Visible-light initiated direct oxysulfonylation of alkenes with sulfinic acids leading to β-ketosulfones

Article abstract of DOI:10.1039/c6gc01403h

Visible light along with 1 mol% eosin Y catalyzed the direct oxysulfonylation of alkenes with sulfinic acids via a photoredox process which has been developed at room temperature under transition-metal-free conditions. The present reaction provides a highly efficient approach to diverse β-ketosulfones in moderate to good yields. It should provide a promising synthesis candidate for the formation of diverse and useful β-ketosulfone derivatives in the fields of synthetic and pharmaceutical chemistry.

Full text of DOI:10.1039/c6gc01403h

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Visibleꢀlight initiated direct oxysulfonylation of alkenes with sulfinic acids
leading to βꢀketosulfones
Daoshan Yang,* Ben Huang, Wei Wei, Jin Li, Gu Lin, Yaru Liu, Jiehua Ding, Pengfei Sun, and Hua Wang*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
leading to βꢀketosulfones have been significantly disclosed.6ꢀ10 In
Visible light along with 1 mol% Eosin Y catalyzed the direct
2013, Lei and coꢀworkers developed a highly efficient aerobic
oxidative difunctionalization of alkynes leading to βꢀketosulfones
in the presence of 4 equiv. pyridine under a dioxygen atmosphere
(Scheme 1b).6 In the same year, our group also reported a copperꢀ
catalyzed oxysulfonylation reaction of alkenes with
sulfonylhydrazides for the synthesis of βꢀketosulfones (Scheme
1c).7 In 2014, Yadav et al. demonstrated a highly efficient
synthetic approach to βꢀketosulfones via AgNO3ꢀcatalyzed
oxysulfonylation of alkenes with thiophenols (Scheme 1d).8
Yadav and coꢀworkers also developed a direct approach to βꢀketo
sulfones via AgNO3/K2S2O8 catalyzed aerobic oxysulfonylation
of alkenes with arenesulfinate salts (Scheme 1d).9 However,
challenges still remain, but it is still highly desirable to develop
more efficient, environmentallyꢀbenign, and sustainable methods
for the construction of βꢀketosulfones.
oxysulfonylation of alkenes with sulfinic acids via
a
photoredox process has been developed at room temperature
under transitionꢀmetalꢀfree conditions. The present reaction
provides a highly efficient approach to diverse βꢀketosulfones
in moderate to good yields. It should provide a promising
synthesis candidate for the formation of diverse and useful βꢀ
ketosulfone derivatives in the fields of synthetic and
pharmaceutical chemistry.
Introduction
βꢀketosulfone, one of the most valuable sulfurꢀcontaining
compounds, has been widely used as an important synthetic
intermediate in the construction of nature products, vinyl sulfones,
polyfunctionalized 4Hꢀpyrans, quinolines, allenes, ketones, and
vinylsulfones.1 Besides that, βꢀketosulfone derivatives are wellꢀ
known to possess various useful biological and medicinal
properties. For example, they can be used in antibacterial and
antifungal drugs, and are also potent nonnucleoside inhibitors.2
As a consequence, extensive efforts have been devoted to the
discovery of efficient and useful methods for βꢀketosulfone
synthesis and functionalization. The conventional methods for the
preparation of βꢀketosulfones mainly foucs on the direct
alkylation of sodium sulfinates with phenacyl halide.3
Nevertheless, the uneasily available precursors and prolonged
reaction times could limit their wide applications. In 2014, Jiang
et al. reported an elegant copperꢀcatalyzed coupling of oxime
acetates with sodium for the construction of βꢀketosulfones
(Scheme 1a).4
OAc
N
+
R2SO2Na
R1
1) Cu(OAc)2, toluene,
Jiang' work
(a)
100 o
C
2) hydrolysis
R1
O
R1
pyridine, O2
Cu(OAc)2, O2
O
S
R2
+
+
R1
R2SO2NHNH2
R2SO2H
Lei's work
(b)
Wang's work
(c)
O
(d)
AgNO3, K2S2O8
Yadav's work
R1
+
R2SH or R2SO2Na
Recently, as one of the promising synthesis strategies, direct
difunctionalization of alkenes or alkynes has attracted
considerable attention because of its high efficiency in the
cascade formation of carbon−carbon or carbon−heteroatom
bonds.5 In this field, some excellent difunctionalization reactions
Scheme 1 Methods for the synthesis of βꢀketosulfones
According to the principles of green chemistry, the
development of some green reaction media, catalysts, and
reaction conditions is still challenging in the current chemistry.11
Visible light can be considered as an ideal reaction promoter for
organic transformations because of it is nonꢀtoxic, inexpensive,
abundant, renewable, and generates no waste. As an alternative,
visibleꢀlight photoredox transformations has been successfully
introduced by MacMillan, Stephenson, Yoon, and other research
groups.12 Recently, tremendous progress has been made in this
respect since it opens a new avenue for the formation of C–C and
a
The Key Laboratory of LifeꢀOrganic Analysis and Key Laboratory of
Pharmaceutical Intermediates and Analysis of Natural Medicine, School
of Chemistry and Chemical Engineering, Qufu Normal University, Qufu
273165,
Shandong,China.
