Electrochemical oxidative radical oxysulfuration of styrene derivatives with thiols and nucleophilic oxygen sources

Article abstract of DOI:10.1039/c8gc01337c

Oxydifunctionalization of olefins represents a powerful tool and yet poses a challenging task. Previous methods have usually required a stoichiometric amount of a strong oxidant and an expensive transition-metal catalyst. This work describes the first example of the electrochemical oxysulfuration reaction of olefins with thiols and nucleophilic oxygen sources. This electrochemical difunctionalization reaction is conducted under catalyst- and oxidant-free conditions, and shows good substrate generality, affording thio-substituted alcohols, ethers and γ-lactones in good chemical yields and with excellent regioselectivities. This work represents a new and green strategy for the difunctionalization of olefins, and also provides a complementary and highly valuable prospect for current methodologies for the synthesis of thio-substituted compounds.

Full text of DOI:10.1039/c8gc01337c

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Electrochemical oxidative radical oxysulfuration of styrene
derivatives with thiols and nucleophilic oxygen sources
Yang Wang,a Lingling Deng,a Haibo Mei,*a Bingnan Du,*b Jianlin Han*a and Yi Pana
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Oxydifunctionalization of olefins represents a powerful tool and cascade reactions for the C-C,7,12 C-O,13 C-N,6a,8b,10b,14 C-
yet
a
challenging task. Previous methods usually require
a
S,9c,10c,15 N-S,16 N-N,6c and N-P17 bond formations.
stoichiometric amount of a strong oxidant and an expensive
Olefin is a kind of common building block in organic
transition-metal catalyst. This work describes the first example of synthesis and fundamental structure unit existing in numerous
the electrochemical oxysulfuration reaction of olefins with thiols natural products and pharmaceuticals.18 The oxidative
and nucleophilic oxygen sources. This electrochemical difunctionalization of the easily available olefins is an
difunctionalization reaction is conducted under catalyst- and attractive method for the construction of the ubiquitous
oxidant-free conditions, and shows good substrate generality, scaffold. Especially the oxydifunctionalization of olefins, such
affording thio-substituted alcohols, ethers and γ-lactones in good as oxytrifluoromethy-lation,19 oxyarylation,20 oxyalkylation21
chemical yields and excellent regioselectivities. This work and oxysulfuration,22 have attracted many research interests.
represents a new and green strategy for the difunctionalization of Usually, these reported reaction systems need an oxidant and
olefins, and also provides a complementary and highly valuable optionally a transition-metal catalyst. The use of large excess
vista for the current methodologies of thio-substituted of oxidants, expensive and toxic metals or additives usually
compounds synthesis.
generates chemical wastes.
Electrochemical difunctionalization of alkenes currently
emerged as a new approach for olefin difunctionalization that
maximizes substrate generality, avoids using a strong oxidant,
and minimizes by-product formation. The pioneering work was
reported by the Lin group23 on the difunctionalization of
alkenes in which a single Mn-based electrocatalytic cycle was
used to promote the addition to the C-C bond, which provides
an environmentally friendly method that converts alkenes to
1,2-diazides, 1,2-dichlorides, and chlorotrifluoromethylated
compounds. In the recent years, the S-H activation is also one
of the most hot topics in organic chemistry, and a notable
development has been made.10a,24 To the best of our
Electrochemistry has been looked as one of the most direct
ways of interacting with molecules, and electrons could
interact with nucleus directly at anode and cathode.1 This
specialty of electrochemistry can be regarded as a kind of
oxidant or reductant, which means that the organic synthesis
could avoid the use of chemical oxidant or reductant in
electricity environment. Thus, electrosynthesis has been
recognized as a green technology2 since it does not generate
reagent waste.2a,3 Furthermore, this process can be precisely
controlled and conveniently stopped via the variation of
voltage. Electrochemistry has been developed for a long
history1,4 and currently is gaining rising attention.5 The Baran,6
