Synthesis of Diaryliodonium Salts Having Pentafluorosulfanylarenes and Their Application to Electrophilic Pentafluorosulfanylarylation of C-, O-, N-, and S-Nucleophiles

Article abstract of DOI:10.1021/acs.orglett.5b01323

Novel reagents for the electrophilic introduction of pentafluorosulfanyl (SF₅) arenes into target molecules are disclosed. Unsymmetrical diaryliodonium salts 1 having SF₅-arenes were synthesized by a one-pot process from iodo-SF₅-benzenes 2 in good yields. The SF₅-aryliodonium salts 1 were found to be efficient for the electrophilic SF₅-arylation of carbon and heterocentered nucleophiles to furnish the corresponding substituted SF₅-arenes in good to high yields.

Full text of DOI:10.1021/acs.orglett.5b01323

Letter
pubs.acs.org/OrgLett
Synthesis of Diaryliodonium Salts Having Pentafluorosulfanylarenes
and Their Application to Electrophilic Pentafluorosulfanylarylation of
C‑, O‑, N‑, and S‑Nucleophiles
Kohei Matsuzaki,† Kenta Okuyama,† Etsuko Tokunaga,† Norimichi Saito,‡ Motoo Shiro,§
and Norio Shibata*,†
†Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan
‡Pharmaceutical Division, Ube Industries, Ltd., Seavans North Building 1-2-1 Shibaura, Minato-ku, Tokyo 105-8449, Japan
§Rigaku Corporation, 3-9-12 Mastubara-cho, Akishima, Tokyo 196-8666, Japan
S
* Supporting Information
ABSTRACT: Novel reagents for the electrophilic introduc-
tion of pentafluorosulfanyl (SF5) arenes into target molecules
are disclosed. Unsymmetrical diaryliodonium salts 1 having
SF5-arenes were synthesized by a one-pot process from iodo-
SF5-benzenes 2 in good yields. The SF5-aryliodonium salts 1
were found to be efficient for the electrophilic SF5-arylation of
carbon and heterocentered nucleophiles to furnish the corresponding substituted SF5-arenes in good to high yields.
romatic molecules bearing fluorinated functional groups are
prevalent in a variety of pharmaceuticals and agro-
A
chemicals.1 Drug candidates in the developmental pipeline also
highly likely contain fluorinated aromatics in their structures. In
particular, trifluoromethylated arene (CF3-Ar)-containing com-
pounds are one of the major families on the drug market;2
examples include aprepitant (antiemetic) and travoprost (for
glaucoma). Thus, the incorporation of a CF3-Ar unit into an
organic compound could form the basis for the development of
new drugs. On the other hand, the pharmaceutical industry has
faced difficulties in bringing new drugs onto the market in recent
years.3 One of the reasons is that rational drug designs to improve
challenging human life-threatening diseases have still not been
found, even in the 21st century.4 Pentafluorosulfanyl arenes
(SF5-Ar) have recently emerged as prospective drug units due to
the chemical similarity of CF3 and SF5.5 The SF5 moiety is
thermally stable (>300 °C) and also more stable under acidic and
basic hydrolysis than a CF3 group.6 Electrostatic potential maps
of CF3-Ph and SF5-Ph clearly indicate their three-dimensional
resemblance of charge distributions and molecular size (Figure
1a).7 However, the SF5 group has a much higher impact on the
benzene ring attached to CF3 since it is more electronegative
(Hammett substituent constants: for SF5 σI = 0.55, for CF3 σI =
0.39),6 has higher intrinsic lipophilicity (Hansch hydrophobicity
constants: for SF5 π = 1.51, for CF3 π = 1.09),8 bulkier size of van
der Waals volume (Å3) for SF5Ph 152.9, for CF3Ph 129.0, for
HPh 96.6),7 and higher chemical and thermal stability.6 Thus,
replacement of the CF3-Ar moiety in a drug or drug candidate by
SF5-Ar could become an alternative fine-tuning mechanism for
drug design and might result in an improvement of the
physiological and/or biological properties compared to the
parent drugs.9 In addition, both sulfur and fluorine are among the
most used elements in marketed drugs.4b The SF5 analogues of
Figure 1. (a) Electrostatic potential maps of CF3-Ph and SF5-Ph. (b)
Drug-containing CF3-arenes and their SF5 analogues.