Eꢀmail:yangdaoshan@tsinghua.org.cn;
huawang_qfnu@126.com
† Electronic Supplementary Information (ESI) available: Experimental
details. See DOI: 10.1039/b000000x/
This journal is © The Royal Society of Chemistry [year]
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DOI: 10.1039/C6GC01403H
C–heteroatom bonds. In comparison to iridium, ruthenium or
copper complexes, organic dyes have been shown better prospect
in visible lightꢀinduced organic transformations owing to its
cheapness and nonꢀtoxicity. Until now, Eosin Y, Eosin B,
Fluorescein and Rose Bengal have been proven to be as efficient
catalyst in different visibleꢀlightꢀpromoted reactions.13 For
example, König et al. demonstrated an elegant eosin Y and
visible lightꢀcatalyzed method for the synthesis of vinyl sulfones
from aryl sulfinates.14 On the other hand, arylsulfinic acids are
more readily available in some cases and are easy to store and
handle. Importantly, sulfinic acids as sulfonylating source have
been employed for constructing sulfoneꢀcontaining compounds
via visibleꢀlight initiated organic transformations. In 2013, Lei
and coꢀworkers developed a highly efficient oxysulfonylation
method to construct βꢀhydroxysulfones with readily available
sulfinic acids.15 In 2014, Wang and Miao reported a novel and
efficient visible lightꢀinduced synthesis of sulfonated oxindoles
from Nꢀarylacrylamides and arylsulfinic acids.16 In 2015, Wang
et al. also developed an excellent visibleꢀlight initiated oxidative
cyclization of phenyl propiolates with sulfinic acids for the
formation of coumarin derivatives.17 Nevertheless, to the best of
our knowledge, visibleꢀlight initiate direct oxysulfonylation of
alkenes with sulfinic acids to form C−S bonds has never been
exploited. Inspired and encouraged by these pioneering works
and with part of our continuous interest in sulfurꢀcontaining
organic compounds synthesis,18 we herein wish to describe a new
visibleꢀlight initiated direct oxysulfonylation of alkenes with
sulfinic acids leading to βꢀketosulfones under mild conditions
(Scheme 2).
(v1/v2 = 4:1) was superior to the others (compare entries 7ꢀ11,
Table 1). Also, we attempted to use different oxidants such as
H2O2, DTBP, and K2S2O8, and TBHP was found to be more
suitable for this reaction (compare entries 11ꢀ14, Table 1). It
should be noted that, no reaction could proceed in the absence
of a light (entry 15, Table 1). Interestingly, the green LED
also gave the same yield (entry 16, Table 1). In addition, when
the reaction was performed under air atmosphere, it gave a
slightly lower yield (entry 17, Table 1). After the optimization
process for catalysts, oxidants, and solvents, the various βꢀ
ketosulfones were synthesized under our standard conditions:
1.0 mol% of Eosin Y as the photoredox catalysts, 3.0 equiv of
TBHP as the oxidant, and 2.0 mL of EtOH/H2O (v1/v2 = 4:1)
as the solvent at room temperature under nitrogen atmosphere.
Table 1 Optimization of the Reaction Conditionsa,b
Entry
Photoredox
Catalyst
Eosin Y
Na2ꢀeosinY
Rose bengal
Eosin B
Rhodamine B
Acridine Red
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Oxidant
Solvent
Yield b
(%)
70
14
54
59
61
38
37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
DTBP
H2O2
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
CH3CN
H2O
THF
DCE
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
Scheme 2 Strategy to βꢀketosulfones via visibleꢀlight initiated
direct oxysulfonylation of alkenes with sulfinic acids
Results and Discussion
6
67
44
75
65
34
55
Initially, styrene (1a) and benzenesulfinic acid (2a) were
chosen as the model substrates to optimize reaction conditions
including the photoredox catalysts, oxidants and solvents
under nitrogen atmosphere. As shown in Table 1, six
photoredox catalysts such as Eosin Y, Na2ꢀeosinY, Rose
bengal, Eosin B, Acridine Red, and Rhodamine B were tested
in EtOH under irradiation of an 11w whiteꢀlightꢀemitting
diode (LED) for 24h at room temperature by using 3.0 equiv
of tertꢀbutyl hydroperoxide TBHP (relative to amount of 1a)
as the oxidant, and Eosin Y gave the highest yield (70%)
(entries 1ꢀ6, Table 1). It should be note that, when Na2ꢀeosin
Y was used as the catalyst, only 14% of the desired product
was obtained. We supposed that the Na2ꢀEosin Y might not be
K2S2O8
TBHP
TBHP
TBHP
N.R.c
75d
71e
a
Reaction conditions: under nitrogen atmosphere, 1a (0.2mmol), 2a (0.3
mmol), catalyst (1.0 mol%), oxidant (3.0 equiv.), solvent mL,
2
b
c
EtOH/H2O (v1/v2 = 4:1), at room temperature for 24 h. Isolated yield.