Waldvogel,7 Yoshida,8 Xu,9 Lei10 and other groups have
independently developed a series of elegant electroorganic
dehydrogenation cross-coupling reactions11 and radical
knowledge, the oxysulfuration of
alkenes under
electrochemical conditions has never been explored. Also, it
was found that the use of oxidants in the previous
oxysulfuration reactions, thiols/thiophenols can be easily over-
oxidized to generate undesirable side products, such as
sulfoxides and sulfones.22a,25 Thus, the use of electrooxidation
could provide a solution to the above over-oxidation problem,
as the oxidative ability could be conveniently adjusted and by
the variation of voltage.10a Notably, the Yoshida group
developed an addition reaction of diaryl disulfides to carbon–
carbon multiple bonds using electrochemistry affording the
corresponding diarylthio-substituted compounds in good
yields.26
a.School of Chemistry and Chemical Engineering, State Key Laboratory of
Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials,
Nanjing University, Nanjing, 210093, China. E-mail: hanjl@nju.edu.cn
b.State Key Laboratory of Chirosciences and Department of Applied Biology and
Chemical Technology, The Hong Kong Polytechnic University, Hung Hum,
Kowloon, Hong Kong. E-mail: bingndu@polyu.edu.hk
† Footnotes relaꢀng to the ꢀtle and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [general reaction
procedures, characterization data, and copies of NMR spectra]. See
DOI: 10.1039/x0xx00000x
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Journal Name
Entry
Voltage (V)
Electrolyte (equiv)
Time
(h)
5
Yield (%)b
Inspired by recent developments in the area of synthetic
electrochemistry23 and challenged by the problems in the
previous systems,22a,25 we herein reported the first example of
electrochemical radical oxysulfuration of olefins with thiols
and nucleophilic oxygen sources. This reaction was conducted
at room temperature and did not need any oxidative reagent,
catalyst or additive. Furthermore, this reaction showed wide
substrate scope, broad functional group tolerance, and
excellent regioselectivity, which represents a new and green
strategy for the difunctionalization of olefins.
1
2
3.0
4.0
5.0
3.0
3.0
3.0
3.0
3.0
3.0
NaCl (0.5)
NaCl (0.5)
51
49
45
33
56
62
76
80
83
5
3
NaCl (0.5)
5
4
NaCl (1.0)
5
5
Bu4NBr (0.5)
Bu4NBF4 (0.5)
Bu4NBF4 (0.5)
Bu4NBF4 (0.5)
Bu4NBF4 (0.5)
5
6
7c
5
5
8
9d
8
8
a Reaction conditions: 1a (0.2 mmol), 2a (0.6 mmol), water (2 mL) and MeCN
(3 mL) under argon. b Isolated yield based on 1a. c 4 equivalent of 2a. d 4 mL
of MeCN was added.
This work:
the first example of electrochemical oxysulfuration of alkenes
R5
O
R2
R1
3
R1
R
Pt
Pt
R4
R3
HO R5
R2
+
+
Ar SH
H2O/CH3CN, rt
undivided cell
S
R4
Ar
With the optimal reaction conditions in hand, we then
investigated the substrate scope of this reaction by using
various thiophenols, alkenes, and nucleophilic oxygen sources
(Table 2).
catalyst-free, oxidant-free
gram-scale synthesis
varieties of oxygen sources
green method for difunctionaliztion of alkenes
Scheme 1 Electrochemical difunctionalization of olefins.
Table 2 Substrate scope of alkenes and thiols.a,b
Initially, the electrochemical reaction of prop-1-en-2-
ylbenzene 1a with 4-methoxybenzenethiol 2a by the use of
platinum-plate anode and cathode, and NaCl as an electrolyte,
was conducted at 3.0 V cell potential in H2O/MeCN at room
temperature under argon atmosphere for
5
h. The
1-((4-methoxyphenyl)thio)-2-
4 was obtained in 51% isolated yield (entry
corresponding
product
phenylpropan-2-ol
1, Table 1). Then, the voltage for this reaction was screened,
and the results in entries 1-3 indicated that 3 v was the best
one. Next, it was found that increasing the loading amount of
electrolyte NaCl from 0.5 to 1.0 equiv, resulting in a decreased
chemical yield (33%, entry 4). To further optimize the reaction
conditions, other electrolytes, such as Bu4NBr and Bu4NBF4
were used in the reaction (entries 5-6). Bu4NBF4 worked better
in this reaction and afforded obviously improved yield (62%,
entry 6). When 4 equivalent of thiophenol 2a was used in the
reaction, a further increased yield of product
4 was obtained
(76%, entry 7). 80% yield of the product 4 was obtained when
the reaction time was prolonged to 8 hours. Finally, when
acetonitrile (4 mL) was added as the co-solvent for this
reaction, the desired product 4 was obtained in a slightly
higher chemical yield (83%, entry 9).
