 (q,
J = 295 Hz), 116.8 ppm. 19F NMR (376 MHz, DMSO-d6): δ -73.42 ppm.
HRMS (ESI): m/z calcd for C12H10I+: 280.9822; found: 280.9822.
Mesityl(phenyl)iodonium trifluoroacetate (6a)
The reaction of iodobenzene 1a (0.898 mmol, 183 mg, 100 µL), mesitylene
5a (1.087 mmol, 130 mg) and TFA (2.92 mL) according to the general
procedure afforded 352 mg (90%) of mesityl(phenyl)iodonium
trifluoroacetate 6a as a white crystalline solid; mp: 142-144 ºС (lit 137-138
ºС [9a]). 1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 7.7 Hz, 2H), 7.49 (t, J =
7.4 Hz, 1H), 7.37 (t, J = 7.8 Hz, 2H), 7.08 (s, 2H), 2.62 (s, 6H), 2.34 (s,3H)
ppm. 13C NMR (100 MHz, CDCl3): δ161.0 (q, J = 37Hz, CF3COO-), 144.4,
142.4, 132.9, 132.2, 131.7, 130.4, 121.3, 115.9 (q, J = 289Hz, CF3COO-),
113.3, 27.1, 21.2 ppm. 19F NMR (376 MHz, CDCl3): δ -75.67 ppm. HRMS
(ESI): m/z calcd for C15H16I+: 323.0297; found: 323.0299.
Phenyl(4-(trifluoromethoxy)phenyl)iodoniumtrifluoroacetate (6f)
The reaction of iodobenzene 1a (0.898 mmol, 183 mg, 100 µL), 4-
trifluoromethoxyphenylboronic acid 5f (1.087 mmol, 204 mg) and TFA
(2.92 mL) according to the general procedure afforded 325 mg (76%) of
phenyl(4-(trifluoromethoxy)phenyl)iodonium trifluoroacetate 6f as a white
crystalline solid; mp: 192-194 ºС. 1H NMR (400 MHz, CDCl3): δ 8.01 – 7.96
(m, 4H), 7.56 (t, J = 7.6 Hz, 1H), 7.40 (t, J = 7.6 Hz, 2H), 7.19 (d, J = 8.4
Hz, 2H) ppm. 13C NMR (100 MHz, CDCl3): δ 161.5 (q, J = 36 Hz), 151.7,
136.8, 135.1, 132.1, 132.0, 123.7,120.3 (q, J = 258 Hz), 117.5, 116.0 (q, J
= 290 Hz), 113.9 ppm. 19F NMR (376 MHz, CDCl3): δ -57.84, -75.53 ppm.
HRMS (ESI): m/z calcd for C13H9F3IO+: 364.9645; found: 364.9645.
Phenyl(thiophen-2-yl)iodonium trifluoroacetate (6b)
The reaction of iodobenzene1a (0.898 mmol, 183 mg, 100 µL),
thiophene5b(1.087 mmol, 91 mg) and TFA (2.92 mL) according to the
general procedure afforded 242 mg (67%) of phenyl(thiophen-2-
yl)iodonium trifluoroacetate 6b as a beige crystalline solid; mp 152-154 ºС.
1H NMR (400 MHz, CDCl3): δ 7.97 (d, J = 7.6 Hz, 2H), 7.72 (dd, J = 4.0,
1.2 Hz, 1H), 7.59 (dd, J = 5.2, 1.2 Hz, 1H), 7.52 (t, J = 7.6 Hz, 1H), 7.39 (t,
J = 7.6 Hz, 2H), 7.06 (dd, J = 5.2, 3.6 Hz, 1H) ppm. 13C NMR (75 MHz,
CDCl3): δ 160.9 (q, J = 38 Hz), 141.1, 137.4, 133.9, 132.5, 132.3, 130.2,
118.3, 115.6 (q, J = 287Hz), 97.0 ppm. 19F NMR (376 MHz, CDCl3) δ -
75.30 ppm. HRMS (ESI): m/z calcd for C10H8IS+: 286.9391; found:
286.9389.
