Transition-Metal-Free Electrophilic Fluoroalkanesulfinylation of Electron-Rich (Het)Arenes with Fluoroalkyl Heteroaryl Sulfones via C(Het)?S and S=O Bond Cleavage

Article abstract of DOI:10.1002/adsc.201900959

A novel Ph₂P(O)Cl-mediated direct fluoroalkanesulfinylation of electron-rich (het)arenes using fluoroalkyl heteroaryl sulfones as the R_fSO source (R_f=C₄F₉, CF₂Cl, CF₂Br, and CF₂COOEt) was developed. This is the first example where 2-HetSO₂R_f performs as the R_fSO synthon in organic synthesis via both C(Het)?S and S=O bond cleavage. (Figure presented.).

Full text of DOI:10.1002/adsc.201900959

Title: Transition-Metal-Free Electrophilic Fluoroalkanesulfinylation of
Electron-Rich (Het)Arenes with Fluoroalkyl Heteroaryl Sulfones
via C(Het)-S and S=O bond cleavage
Authors: Jun Wei, Kun Bao, Chengcheng Qi, Yao Liu, Chuanfa Ni,
Rong Sheng, and Jinbo Hu
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
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using the Digital Object Identifier (DOI) given below. The VoR will be
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content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900959
Link to VoR: http://dx.doi.org/10.1002/adsc.201900959

Advanced Synthesis & Catalysis
10.1002/adsc.201900959
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Transition-Metal-Free Electrophilic Fluoroalkanesulfinylation
of Electron-Rich (Het)Arenes with Fluoroalkyl Heteroaryl
Sulfones via C(Het)-S and S=O Bond Cleavage
a
a
a
a
b
a,
Jun Wei, Kun Bao, Chengcheng Qi, Yao Liu, Chuanfa Ni, Rong Sheng, * Jinbo
b,c,
Hu *
a
College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058, China
Fax/Tel: (+86)-571-8820-8458; e-mail: shengr@zju.edu.cn or jinbohu@sioc.ac.cn
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of
b
Organic Chemistry, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai 200032, China
School of Physical Science and Technology, ShanghaiTech University, 100 Haike Road, Shanghai 201210, China
c
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract.
fluoroalkanesulfinylation of electron-rich (het)arenes
using fluoroalkyl heteroaryl sulfones as the R SO source
= C , CF Cl, CF Br, and CF COOEt) was
developed. This is the first example where 2-HetSO
performs as the R SO synthon in organic synthesis via
A
novel Ph
2
P(O)Cl-mediated direct
CF
However, traditional direct methods need the use of
trifluoromethanesulfinyl halides CF S(O)X (X=F, Cl),
which suffers from high toxicity, volatility and poor
3
S(O) group into molecule is more attractive.
f
3
(
R
f
4
F
9
2
2
2
[9]
2
R
f
stability.
scalable
Therefore, a new, easily accessible,
and shelf-stable
f
both C(Het)–S and S=O bond cleavage.
trifluoromethanesulfinylation reagent is highly
desirable. In previous years, a few direct methods
Keywords: fluoroalkanesulfinylation; fluoroalkyl
heteroaryl sulfones
have been reported using Langlois reagent CF
3
SO Na
2
[10]
[11]
[12]
in the presence of TfOH,
PCl
3
or POCl
3
(
Scheme 1c-e). In 2003, 1-(trifluoromethanesulfinyl)-
pyrrolidine-2,5-dione was also developed as a direct
trifluoromethanesulfinylation reagent by Bertrand’s
group (Scheme 1f).
[9b]
In recent years, the introduction of fluoroalkyl groups
into molecules has been of growing interest due to
their high lipophilicity and electron-withdrawing
character.[ Sulfoxide, an oxidized form of thioether,
also plays a significant role in organic synthesis and
medicinal chemistry.[ In this context, fluoroalkyl
sulfoxides have become a subject of special interest
owing to the combination of two chemical moieties.