In the darkness. d 11 W green LED. under air atmosphere. N.R. = no
d
reaction. TBHP= tertꢀbutyl hydroperoxide solution 5.5M in decane.
DTBP = diꢀtertꢀbutyl peroxide.
completely converted into Eosin
Y under the standard
conditions, and the coexist of Na2ꢀeosin Y and Eosin Y in the
reaction system might affect the conversion efficiency.
Furthermore, the solvents, including CH3CN, H2O, THF, DCE
With the optimum reaction conditions in hand, we turned our
attention to investigating the scope of the substrates for the
visibleꢀlight initiated direct oxysulfonylation of alkenes (1) with
sulfinic acids (2) leading to βꢀketosulfones (3). As shown in
and EtOH/H2O were tested by using Eosin
Y as the
photoredox catalyst at room temperature, and EtOH/H2O
2
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a
Reaction conditions: under nitrogen atmosphere, 1a (0.2mmol), 2a
Table 2, a variety of alkenes, bearing either electronꢀdonating
groups (R = OMe, Me) or electronꢀwithdrawing groups (R = Cl,
Br, CN, NO2) on the aryl ring, reacted smoothly with sulfinic
acids, affording the corresponding βꢀketo sulfones 3a−3v in
moderate to good yields. Notably, alkenes bearing a strong
electronꢀwithdrawing group such as nitro and cyano were also
compatible with the domino sequence (3q, 3r, 3s, and 3t).
Additionally, a naphthyl group could also participate in this
transformation with a good reactivity (3d, 3h, 3k, 3o, 3u and 3v).
Furthermore, the effects of the substituent on alkenes was also
investigated. The catalytic efficiency was not obviously affected
by steric hindrance in alkenes, and gave the corresponding 3l in
51% yield (Table 2, 3l). Unfortunately, aliphatic alkene, such as
butꢀ1ꢀene, did not work in the reaction (Table 2, 3w). The visible
light visibleꢀlight initiated domino reactions could tolerate some
functional groups such as alkyl group, ether, cyano, C–Cl bonds,
C–Br bonds, which could be used for further modifications at the
substituted positions.
(0.3 mmol), Eosin Y (1.0 mol%), TBHP (3.0 equiv.), solvent 2 mL,
EtOH/H2O (v1/v2 = 4:1), at room temperature for 24 h. Isolated
yield.
b
In order to gain some more information on the reaction
mechanism, several control reactions were performed as shown in
Scheme 3. When the reaction of 1a with 2a was carried out in
presence of a stoichiometric amount of 2,2,6,6ꢀtetramethylꢀ1ꢀ
piperidinyloxy (TEMPO, a well known radicalꢀcapturing species),
the present reaction was completely suppressed [eq (1), Scheme
3]. This result suggested that a radical process might be involved
in this transformation. To further probe the original source of
oxygen atom incorporated in the βꢀketosulfones, the reaction
between 1a and 2a under H2O18 was carried out under the
standard conditions for 24 h, and 52% 18Oꢀ3a and 48% 16Oꢀ3a
were detected, indicating carbonyl oxygen atom of the βꢀ
ketosulfones came from both TBHP and H2O [eq (2), Scheme 3,
HRMS, see ESI†]. Moreover, treatment propꢀ1ꢀenꢀ2ꢀylbenzene 4
with 4ꢀmethylbenzenesulfinic acid 2b under the standard
conditions led to 2ꢀphenylꢀ1ꢀtosylpropanꢀ2ꢀol 5 in 72% yield [eq
(3), Scheme 3]. Additionally, the reaction of 1a with sodium
benzenesulfinate 6b was tested under the standard conditions. As
expected, no conversion was observed [eq (4), Scheme 3].