Mesityl(p-tolyl)iodoniumtrifluoroacetate (6g)
The reaction of 4-iodotoluene 1b (0.898 mmol, 194 mg), mesitylene 5a
(1.087 mmol, 130 mg) and TFA (2.92 mL) according to the general
procedure afforded 380 mg (94%) of mesityl(p-tolyl)iodoniumtrifluoro-
acetate 6g as a white crystalline solid; mp: 155-156 ºС. 1H NMR (400
MHz,CDCl3): δ 7.57 (d, J = 8.4 Hz, 2H), 7.15 (d, J = 8.4 Hz, 2H), 7.04 (s,
2H), 2.62 (s, 6H), 2.33 (s, 3H), 2.32 (s, 3H) ppm. 13C NMR (100 MHz,
CDCl3): δ 161.2 (q, J = 36 Hz), 143.7, 142.1, 132.9, 132.7, 130.2, 123.1,
166.8, 116.1 (q, J = 290 Hz), 111.5, 27.1, 21.4, 21.2 ppm. 19F NMR (376
MHz, CDCl3): δ -75.52 ppm. HRMS (ESI): m/z calcd for C16H18I+: 337.0448;
found: 337.0447.
(4-Methoxyphenyl)(phenyl)iodonium trifluoroacetate (6c)
The reaction of iodobenzene 1a (0.898 mmol, 183 mg, 100 µL), anisole 5c
(1.087 mmol, 117 mg) and TFA (2.92 mL) according to the general
procedure afforded 247 mg (64%) of (4-methoxyphenyl)(phenyl)iodonium
trifluoroacetate 6c as a beige crystalline solid; mp: 162-164 ºС (lit 137-138
ºС [22]). 1H NMR (400 MHz, CDCl3): δ 7.90 (d, J = 7.6 Hz, 2H), 7.86 (d, J =
8.8 Hz, 2H), 7.52 (t, J = 7.6 Hz, 1H), 7.38 (t, J = 7.6 Hz,2H), 6.89 (d, J =
p-Tolyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate (6h)
The reaction of 4-iodotoluene 1b (0.898 mmol, 196 mg), 1,3,5-
trimethoxybenzene 5d (1.037 mmol, 174 mg) and TFA (2.92 mL)
according to the general procedure afforded 320 mg (72%) of p-tolyl(2,4,6-
trimethoxyphenyl)iodonium trifluoroacetate 6h as a beige crystalline solid;
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201900220
European Journal of Organic Chemistry
FULL PAPER
mp 161-163 ºС (lit 163-165 ºС [8d]). 1H NMR (400 MHz, CDCl3): δ 7.76 (d,J
= 8.4 Hz, 2H), 7.11 (d, J = 8.4 Hz, 2H), 6.15 (s, 2H), 3.86 (s, 6H), 3.84 (s,
3H), 2.32 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ 166.8, 161.0 (q, J =
33 Hz), 160.5, 142.2, 134.0, 132.3, 116.2 (q, J = 290 Hz), 113.5, 91.5, 86.3,
56.9, 56.0, 21.4 ppm. 19F NMR (376 MHz, CDCl3): δ -75.38 ppm. HRMS
(ESI): m/z calcd for C16H18IO3+: 385.0295; found: 385.0295.
The reaction of 3,5-dimethyliodobenzene 1e (0.898 mmol, 208 mg), 1,3,5-
trimethoxybenzene 5d (1.037 mmol, 174 mg) and TFA (2.92 mL)
according to the general procedure afforded 232 mg (50%) of (3,5-
dimethylphenyl)(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 6m as a
1
pale yellow crystalline solid; mp: 187-189 ºС. H NMR (400 MHz, CDCl3):
δ 7.51 (s, 2H), 7.07 (s, 1H), 6.16 (s, 2H), 3.88 (s, 6H), 3.86 (s, 3H), 2.28
(s, 6H) ppm. 13C NMR (100 MHz, CDCl3): δ 166.8, 160.5, 160.5 (q, J = 35
Hz), 141.7, 133.4, 131.5, 116.8, 115.9 (q, J = 289 Hz), 91.6, 86.1, 56.9,
56.0, 21.4 ppm. 19F NMR (376 MHz, CDCl3): δ -75.79 ppm. HRMS (ESI):
m/z calcd for C17H20IO3+: 399.0452; found: 399.0453.