Table 1 Optimization of the reaction conditions.a
a
Reaction conditions: Pt anode, Pt cathode, at 3.0 V cell potential, alkenes (0.2
mmol), thiophenol (0.8 mmol), Bu4NBF4 (0.1 mmol), water (2 mL) and MeCN (4
mL) under argon, at room temperature for 8 h. b Isolated yields.
Thiophenols
4
–
10 bearing substituted group, such as
) and halo ( 10) on the para-position
methoxyl (4), alkyl (
5–
7
9–
of the aromatic ring, worked very well in this system resulting
in the corresponding product in good yields (50-83%).
Reactions of the meta-substituted thiophenols also proceeded
smoothly to give the desired product with good to excellent
yields (51-85%, 11–13). We then turned our attention to
investigate another part of substrate generality by using a
2 | J. Name., 2012, 00, 1-3
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a
Reaction conditions: Pt anode, Pt cathode, at 3.0 V cell potential, alkenes (0.2
mmol), thiophenol (0.8 mmol), Bu4NBF4 (0.1 mmol), 4 Å molecular sieve (200
mg), alcohol (2 mL) and MeCN (4 mL) under argon at room temperature for 8 h. b
Isolated yield. c 4-phenylpent-4-en-1-ol (40) (0.2 mmol), MeCN (6 mL) used.
different kind of alkenes in this electrochemical oxidative
radical oxysulfuration reaction (14
that the para-substituted prop-1-en-2-ylbenzenes participated
in this reaction very well. Both the electron-donating (14 15
and electron-withdrawing groups (16 18), even the strong
–32). It was pleased to find
–
)
–
Thio-substituted γ-lactone is a kind of useful drug molecular
framework. It has been proven that there is antiviral activity
against poliovirus, RNA virus and herpes simplex virus type 1
(HSV-1).27 Unsaturated carboxylic acid is a simple, easy to
prepare and efficient intermediate to construct these
substituted lactone derivatives via cascade thiolation and
intramolecular cyclization. Our group developed the first
example of thio-substituted γ-lactone synthesis by using
unsaturated carboxylic acid in the presence of a chemical
oxidant.28 It gives us the inspiration to demonstrate the
application of the current electrochemical oxysulfuration
approach in the synthesis of thio-substituted γ-lactones (Table
4). Thus, a series of substituted thiophenols and unsaturated
carboxylic acids were tested in this electrochemical system.
electron-withdrawing group, trifluoromethyl, were well
tolerated and afforded the satisfactory results. Next, we
investigated the steric hindrance of this reaction by using the
ortho- and meta-substituted prop-1-en-2-ylbenzene as
substrates (19
effect in this system, as the obviously decreased yields were
obtained for the ortho-substituted alkenes (41-61%, 19 20).
–22). It was found that there was a strong steric
–
Especially, an excellent yield (88%) was obtained when 1,3-
dimethyl-5-(prop-1-en-2-yl)benzene was used (23). To further
extend the alkene scope of the reaction, a series of styrene
derivatives were examined in this system. However, obviously
lower chemical yields were obtained (38-44%, 24–27). It is
mainly because that this reaction proceeds via a radical
process, and the tertiary benzyl radical, generated from sulfur
radical addition to styrene, is less stable than quaternary
carbon radical. Finally, different terminal olefins were tried in
Generally, both electron-donating group (41–43) and electron-
withdrawing group (44–45) substituted thiophenols were all
compatible in this system, and gave the corresponding
lactones with good to excellent yields (58-87%). Different kind
of unsaturated carboxylic acids, like 5-(4-methoxyphenyl)hex-
5-enoic acid and 2-(1-(p-tolyl)vinyl)benzoic acid were also
suitable substrates and gave the corresponding lactones with a
six-membered ring (47) or benzohetercyclic ring (48).
this electrochemical system (28–32). Styrenes with different α-
substituted alkyl, include ethyl, isopropyl, and cyclohexyl, were
all suitable substrates for this reaction, giving the expected
product in good yields (28–30). Even the reaction of 5-(but-1-
en-2-yl)benzo[d][1,3]dioxole also could proceed well to give
the corresponding product in a good yield (82%, 31). In
particular, a carbonylation product 32 could be obtained when
2-phenylacrylic acid (33) was chosen as the alkene.
