Trifluoromethylthiolation of Unsymmetrical λ3-Iodane Derivatives: Additive-Free, Selective and Scalable Introduction of the SCF3 Group

Article abstract of DOI:10.1002/ejoc.201501623

The reaction of copper trifluoromethyl sulfide with diaryliodonium salts provides a straightforward pathway for the synthesis of aryl trifluoromethyl thioethers under mild reaction conditions and within short reaction times. High chemoselectivity was achieved by using mesityl as a leaving group. A large range of novel [(het)aryl](mesityl)iodonium salts underwent this reaction under the optimized conditions to give the desired products in moderate to good yields.

Full text of DOI:10.1002/ejoc.201501623

DOI: 10.1002/ejoc.201501623
Communication
Trifluoromethylthiolation
Trifluoromethylthiolation of Unsymmetrical λ3-Iodane
Derivatives: Additive-Free, Selective and Scalable Introduction
of the SCF3 Group
Pavlo Nikolaienko,[a] Tülay Yildiz,[a] and Magnus Rueping*[a]
Abstract: The reaction of copper trifluoromethyl sulfide with ity was achieved by using mesityl as a leaving group. A large
diaryliodonium salts provides a straightforward pathway for the range of novel [(het)aryl](mesityl)iodonium salts underwent this
synthesis of aryl trifluoromethyl thioethers under mild reaction reaction under the optimized conditions to give the desired
conditions and within short reaction times. High chemoselectiv- products in moderate to good yields.
Introduction
In recent years fluorinated compounds received increased at-
tention due to their widespread biological and therapeutic
properties.[1] Among the vast array of fluorinated substances
known to date, those containing perfluoroalkylthio groups (e.g.
F3CS, C2F5S) anchored to aromatic rings emerged as a valuable
class of compounds[2a–2d] for the pharmaceutical and agro-
chemical industries.[2e] Compared with the parent alkylthio and
perfluoroalkyl derivatives, the perfluoroalkylthio-containing
compounds possess unique physical, chemical and biological
properties.[3] In particular, the unusual high lipophilicity com-
bined with the high electron-withdrawing ability of the perfluo-
roalkylthio groups raised more and more the interest of re-
searchers for exploring new biologically active compounds con-
taining such units. For example, tiflorex (flutiorex) is used in the
treatment of nervous anorexia,[4a,4b] N-alkyl-4-(5H-dibenzo[a,d]-
[7]annulen-5-ylidene)piperidines are being tested as dopamine
antagonists,[4c,4d] toltrazuril is used as an antiprotozoal agent,[4e]
and the thio analogue of riluzole has been tested for its poten-
tial biological activities[4f] (Figure 1).
Such aromatic derivatives containing one or more SCF3 sub-
stituents are usually prepared according to two main synthetic
strategies. One route toward aryl trifluoromethyl sulfides (Ar–
SCF3) is based on reactions of substrates that already contain
sulfur. This route includes the fluorine/chlorine exchange of Ar–
SCl3 compounds[5] and trifluoromethylation of Ar–SX (X = H, Cl,
CN, SR) with either CF3X (X = I, Br), nucleophilic CuCF3 or
TMSCF3/F–.[6] The second route consists of the direct transfer of
the SCF3 group from special reagents to the aromatic sub-
strates.[7]
Figure 1. Biologically active compounds containing an SCF3 group.
However, more recently more convenient nucleophilic and
electrophilic reagents have been introduced for the tri-
fluoromethylthiolation.[8–12] Typical nucleophilic reagents are
M(SCF3)n where M = Hg, Cu, Ag, K, Cs, [Alk4N]+.[8] On the other
hand, various electrophilic reagents containing SCF3 groups[9]
as well as trifluoromethylsulfonyl hypervalent iodonium ylide[10]
were applied for the synthesis of aryl trifluoromethyl sulfides.