Mesityl(m-tolyl)iodoniumtrifluoroacetate (6i)
The reaction of 3-iodotoluene 1d (0.898 mmol, 196 mg), mesitylene 5a
(1.087 mmol, 130 mg) and TFA (2.92 mL) according to the general
procedure afforded 388 mg (96%) of mesityl(m-tolyl)iodoniumtrifluoro-
acetate 6i as a yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.53 (s, 1H), 7.39
(d, J = 8.0 Hz, 1H), 7.34 (d, J = 7.2 Hz, 1H), 7.27 (t, J = 7.6 Hz, 1H), 7.11
(s, 2H), 2.61 (s, 6H), 2.36 (s, 3H), 2.35 (s, 3H) ppm. 13C NMR (75 MHz,
CDCl3): δ 160.8 (q, J = 36 Hz), 144.7, 143.3, 142.6, 133.4, 133.0, 132.1,
130.6, 129.8, 119.9, 115.8 (q, J = 288 Hz), 112.0, 27.1, 21.5, 21.2 ppm.
19F NMR (376 MHz, CDCl3): δ -75.80 ppm. HRMS (ESI): m/z calcd for
C16H18I+: 337.0453; found: 337.0456.
Mesityl(4-(trifluoromethoxy)phenyl)iodonium trifluoroacetate (6n)
The reaction of 4-trifluorometoxyiodobenzene 1f (0.898 mmol, 257mg),
mesitylene 5a (1.087 mmol, 130 mg) and TFA (2.92 mL) according to the
general procedure afforded 364 mg (78%) of mesityl(4-
(trifluoromethoxy)phenyl)iodonium trifluoroacetate 6n as
a
white
crystalline solid; mp: 167-169 ºС. 1H NMR (400 MHz, CDCl3): δ 7.73 (d, J
= 9.2 Hz, 2H), 7.18 (d, J = 8.4 Hz, 2H), 7.07 (s, 2H), 2.62 (s, 6H), 2.33 (s,
3H) ppm. 13C NMR (100 MHz, CDCl3): δ 161.7 (q, J = 35 Hz), 151.3(q, J =
2 Hz), 143.9, 142.0, 134.7, 130.2, 123.8, 123.3, 120.3 (q, J = 258 Hz),
116.2 (q, J = 291 Hz), 111.7, 27.1, 21.2 ppm. 19F NMR (376 MHz, CDCl3):
δ -57.89, -75.47 ppm. HRMS (ESI): m/z calcd for C16H15F3IO+: 407.0114;
found: 407.0113.
Thiophen-2-yl(m-tolyl)iodoniumtrifluoroacetate (6j)
The reaction of 3-iodotoluene 1d (0.898 mmol, 196 mg), thiophene 5b
(1.087 mmol, 91 mg) and TFA (2.92 mL) according to the general
procedure
afforded
308
mg
(83%)
of
thiophen-2-yl(m-
tolyl)iodoniumtrifluoroacetate 6j as a yellow oil. 1H NMR (400 MHz, CDCl3):
δ 7.79 – 7.78 (m, 2H), 7.74 (d, J = 8.0 Hz, 1H), 7.66 (dd, J = 5.2, 1.2 Hz,
1H), 7.37 (d, J = 7.6 Hz, 1H), 7.30 (t, J = 8.0 Hz, 1H), 7.11 (dd, J = 5.6, 4.0
Hz, 1H), 2.37 (s, 3H) ppm. 13C NMR (75 MHz, CDCl3): δ 161.0(q, J = 38
Hz), 143.1, 140.8, 137.1, 134.2, 133.3, 131.9, 130.9, 130.1, 118.5, 115.7(q,
J = 287 Hz), 97.7, 21.5 ppm. 19F NMR (376 MHz, CDCl3): δ -75.72 ppm.
HRMS (ESI): m/z calcd for C11H10SI+: 300.9548; found: 300.9548.