Two years later, Larock’s
group reported an intermolecular S−N addition of
trifluoromethanesulfinamides to arynes for the
preparation of ortho- trifluoromethanesulfinyl
1]
[13]
anilines (Scheme 1g).
reported the direct trifluoromethanesulfinylation of
hereroarenes using the CF SO Cl/PCy (Cy =
cyclohexyl) system at low temperature (–78 °C)
Recently, Cahard’s group
3]
3
2
3
[14]
In terms of electron-withdrawing character, CF
3
S(O)
(Scheme 1h).
has a much higher Hammett substituent constant than
Fluoroalkyl heteroaryl sulfones 1 are easy to
prepare, bench-stable and non-hygroscopic solid,
allowing for widespread use in the pharmaceutical
4]
the SCF
3
and the CF
3
group,[ and the enhancement
of biological activity has also been found in some
CF S(O)-containing compounds, such as the
insecticide fipronil and its analogues. Furthermore,
the “intermediate valence” character of the CF S(O)
group enables it to prepare other fluorinated moieties,
[
15]
and fluorine chemical fields.
PySO CF H (Hu reagent) was employed as a robust
gem-difluoroolefination and formal nucleophilic
Previously, 2-
3
[5]
2
2
3
[16]
halodifluoromethylation reagent (Scheme 2a), and
[6]
such as trifluoromethylsulfoximine CF
trifluoro-methylsulfone CF SO , trifluoromethylthio
CF S, and so on.
The traditional methods for the construction of
CF S(O) moiety involve the monooxidation of CF
Scheme
trifluoromethylation of sulfinyl halides or sulfinic
3
SO(NH),
2-BTSO
2
R have been used as fluoroalkanesulfinate
f
[17]
precursors (Scheme 2b). Hu’s group also reported
3
2
the visible light mediated radical fluoroalkylation of
3
[18]
isocyanides with 2-BTSO
2
R
f
(Scheme 2c).
In
S
addition, the iron-catalyzed difluoromethylation of
ArM (M=Mg, Zn) with 2-PySO CF H was disclosed
However, despite
3
3
(
1a)[
7]
and
the
nucleophilic
2
19]
2
[
more recently (Scheme 2d).
8]
esters with TMSCF
3
(Scheme 1b).[ Compared with
great advances in nucleophilic and radical
fluoroalkylation with fluoroalkyl heteroaryl sulfones
these indirect methods, the direct method to introduce
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201900959
1
, while to the best of our knowledge, compound 1 as
Table 1. Optimization of reaction conditionsa)
electrophile has not yet been reported. Consistent
with our ongoing research on this field, we herein
report an efficient method for the direct electrophilic
fluoroalkanesulfinylation of electron-rich (het)arenes
with 2-BTSO
CF COOEt) (Scheme 2e).
2
R
f
(R
f
= C F
4 9
, CF
2
Cl, CF Br, and
2
2
Entry
P reagent
Additive Solvent
3ab)
1
2
3
4
Ph
Ph
Ph
Ph
Ph
Ph
2
2
2
2
2
2
PCl
PCl
PCl
PCl
PCl
PCl
TMSCl
TMSCl
TMSCl
TMSCl
MeCN
THF
toulene
DCM
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
55
17
43
0
29
56
41
0
c)
5
TMSCl
6
7
8
9
1
1
a)
-
-
-
-
-
-
(EtO)
(EtO)
POCl
Ph P(O)Cl
(MeO) P(O)Cl
2
P(O)H
2
PCl
3
30
d)
0
1
2
94
2
54
Scheme 1. Previous work of trifluoromethanesulfinylation.
Reaction conditions: 1a (0.2 mmol, 1.0 equiv), 2a (0.2
mmol, 1.0 equiv), P reagent (0.2 mmol, 1.0 equiv),
b)
additive (150 mol%), solvent (1 mL), N
2
, 60 ℃, 1 h.
1
9
Yields were determined by F NMR using PhCF as an
3
c)
d)
internal standard. 90 ℃for 1 h. Isolated yield.