Due to the steadily increasing usefulness and importance
of this class of compounds, we were interested in devising a
convenient, direct method for their synthesis under mild reac-
tion conditions. For this purpose, our attention was drawn to
diaryliodonium salts as electrophilic reagents.[13] Whereas sym-
metrical diaryliodonium salts were successfully applied as elec-
trophilic arylating reagents either under transition-metal cataly-
sis or metal-free reactions,[13] unsymmetrical diaryliodonium
salts are less common as the presence of two different aromatic
rings can potentially lead to the formation of a mixture of pro-
ducts. However, regiocontrol can be attained by discrimination
of electronic and steric properties of the aromatic units.[13a] De-
spite significant developments in the reactions of diaryliodo-
nium salts with various nucleophiles, there are no reports on
their reaction with CuSCF3.
[a] Institute of Organic Chemistry, RWTH Aachen University
Landoltweg 1, 52074 Aachen, Germany
E-mail: Magnus.Rueping@rwth-aachen.de
www.oc3.rwth-aachen.de/rueping/
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejoc.201501623.
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It has been postulated that diaryliodonium salts react with hand, we applied various (aryl)(mesityl)iodonium triflates as
CuI salts by oxidative insertion to form highly electrophilic CuIII starting materials in this transformation (Table 1).
species.[13a] Under these circumstances, we anticipated that
CuSCF3 reacts with diaryliodonium salts by ligand exchange to
form ion pair A, which undergoes oxidative insertion to give
the ArCuIIISCF3 species B (Scheme 1). The latter undergoes re-
ductive elimination (C) to result in the formation of ArSCF3 pro-
ducts. We also presume that the reaction can be mediated by
the resulting CuOTf, which undergoes oxidative insertion more
easily and then, by triflate counterion exchange with F3CS–, the
ArCuIIISCF3 species B forms much faster.
Table 1. Trifluoromethylthiolation of unsymmetrical diaryliodonium salts un-
der the optimized reaction conditions.[a]
Scheme 1. Proposed mechanism for the formation of Ar–SCF3 by oxidative
addition of CuISCF3 and reductive elimination of the resulting CuIII complex.
Results and Discussion
The reaction of CuSCF3 with (p-bromophenyl)(mesityl)iodonium
triflate (1a) was chosen as model and was performed in differ-
ent solvents at room temperature for 1 h (see Table SI1 in the
Supporting Information). Due to the low solubility of the start-
ing materials, poor or no reactivity was observed in acetone,
Et2O, EtOAc, DCM, DCE and 1,4-dioxane. In CH3CN and pyridine
no reaction was observed, probably due to the copper ability
to coordinate to the solvent. DMF and DMSO allowed the reac-
tion to take place, and the desired product was formed in 65
and 60 % yield, respectively, although side products were also
detected by TLC (Table SI1, Entries 1 and 2). 19F NMR spectra
show the formation of products with high regioselectivity
(> 98:2) and unreacted CuSCF3. Unfortunately, additional stir-
ring and/or heating of the reaction mixture did not increase the
yield. Solvents structurally similar to DMF, such as DMA, NMP,
DMPU, TMU and others (Table SI1, Entries 12–17) were also
tested; however, no improvement of the yield was observed.
Given these findings, we decided to evaluate the influence of
additives on the outcome of the reaction. It was found that
[a] Reaction conditions: 1 (0.5 mmol), CuSCF3 (0.75 mmol), DMF (2.5 mL), see
Supporting Information for details; yields for isolated compounds. [b] 19F
NMR yields (PhCF3 was used as internal standard).