(4-(Trifluoromethoxy)phenyl)(2,4,6-trimethoxyphenyl)iodonium
trifluoroacetate (6o)
The reaction of 4-trifluorometoxyiodobenzene 1f (0.898 mmol, 257mg),
1,3,5-trimethoxybenzene 5d (1.037 mmol, 174 mg) and TFA (2.92 mL)
according to the general procedure afforded 338 mg (66%) of (4-
(trifluoromethoxy)phenyl)(2,4,6-trimethoxyphenyl)iodonium
trifluoro-
acetate 6o as a pale yellow crystalline solid; mp: 177-179 ºС. 1H NMR (400
MHz, CDCl3): δ 7.95 (d, J = 8.8 Hz, 2H), 7.15 (d, J = 8.2 Hz, 2H), 6.17 (s,
2H), 3.89 (s, 6H), 3.85 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ 167.0,
161.3 (q, J = 36 Hz), 160.5, 151.2 (q, J = 2 Hz), 135.8, 123.4, 120.3 (q, J
= 258 Hz), 116.2 (q, J = 290 Hz), 113.6, 91.6, 86.8, 57.0, 56.0 ppm. 19F
NMR (376 MHz, CDCl3): δ -57.84, -75.59 ppm. HRMS (ESI): m/z calcd for
C16H15F3IO4+: 454.9962; found: 454.9963.
(4-Methoxyphenyl)(m-tolyl)iodoniumtrifluoroacetate (6k)
The reaction of 3-iodotoluene 1d (0.898 mmol, 196 mg), anisole 5c (1.087
mmol, 117 mg) and TFA (2.92 mL) according to the general procedure
afforded
365
mg
(93%)
of
(4-methoxyphenyl)(m-
tolyl)iodoniumtrifluoroacetate 6k as a yellow oil. 1H NMR (500 MHz, CDCl3):
δ 7.87 (d, J = 9.0 Hz, 2H), 7.72 (s, 1H), 7.67 (d, J = 8.5 Hz, 2H), 7.38 (d, J
= 7.5 Hz, 1H), 7.31 (t, J = 8.0 Hz, 1H), 6.95 (d, J = 9.5 Hz, 2H), 3.83 (s,
3H), 2.37 (s, 3H) ppm 13C NMR (75 MHz, CDCl3): δ 163.1, 160.3 (q, J =
38 Hz), 143.2, 137.3, 134.7, 133.4, 132.0, 131.3, 118.2,115.8 (q, J = 288
Hz), 114.5, 101.9, 55.9, 21.5 ppm. 19F NMR (471 MHz, CDCl3) δ -75.80
ppm. HRMS (ESI): m/z calcd for C14H14OI+: 325.0089; found: 325.0094.
(4-Chlorophenyl)(4-methoxyphenyl)iodoniumtrifluoroacetate (6p)
The reaction of 4-chloroiodobenzene 1g (0.898 mmol, 214 mg), anisole 5c
(1.087 mmol, 117 mg) and TFA (2.92 mL) according to the general
procedure
afforded
230
mg
(56%)
of
(4-chlorophenyl)(4-
methoxyphenyl)iodonium trifluoroacetate 6p as a white crystalline solid;
1
mp: 162-164 ºС. H NMR (400 MHz, CDCl3): δ 7.87 – 7.83 (m, 4H), 7.31
(3,5-Dimethylphenyl)(4-methoxyphenyl)iodoniumtrifluoroacetate (6l)
(d, J = 8.4 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 3.81 (s, 3H) ppm. 13C NMR
(100 MHz, CDCl3): δ 162.6, 161.4(q, J = 36 Hz), 138.5, 137.1, 135.7, 131.9,
117.7, 116.2(q, J = 291 Hz), 114.7, 105.7, 55.8 ppm. 19F NMR (376 MHz,
CDCl3) δ -75.41 ppm. HRMS (ESI): m/z calcd for C13H11ClIO+: 344.9538;
found: 344.9539.
The reaction of 3,5-dimethyliodobenzene1e (0.898 mmol, 208 mg), anisole
5c(1.087 mmol, 117 mg) and TFA (2.92 mL) according to the general
procedure afforded 369 mg (88%) of (3,5-dimethylphenyl)(4-
methoxyphenyl)iodonium trifluoroacetate6las a beige crystalline solid; mp
160-162 ºС. 1H NMR (400 MHz, CDCl3): δ 7.85 (d,J = 8.0 Hz, 2H), 7.51 (s,
2H), 7.12 (s, 1H), 6.89 (d, J = 8.4 Hz, 2H), 3.81 (s, 3H), 2.29 (s, 6H) ppm.