Furthermore, an energy transfer process between Eosin Y and
TBHP was confirmed by fluorescence quenching experiments
(Support Information (SI) for detail). In order to verify the effect
of photoirradiation, an on/off visible light irradiation experiment
was performed. The graph preliminarily shows that the present
transformation required continuous visible light irradiation
(Scheme 3). Besides that, the quantum yield in the reaction 1a
with 2a was estimated to be 0.144, which is supporting evidence
for the proposed mechanism. However, the possibility of the
radical chain process is not completely excluded, further
investigations on the more detailed mechanism are underway in
our laboratory.
Table
2
Substrate scope of the visibleꢀlight initiated direct
oxysulfonylation of alkenes with sulfinic acids a, b
OMe
Me
O
O
O
O
O
O
S
O
S
O
S
O
3c (64%)
3a (75%)
3b (69%)
Me
O
O
S
O
O
O
O
S
S
O
O
O
Me
Me
3e (66%)
3f (74%)
3d (58%)
OMe
O
O
O
O
S
O
O
Me
S
S
O
O
O
Me
3i (76%)
Me
Me
3h (68%)
3g (52%)
Me
O
O
S
O
O
O
O
S
O
O
Me
S
O
Me
3l (51%)
3j (72%)
3k (63%)
OMe
O
O
O
O
O
O
S
S
O
S
O
O
Cl
Cl
3o (48%)
3m (84%)
Cl
3n (52%)
CH3
O
O
S
O
O
S
O
O
O
S
O
O
NC
NC
Br
3r (63%)
3p (80%)
3q (71%)
CH3
O
O
O
O
S
O
O
S
O
O
S
3u (64%)
O
O2N
·visible light irradiation on/off experiment
3t (58%)
O2N
3s (62%)
Me
O
O
O
O
S
S
O
O
3w (0%)
3v (42%)
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ligand or additive; (d) easy workup procedure; (e) at room
temperature; (f) outstanding tolerance of functional groups. With
these merits meeting the requirements of green and sustainable
synthesis chemistry, the developed synthesis approach would
extend the scope of synthetic methods for diverse βꢀketosulfones
in the academic and industrial fields. Further investigation on the
practical application of this method is in progress.
Acknowlegement
The authors gratefully acknowledge the financial support from
the National Natural Science Foundation of China (Nos.
21302110, 21302109 and 21375075), the Taishan Scholar
Foundation of Shandong Province, the Project of Shandong
Province Higher Educational Science and Technology Program
(J13LD14), and the Natural Science Foundation of Shandong
Province (ZR2013BQ017 and ZR2015JL004). We thank
Lingduan Meng in this group for reproducing the results of 3e
and 3q.
Scheme 3 Control experiments
On the basis of these preliminary results above, a proposal
mechanism would be herein presented (Scheme 4). Under the
visibleꢀlight irradiation, Eosin Y was converted to the excited
Eosin Y*. A single electron transfer between Eosin Y* and
TBHP afforded a tertꢀbutoxyl radical and hydroxyl anion. Then
sulfinic acids 2 reacted with a tertꢀbutoxyl radical to furnish the
corresponding sulfony radical A. Subsequent radical addition of
A to alkenes 1 produced carbonꢀcentered radical B, which could
be further transformed into carbocation intermediate C through
single electron transfer (SET) with Eosin Y·+. Subsequently,
nucleophilic attack of hydroxyl anion and H2O on the carbocation
intermediate produced the intermidate E, which was transformed
into the desired product 3 under the oxidative conditions. Further
investigations on the more detailed mechanism are ongoing in our
laboratory.
Notes and references
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Scheme
transformation.
4
A
proposed mechanism for the direct
Couclusions
In summary, we have developed an efficient Eosin Yꢀcatalyzed,
visible lightꢀinitiated direct oxysulfonylation of alkenes with
arylsulfinic acids to access βꢀketosulfones. A wide range of
functional groups can be tolerated well in the reaction conditions,
and the corresponding βꢀketosulfones were obtained in moderate
to good yields. This method can enjoy the following advantages:
(a) commercially available Eosin Y as the photoredox catalyst;
(b) ethanol and water as the solvent; (c) no addition of any base,
13 For selected examples, see: (a) A. K. Yadav and L. D. S. Yadav,
Tetrahedron Lett., 2014, 55, 2065; (b) Y. Pan, C. W. Kee, L. Chen
and C.ꢀH. Tan, Green Chem., 2011, 13, 2682; (c) T. Xiao, L. Li, G.
4
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DOI: 10.1039/C6GC01403H
Highly efficient visibleꢀlight initiated direct oxysulfonylation of alkenes with sulfinic
acids leading to βꢀketosulfones has been realized under metalꢀfree conditions.