the antidepressant drug fluoxetine, the antiobesity drug fenflur-
amine, and the antimalaria drug mefloquine are three
representative examples (Figure 1b) that have recently been
prepared.10 Moreover, SF5-arenes have attracted considerable
interest as a potential unit of functional materials.11
While many synthetic routes toward CF3-arene compounds
have been explored,12 only a handful of synthetic methods for
SF5-arenes have been reported,13 and the chemistry of SF5-
arenes is somewhat under-investigated. The direct construction
of an SF5 unit on benzene rings is possible from aryl disulfides
using HF/Cl2, AgF2, or F2 methodology.13 However, the
methods are limited to simple SF5-arenes, and more effective
and convenient methods are required. By virtue of the fact that
simple SF5-arenes are now commercially available,14 it is hoped
Received: May 6, 2015
© XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.5b01323
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Letter
that direct functionalization of simple SF5-arenes at all positions
of the benzene ring could allow for the synthesis of more complex
SF5-arenes.15 Recently, we reported two valuable building blocks,
3,5-bis(SF5)phenylboronic acid16 for the Suzuki−Miyaura
coupling reaction and bis(SF5)-5-azido-1,3-phenylene17 as a
tool for click chemistry, which furnish functional dyes and
antitumor compounds, respectively (Scheme 1a). We envisaged
Scheme 2. Synthesis of SF5-Arylaryliodonium Salts 1
Scheme 1. (a) SF5-arenes for Coupling and Click Reactions;
(b) Cationic Species for Late-Stage Derivatization; (c) SF5-
Arylaryliodonium Salts 1 for SF5-Arylations
Figure 2. X-ray crystallographic structure of 1c (CCDC 1062829).
Scheme 3. SF5-Arylation of 1,3-Dicarbonyl Compounds 3
with Reagents 1a and 1c
that if cationic species represented by [SF5-Ar]+ are generated
(Scheme 1b), the late-stage derivatization of target molecules to
SF5-aryl compounds would be realized. As part of our ongoing
research program committed to the development of late-stage
fluorinated functionalized reagents,18 herein we disclose the
synthesis of unsymmetrical diaryl-λ3-iodanes 1, diaryliodonium
salts having SF5-arenes, and their wide utility as electrophilic
regents for pentafluorosulfanylarylation (SF5-arylation) reac-
tions. 1,3-Dicarbonyl compounds smoothly react with SF5-
arylaryl-λ3-iodanes 1 to provide SF5-arylation products having a
quaternary carbon center in good to high yields. The SF5-
arylation by 1 was also found to be effective for a wide variety of
heterocentered nucleophiles (Scheme 1c). The application of
this method for the late-stage derivatization of biologically
important molecules, affording SF5-arene analogues, is also
described.
a
Diaryliodonium salts have gained attention as arylation agents
with a variety of nucleophiles under metal-free or metal-catalyzed
conditions.19 An ideal transformation can be obtained using
symmetrical diaryliodonium salts; however, the symmetrical
diaryliodonium salts are not suitable for SF5-arylation since half
of the “expensive” SF5-aryl must be sacrificed to achieve a desired
reaction. On the other hand, unsymmetrical diaryliodonium salts
sometimes encounter poor regioselectivity for arylation.20 On
the basis of the vast number of investigations on the chemistry of
diaryliodonium salts,19 regioselectivity for arylation could be
controlled by the balance of electronic differences of the two
independent aryl groups and their steric factors, and the electron-
deficient aryl moiety tends to be preferably transferred.20
Fortunately, the SF5-aryls are fundamentally electron-deficient;
thus, electron-rich aryl groups with or without steric hindrance
could be considered as dummy aryl ligands, i.e., the mesitylene or
anisole group. Designed SF5-arylaryliodonium salts 1 were easily
synthesized in a one-pot process from iodo-SF5-aryls with
mesitylene or anisole using m-CPBA and trifluoromethanesul-
fonic acid at room temperature (Scheme 2).19c,d The iodonium
salts 1 were characterized by spectroscopic analysis and X-ray
crystallography in the case of 1c (Figure 2).