13C NMR (100 MHz, CDCl3) δ 162.4,161.3 (q, J = 36 Hz), 142.1, 136.8,
133.7, 131.8, 117.6, 116.8, 116.1 (q,J = 290 Hz), 105.1, 55.7, 21.4 ppm.
19F NMR (376 MHz, CDCl3): δ -75.50 ppm. HRMS (ESI): m/z calcd for
C15H16IO+: 339.0240; found: 339.0240.
(4-Chlorophenyl)(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate
(6q)
The reaction of 4-chloroiodobenzene 1g (0.898 mmol, 214 mg), 1,3,5-
trimethoxybenzene 5d (1.037 mmol, 174 mg) and TFA (2.92 mL)
according to the general procedure afforded 276 mg (59%) of (4-
chlorophenyl)(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 6q as a
(3,5-Dimethylphenyl)(2,4,6-trimethoxyphenyl)iodonium
trifluoroacetate (6m)
pale yellow crystalline solid; mp: 167-169 ºС (lit 168-172 ºС [8d]). H NMR
1
(400 MHz, CDCl3): δ 7.85 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.8 Hz, 2H), 6.18
(s, 2H), 3.90 (s, 6H), 3.87 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201900220
European Journal of Organic Chemistry
FULL PAPER
166.9, 161.5 (q, J = 35 Hz),160.5, 137.9, 135.2, 131.5, 116.4 (q, J = 292
Hz), 114.3, 91.5, 86.5, 56.9, 56.0 ppm. 19F NMR (376 MHz, CDCl3): δ -
75.49 ppm. HRMS (ESI): m/z calcd for C15H15ClIO3+: 404.9749; found:
404.9748.
solid; mp: 102-104 ºС. 1H NMR (400 MHz, CDCl3): δ 8.20 – 8.19 (m, 2H),
7.80 – 7.77 (m, 2H), 7.64 (dd, J = 5.2, 1.2 Hz, 1H), 7.54 (t, J = 8.4 Hz, 1H),
7.10 (dd, J = 5.2, 4.0 Hz, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ 162.0
(q, J = 36 Hz), 140.4, 137.1, 136.5, 133.6 (q, J = 34 Hz), 132.0, 130.6 (q,
J = 4 Hz), 129.9, 128.5 (q, J = 4 Hz),122.3 (q, J = 272 Hz), 120.0, 116.0
(q, J = 291 Hz), 102.1 ppm. 19F NMR (376 MHz, CDCl3): δ -62.89, -75.59
ppm. HRMS (ESI): m/z calcd for C11H7F3IS+: 354.9260; found: 354.9259.
(4-Fluorophenyl)(mesityl)iodonium trifluoroacetate (6r)
The reaction of 4-fluoroiodobenzene 1h (0.898 mmol, 199 mg), mesitylene
5a (1.087 mmol, 130 mg) and TFA (2.92 mL) according to the general
procedure afforded 318 mg (78%) of (4-fluorophenyl) (mesityl)iodonium
trifluoroacetate 6r as a white crystalline solid; mp: 146-148 ºС. 1H NMR
(400 MHz, CDCl3): δ 7.69 (dd, J = 8.8, 4.8 Hz, 4H), 7.08 – 7.03 (m, 4H),
2.62 (s, 6H), 2.32 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ 164.3 (d, J
= 252 Hz), 161.7 (q, J = 35 Hz), 143.8, 141.9, 135.3 (d, J = 9 Hz), 130.2,
123.4, 119.3 (d, J = 23 Hz), 116.3 (q, J = 292 Hz), 108.6 (d, J = 3 Hz), 27.1,
21.2 ppm. 19F NMR (376 MHz, CDCl3): δ -75.43, -107.25 ppm. HRMS
(ESI): m/z calcd for C15H15FI+: 341.0197; found: 341.0196.