A wide range of electron-rich as well as electron-deficient
additives such as phosphines, diketones and azines (Table SI2, diaryliodonium triflates 1a–u was converted into the corre-
Entries 1–10) almost inhibit the reaction. Additives such as tet- sponding aryl trifluoromethyl sulfides 2a–u under simple reac-
raalkylammonium halides and tetrafluoroborates (Table SI2, En- tion conditions. The transformation tolerates many functional
tries 11–15) did not improve the yield either. An 19F NMR exper- groups, and products containing groups such as halogens (2a–
iment performed in [D7]DMF (Table SI5) showed no reaction d), electron-donating alkyl, alkoxy, phenoxy, and aryl groups
with AgSCF3, poor yield with the addition of 20 mol-% of CuBr, (2e, 2f, 2h, 2m, 2k), as well as electron-withdrawing methoxy-
and good yield when 1.5 equiv. of CuSCF3 was used. After ex- carbonyl, benzoyl and nitro groups (2j, 2l, 2q) were obtained
tensive evaluation of different temperatures, stoichiometries, in good yields. It should be noted, that we faced some difficul-
concentrations and counterions (see Supporting Information, ties during the preparation of the iodonium salt starting materi-
Tables SI3–6) the optimal conditions were found as follows: als containing a nitrogen atom in the molecule. Normally, we
1 equiv. of diaryliodonium salt, 1.5 equiv. of CuSCF3 in DMF used a procedure, which requires iodoarene, mesitylene and m-
(0.2
M
), 70 °C, 1.5 h. With the optimal reaction conditions in CBPA mixed at room temperature in DCM, and slow addition of
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TfOH at 0 °C or –15 °C. When a nitro group is present, the ability Conclusions
of iodine to be oxidized to (p-nitro)iodosobenzene dramatically
We have developed a novel method for the Cu-mediated
Csp2–SCF3 bond-forming reaction.[16] Extensive investigations
showed that no ligand and additives are necessary. By applying
this mild and rapid protocol, a variety of diaryliodonium salts
were converted into their corresponding aryl trifluoromethyl
thioethers in good yields Moreover, the scope was widened
by utilizing heteroaromatic iodonium salts, and many of the
presented (heteroaryl)(mesityl)iodonium salts were unknown
prior this work. Due to the wide spectrum of biological activi-
ties exhibited by Ar–SCF3 compounds, mild reaction conditions
and the simplicity of our protocol, we expect this method to
be added to the range of synthetic approaches affording aryl
trifluoromethyl sulfides.
decreases.[14] In order to prepare such an iodonium salt, the
mixture of iodoarene and m-CPBA had to be heated at reflux
in DCM prior to the addition of mesitylene and TfOH. Moreover,
under such conditions iodoanilines or iodobenzylamines react
with m-CPBA to form N-oxides rather than iodoso derivatives.
However recently, Olofsson et al.[15] reported an important ad-
vancement for the synthesis of a (mesityl)(pyridyl)iodonium salt,
where it was postulated that basic N-atom is not prone to be
oxidized when protonated by a strong acid (TfOH). The reaction
requires elevated temperatures due to the electron-withdraw-
ing effect of the quaternary nitrogen atom. Utilizing this ap-
proach offered us the possibility to synthesize various N-hetero-
cycle- and amine-containing mesityliodonium salts in good
yields (see Supporting Information). The results of reactions be-
tween the above-mentioned iodonium salts with CuSCF3 are
also presented in Table 1. Aniline derivatives 1n–p, nitrogen-
containing heterocycles 1r, 1s, 1u as well as thiophene deriva-
tive 1t were prepared and reacted smoothly under the typical
reaction conditions. To isolate the products without copper
contamination, the reaction mixture was treated with methano-
lic ammonia prior to the typical workup procedure without any
loss in yield. It should be noted that – except for 4-(trifluoro-
methylthio)-1-iodobenzene (2d), which was obtained with 2:1
regioselectivity – all trifluoromethylthiolated products were ob-
tained with very good regioselectivity (> 97:3).
Acknowledgments
T. Y. thanks the Republic of Turkey Council of Higher Education
(CoHE) for a fellowship.
Keywords: Fluorine · Diaryliodonium salts · Cross-coupling ·
Trifluoromethyl thioethers · Copper catalysis
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Scheme 3. Scale-up of the trifluoromethylthiolation of diaryliodonium salts.
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Received: December 30, 2015
Published Online: February 1, 2016
Eur. J. Org. Chem. 2016, 1091–1094
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