The reaction of 3 (0.10 mmol) with reagent 1a or 1c (0.11 mmol)
was carried out in the presence of NaH (0.12 mmol) in DMF (1.0
mL) at rt. The reaction was carried out with malonate 3f (0.30
mmol), reagent 1a (0.39 mmol), and NaH (0.39 mmol) in DMF (1.17
mL).
b
the reagent 1a, having a steric mesityl group, was found to be
preferred, giving the desired 4aa in better yield (64% by 1b vs
84% by 1a).20 Both electron-donating (OMe, Me) and electron-
withdrawing (Cl) functional groups on substrates 3 were
acceptable for electrophilic SF5-arylation by 1a providing
corresponding products with an SF5-arene on the quaternary
carbon center in good to high yields (4aa−dc). Less reactive
malonate 3f also reacted with 1a,c to furnish SF5-arylation
products 4fa and 4fc in 84% and 52% yield, respectively, under
the same conditions.
Phenols and alcohols were next examined in the SF5-arylation
with 1 (Scheme 4).19p It should be noted that reagent 1b with
anisole as a dummy ligand gave considerably better yields in most
cases than 1a under NaOH/H2O conditions (Table S1,
Supporting Information). A clear advantage is that the SF5-
arylation of less reactive nitrophenol by 1b furnished 6db in 91%
yield, while only a 24% yield of 6db was isolated using 1a. The
reaction proceeded smoothly not only for phenols but also other
oxygen nucleophiles such as naphthylmethanols, benzyl alcohol,
and cinnamyl alcohol using 1b and 1d. It is noteworthy that SF5-
With the reagents 1 in hand, we first attempted the
electrophilic SF5-arylation of cyclic β-keto esters 3 with 1 in
the presence of NaH in DMF (Scheme 3).19j Compared to the
iodonium salt 1b with anisole in the dummy part of the ligand,
B
DOI: 10.1021/acs.orglett.5b01323
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Organic Letters
Letter
a
a
Scheme 4. SF5-Arylation of Phenols and Alcohols 5 with 1
Scheme 6. SF5-Arylation of Anilines 13 with 1a or 1c
a
The reaction of 13 (0.20 mmol) with reagent 1a or 1c (0.22 mmol)
was carried out in the presence of Cu (0) (0.020 mmol) in NMP (0.4
mL) at 80 °C.
demanding ortho position, had no effect on yields. We succeeded
in synthesizing a medicinally attractive SF5-analogue of the anti-
inflammatory agent ufenamate in 97% yield under the same
conditions (Scheme 6).
a
The reaction of 5 (0.20 mmol) with reagent 1b or 1d (0.22 mmol)
was carried out in the presence of NaOH (0.40 mmol) in H2O (1.0
mL) at 50 °C, unless noted otherwise. Reagent 1a (0.22 mmol) was
employed instead of 1b.
Sodium sulfinates as sulfur nucleophiles were finally examined
b
for the reaction with 1 (Scheme 7).19v,w Copper(I) salts were
Scheme 7. SF5-Arylation of Sulfinates 15 with 1a and 1e
arylation of the druglike estrone derivative progressed nicely to
give 6ka in 82% yield. Chemoselective SF5-arylation of C6′-OH
cinchona alkaloid derivative was observed by 1b to furnish 6lb in
48% yield with a secondary alcohol moiety untouched under
these conditions.
The iodonium salts 1 were reacted with other oxygen
nucleophiles such as N-hydroxyphthalimide (7), carboxylic
acid 8, and sulfonic acid 9 under slightly different conditions in
the presence of t-BuOK in DMF or toluene to provide the
corresponding SF5-arylation products 10−12 in good to high
yields (Scheme 5).19o,r,s
a
The reaction of 15a (0.20 mmol) with reagent 1a (0.22 mmol) was
carried out in the presence of CuI (0.020 mmol) in DMF (0.4 mL) at
90 °C. The reaction of 15b (0.45 mmol) with reagent 1e (0.30
b
mmol) was carried out in the presence of Cu2O (0.015 mmol) in
DMF (1.5 mL) at rt.