(3-(Trifluoromethyl)phenyl)(2,4,6-
trimethoxyphenyl)iodoniumtrifluoroacetate (6u)
The reaction of 3-iodobenzotrifluoride 1c (0.898 mmol, 196 mg), 1,3,5-
trimethoxybenzene 5d (1.037 mmol, 174 mg) and TFA (2.92 mL)
according to the general procedure afforded 89 mg (18%) of (3-
(trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodoniumtrifluoroacetate
1
6u as a pale yellow crystalline solid; mp: 142-144 ºС. H NMR (400 MHz,
CDCl3): δ 8.19 (d, J = 8.0 Hz, 1H), 8.14 (s, 1H), 7.71 (d, J = 8.0 Hz, 1H),
7.47 (t, J = 8.0 Hz, 1H), 6.17 (s, 2H), 3.89 (s, 6H), 3.85 (s, 3H) ppm. 13C
NMR (100 MHz, CDCl3): δ 167.0, 160.9 (q, J = 38 Hz), 160.5, 137.5,133.2
(q, J = 33 Hz), 131.6, 130.7 (q, J = 4 Hz), 128.0 (q, J = 4 Hz),122.8 (q, J =
272 Hz), 117.4, 116.0 (q, J = 289 Hz), 91.7, 87.3, 57.0, 56.0 ppm. 19F NMR
(376 MHz, CDCl3): δ -62.86, -75.79 ppm. HRMS (ESI): m/z calcd for
C16H15F3IO3+: 439.0012; found: 439.0013.
(4-Fluorophenyl)(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate
(6s)
The reaction of 4-fluoroiodobenzene 1h (0.898 mmol, 199 mg), 1,3,5-
trimethoxybenzene 5d (1.037 mmol, 174 mg) and TFA (2.92 mL)
according to the general procedure afforded 269 mg (60%) of (4-
fluorophenyl)(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 6s as a
1
pale yellow crystalline solid; mp: 169-171 ºС (lit 165-169 ºС [8d]). H NMR
Acknowledgements
(400 MHz, CDCl3): δ 7.90 (dd,J = 9.2, 5.2 Hz, 2H), 7.03 – 6.99 (m, 2H),
6.15 (s, 2H), 3.87 (s, 6H), 3.84 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3):
δ 166.8, 164.3 (d, J = 252 Hz), 161.6 (q, J = 35 Hz), 160.5, 136.4 (d, J = 9
Hz), 118.8 (d, J = 23 Hz), 116.4 (q, J = 292 Hz), 110.6 (d, J = 3 Hz), 91.5,
86.6, 56.9, 56.0 ppm. 19F NMR (376 MHz, CDCl3): δ -75.40, -107.20 ppm.
HRMS (ESI): m/z calcd for C15H15FIO3+: 389.0044; found: 389.0044.
This work was supported by the Russian Science Foundation
(RSF-17-73-20066). The authors greatly acknowledge the
Laboratory of Physical–Chemical Analytical Methods of Tomsk
State University for the NMR and HRMS analyses. We thank the
EPSRC National Mass Spectrometry Facility, Swansea, for mass
spectrometric data.
Thiophen-2-yl(3-(trifluoromethyl)phenyl)iodoniumtrifluoroacetate (6t)
The reaction of 3-iodobenzotrifluoride 1c (0.898 mmol, 244 mg), thiophene
5b (1.087 mmol, 91 mg) and TFA (2.92 mL) according to the general
Keywords: flow synthesis • oxone • iodonium salts • Nelder-
Mead • oxidation
procedure
afforded
253
mg
(60%)
of
thiophen-2-yl(3-
(trifluoromethyl)phenyl)iodonium trifluoroacetate 6t as a grey crystalline
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Entry for the Table of Contents
FULL PAPER
Natalia S. Soldatova, Pavel S.
Postnikov, Mekhman S. Yusubov* and
Thomas Wirth*
–
CF3CO2
I
Ar
®
Oxone®
Ar-I
Ar
F3CCO2H, CH2Cl2
21 examples
up to 96% yield
Page No. – Page No.
Ar-H
Flow Synthesis of Iodonium
Trifluoroacetates through Direct
Oxidation of Iodoarenes by Oxone®
Fast Flow Synthesis of diaryliodonium compounds is achieved
by a rapid oxidation of aryliodides in an Oxone cartridge. High
yields of reaction products are obtained in a short period of time.
Key Topic:
Flow Oxidation
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