With optimized reaction conditions in hand, we
explored the substrate scope with various indole
derivatives. The data in table 2 showed that all these
reactions proceeded smoothly and both electron-
withdrawing and electron-donating substituted
Scheme 2. The applications of fluoroalkyl heteroaryl
sulfones.
indoles
can
produce
corresponding
3-
trifluromethanesulfinyl indoles with good to excellent
yields (63-99%), indicating good tolerance of
different substituents and positions on indoles. In
addition, various functional groups on the indole ring
demonstrate good compatibility, including phenyl 2k,
biphenyl 2m, borate 2n and 2o, benzyl 2p, alkenyl 2q,
antipyrine 2r, carbamate 2s, sulfonamide 2t and
chromene 2u, with good to excellent yields of
corresponding indole derivatives 3k-3u. Notably, the
reaction of 1a with 6-(1H-indol-4-yl)-1H-indazole 2v,
the active scaffold of selective PI3K δ inhibitor
Our initial attempt began by employing compound
indole 2a as the model substrate with 2-BTSO
2
CF 1a
3
and Ph
2
PCl/TMSCl in MeCN (1.0 mL) at 60 °C
atmosphere.[
20]
under a N
2
Gratifyingly, the desired
trifluoromethanesulfinylation product 3a was isolated
in 55% yield after 1h (Table 1, entry 1). Further
solvent screening proved that MeCN was more
favorable than others, including THF, toluene and
DCM (Table 1, entries 2-4). Elevating the
temperature to 90℃ decreased the yield of 3a to 29%
[21]
Nemiralisib,
showed excellent selectivity for
indole over indazole to achieve 84% yield of 3v
under the standard conditions. To further expand the
substrate scope of the trifluoromethanesulfinylation
reaction, other electron-rich arenes including 1-
methyl-1H-pyrrole 2w, 2,4-dimethyl-1H-pyrrole 2x,
methyl 2-(1-methyl-1H-pyrrol-2-yl)acetate 2y, 1,3,5-
trimethoxybenzene 2z, and thiophene were tested. As
expected, reactions with substituted pyrroles and
(
Table 1, entry 5). The removal of TMSCl did not
affect the yield of 3a obviously, indicating TMSCl
was not necessary in this reaction (Table 1, entry 6).
Then, several other reducing agents, including
(
(
EtO)
2
P(O)H, (EtO)
2
2
PCl, POCl
3
, Ph
2
P(O)Cl and
PCl in
MeO)
P(O)Cl were employed to replace Ph
2
this reaction (Table 1, entries 7-11). Among these
reagents, Ph P(O)Cl proved to be the best choice and
2
1
,3,5-trimethoxy benzene can produce the
corresponding trifluoromethanesulfinylated products
w-3z in moderate to good yields, while thiophene
produced a 94% yield of product 3a. Therefore, the
best result was obtained with a combination of 1.0
3
equiv of 1a and indole with 1.0 equiv Ph P(O)Cl in
2
only gave a trace amount of product. However, β-
keto esters, oxindoles, and 3-methylindole were not
suitable substrates in this reaction (see the SI). In
addition, the structure of 3g was confirmed by single
MeCN at 60 °C for one hour to furnish 3a in 94%
yield (Table 1, entry 10).
[22]
crystal X-ray analysis (see the SI).
Then, other fluoroalkyl heteroaryl sulfones (2-
BTSO
2
R
f
) with different R groups were used for this
f
transformation. The corresponding products 4a–d,
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201900959
which bearing C
4
F
9
S(O), BrCF
2
S(O), ClCF
2
S(O) and
trifluoromethanesulfinylation can serve as an
effective approach to introduce a sulfoxide S(O)
group. For example, the nucleophilic reaction of
PhMgBr with 3h gave the corresponding sulfoxide 5
in excellent yield (eq 2).
EtOOCCF S(O) groups were obtained in good to
2
excellent yields under standard conditions (70-91%,
Table 3).
Table 2. Trifluoromethanesulfinylation of electron-rich
a)
(
het)arenes.