Scheme 5. SF5-Arylations of N-Hydroxyphthalimide,
Carboxylic Acid, and Sulfonic Acid
a
found to be necessary to obtain good yields of SF5-arylated
sulfones 16. It is noteworthy that highly electron-deficient
benzene derivative 16be was synthesized by this method, and its
potential utility as a nonexplosive alternative to trinitrobenzene
will be examined.15d
In conclusion, this study has revealed that SF5-arylaryl-λ3-
iodanes 1 are effective reagents for the electrophilic SF5-arylation
of 1,3-dicarbonyl compounds, phenols, alcohols, N-hydroxyph-
thalimide, carboxylic acid, sulfonic acid, anilines, and sulfinates. A
wide variety of SF5-arylated compounds can be obtained in the
presence of a base or copper catalyst under mild conditions in
good to high yields. The reagents 1 are applicable for the late-
stage functionalization of medicinally attractive molecules. This
should be a nice application of established arylations using
iodonium salts for the synthesis of SF5-aryl compounds, which
have not been easy to obtain. Further studies on the potential of 1
are now under investigation.
a
The reaction of N-hydroxyphthalimide (7, 0.20 mmol) with reagent
1a or 1c (0.22 mmol) was carried out in the presence of t-BuOK (0.22
mmol) in DMF (0.8 mL) at 60 °C for 1.5 h. The reaction of benzoic
acid or sulfonic acid (11 or 12, 0.10 mmol) with 1a (0.11 mmol) was
carried out in the presence of t-BuOK (0.11 mmol) in toluene (0.6
mL) at reflux for 3 h.
b
We further expanded the scope of these reagents 1 for SF5-
arylation of aromatic amines 13.19j−m After considerable
optimization of the reaction conditions (Table S2), it was
found that 10 mol % of Cu(0) at 80 °C in NMP allowed for the
SF5-arylation of 13 with 1, providing good yields of 14. The
scope of substrate under the optimized conditions is shown in
Scheme 6. Both electron-donating (Me) and electron-with-
drawing (Br, NO2, CF3) groups on the aniline were accepted, and
the position of their substituents, including the sterically
ASSOCIATED CONTENT
* Supporting Information
■
S
Scheme S1, Table S1, experimental details, analytical data
1
(HRMS), copies of H, 13C, and 19F NMR spectra, and X-ray
data (CIF). The Supporting Information is available free of
C
DOI: 10.1021/acs.orglett.5b01323
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
(15) (a) Joliton, A.; Carreira, E. M. Synlett 2015, 26, 737. (b) Okazaki,
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(c) Joliton, A.; Carreira, E. M. Org. Lett. 2013, 15, 5147. (d) Sipyagin, A.
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charge on the ACS Publications website at DOI: 10.1021/
acs.orglett.5b01323.
AUTHOR INFORMATION
Corresponding Author
■
(f) Iakobson, G.; Post
̌
a, M.; Beier, P. Synlett 2013, 24, 855. (g) Beier, P.;
*E-mail: nozshiba@nitech.ac.jp.
Notes
Pastyríkova, T. Beilstein J. Org. Chem. 2013, 9, 411. (h) Frischmuth, A.;
̌
́
́
Unsinn, A.; Groll, K.; Stadtmuller, H.; Knochel, P. Chem.Eur. J. 2012,
̈
The authors declare no competing financial interest.
18, 10234. (i) Vida, N.; Beier, P. J. Fluorine Chem. 2012, 143, 130.
(j) Beier, P.; Pastyrí
̌
kova,
́
T.; Vida, N.; Iakobson, G. Org. Lett. 2011, 13,
1466. (k) Beier, P.; Pastyríkova, T.; Iakobson, G. J. Org. Chem. 2011, 76,
kova, T. Tetrahedron Lett. 2011, 52, 4392.
́
́
̌
́
ACKNOWLEDGMENTS
■
4781. (l) Beier, P.; Pastyrí
(m) Sipyagin, A. M.; Bateman, C. P.; Tan, Y.-T.; Thrasher, J. S. J.
̌
́
́
This research was financially supported in part by the Platform
for Drug Discovery, Informatics, and Structural Life Science from
MEXT Japan, the Advanced Catalytic Transformation (ACT-C)
from the Japan Science and Technology (JST) Agency, Scientific
Research (B) (25288045), Hoansha Foundation, and the
Kobayashi International Scholarship Foundation.
Fluorine Chem. 2001, 112, 287.
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2015, 171, 120. (b) Yang, Y.-D.; Lu, X.; Tokunaga, E.; Shibata, N. J.
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