Scheme 3 The synthetic application of reaction
We then turned our attention on the mechanistic
features of this reaction. Simply heating 2-BTSO
2
CF
P(O)Cl in acetonitrile at 60 ℃ for 1h gave
SOCl (21%, δ -77.32 ppm), CF SO Cl (19%, δ
76.13 ppm) and CF SCl (10%, δ = -46.56 ppm),
3
1a and Ph
2
CF
3
3
2
-
3
19
respectively, which were detected by F NMR
spectroscopic analysis (Scheme 1). According to
previous report that CF
and CF SO Cl by self-disproportionation,
result indicates that CF
in this reaction. Furthermore, the formation of
3
SOCl can convert to CF
3
SCl
[24]
3
2
this
3
SOCl may be an intermediate
19
CF SOCl is also supported by the on line F NMR
3
analysis (see the Supporting Figure 2). On the base of
the above-mentioned experiments and literature
[
20][25]
reports,
was proposed as follow (Scheme 1). First, the oxygen
of 2-BTSO CF attacks the phosphorus center of
Ph P(O)Cl to get intermediate A, which was
converted to Ph P(O)OS(O)CF B (detected by
a plausible mechanism for this reaction
2
3
2
2
3
a)
Reaction conditions: 1a (1.0 mmol, 1.0 equiv), 2 (1.0
mmol, 1.0 equiv), Ph P(O)Cl (1.0 mmol, 1.0 equiv),
MeCN (5 mL), N , 60 ℃ for 1 h. Isolated yields.
LCMS; see SI, Supporting Figure 3) through the
elimination of 2-chloro-benzothiazole. Then, indole
2
2
reacts directly with Ph
2
P(O)OS(O)CF
3
B via
electrophilic trifluoromethanesulfinylation process to
generate product 3 (path a). Meanwhile, the
Table 3. Fluoroalkanesulfinylation of indole.a)
Ph
2
P(O)OS(O)CF
3
B can be nucleophilic attacked by
SOCl,
which reacts with indole to afford the target product
path b).
chloride anion to get a reactive species CF
3
(
a)
Reaction conditions: 1 (1.0 mmol, 1.0 equiv), 2a (1.0
mmol, 1.0 equiv), Ph
2
P(O)Cl (1.0 mmol, 1.0 equiv),
MeCN (5 mL), N , 60 ℃ for 1 h. Isolated yields.
2
To further demonstrate the synthetic application of
this protocol, a gram-scale synthesis was conducted
Scheme 4. Preliminary mechanistic study and proposed
mechanism.
(
scheme 3, eq 1). When 10 mmol of 1-methyl-1H-
indole 2h was reacted with 10 mmol of 1a, the
product 3h can be obtained with excellent yield of
In conclusion, we have developed an
unprecedented application of fluoroalkyl heteroaryl
9
2%. In addition, since the CF
3
group can be readily
sulfones as efficient electrophilic R S(O) sources.
f
[23]
substituted by
a
nucleophile,
and the
Under mild conditions, a range of substituted
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201900959
electron-rich (het)arenes can be converted smoothly
Rolston, D.-P. Kontoyiannis, J. Clin. Microbiol. 2012,
50, 1552-1557.
into CF
3
S(O) decorated products with these reagents
in good to excellent yields. Considering the readily
available reagents and mild conditions (see the SI,
Supporting Table 1), the described protocol promises
more applications in medicinal chemistry and related
fields.
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A mixture of fluoroalkyl heteroaryl sulfone 1 (1.0 mmol,
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complete, the solvent was removed under reduced pressure
and the residue was purified by column chromatography
on silica gel by using a mixture of petroleum ether/EtOAc
as an eluent to provide the desired products 3 or 4.
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Advanced Synthesis & Catalysis
10.1002/adsc.201900959
COMMUNICATION
Transition-Metal-Free
Electrophilic
Electron-Rich
Fluoroalkanesulfinylation
of
(
Het)Arenes with Fluoroalkyl Heteroaryl Sulfones
via C(Het)-S and S=O bond cleavage
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Jun Wei, Kun Bao, Chengcheng Qi, Yao Liu,
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