Table 4 Application of this method in thio-substituted γ-lactones synthesis.a,b
As the next objective of our investigation, we sought to
demonstrate the generality of our approach that other
nucleophilic oxygen sources, such as primary alcohols, could
be also applied in this method to construct corresponding
ether derivatives (Table 3). To eliminate the impact of water
existing in the solvent, 4 Å molecular sieve was added in this
reaction. Gratifyingly, a series of primary alcohols reacted very
well with alkenes 1a and thiols 34 to afford the corresponding
ethers 35
–
38 in good chemical yields (69-80%). To our delight,
40 containing alkenyl and
when 4-phenylpent-4-en-1-ol
(
)
hydroxyl moieties was used as a substrate, a functionalized
tetrahydrofuran 39 was obtained in 51% yield.
Table 3 Substrate scope of primary alcohols.a,b
a
Reaction condition: Pt anode, Pt cathode, at 3.0 V cell potential, unsaturated
carboxylic acids (0.2 mmol), thiophenol (0.6 mmol), Bu4NBF4 (0.1 mmol),
TSOH·H2O (0.2 mmol) and MeCN (6 mL) under argon at room temperature for 8
h. b Isolated yield.
We evaluated the scalability of this electrochemical
oxidative radical oxysulfuration of alkenes by performing this
reaction on a 5 mmol scale. The reaction of prop-1-en-2-
ylbenzene
(
1a), 4-chlorobenzenethiol
(
34
)
and water
was
proceeded smoothly and the desired hydroxysulfide
9
obtained in 62% yield (0.86 g, Scheme 2). This result shows the
great potential of this electrochemical oxidative radical
oxysulfuration of alkenes in practical synthesis.
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Journal Name
OH
S
S
H
Pt (+) Pt (-),
Ecell = 3 V
+
H
O
(20 mL)
Cl
MeCN (40 mL) /
S
2
Ar1
2
H
Cl
Bu4NBF4 (0.5 euqiv)
under argon, rt, 8 h
undivided cell
9
, 62% yield
(0.86g, 3.1 mmol)
1a
34
(2.2 g, 15 mmol)
(0.59g, 5 mmol)
Scheme 2 Gram-scale synthesis.
S
Ar1
H
S
A
Ar1
To get the insight of this electrochemical oxysulfuration
reaction, a series of control experiments were conducted
(Scheme 3). A radical-trapping experiment has been carried
out under standard reaction conditions, with the use of
toluylene (49) as the radical-trapping reagent (Scheme 3).
After the careful isolation of reaction mixture, the trapping
product 50 was obtained with 72% yield. Thus, radical
intermediates are possibly involved in this electrochemical
system. Next, we carried out cyclic voltammetry (CV)
experiments to study the redox potential of the substrates
(Figure 1). An oxidation peak of 34 in acetonitrile was observed
at 1.99 V and reduction peak at -1.33 V. Therefore, between
the reaction voltage, the thiophenol may be both involved in
oxidation and reduction process in this system.
2
R1
Ar2
1
R1
S
Ar1
D
S
S
Ar2
Ar2
Ar1
Ar1
H2
B
H
R1
R1
HO R2
R2O
S
anode
cathode
Ar2
Ar1
C
Scheme 4 Proposed mechanism.
Initially, the aryl sulfur radical
thiophenol
A
is generated from
2
via a SET oxidation at the anode.10a Then, this aryl
sulfur radical
intermediate
intermediate
A
adds to alkene
, which is rapidly oxidized to carbocation
at the anode. Then, this carbocation is
1 affording the radical
B
C
SH
Pt (+) Pt (-),
Ecell = 3 V
O
H
+
C
S
H O
MeCN/
2
Cl
Bu4NBF4 (0.5 euqiv)
rt, 8 h, under argon
undivided cell
trapped by the nucleophile to afford the final oxysulfuration
product as well as a hydrogen ion. At the same time,
Cl
34
49
50, 72% yield
Scheme 3 Mechanistic studies.
thiophenol
2 is reduced to release hydrogen gas and aryl sulfur
anion D at the cathode, which reacts with hydrogen ion to
regenerate thiophenol 2 for the next cycle.
0.00006
0.00004
0.00002
0.00000
-0.00002
-0.00004
-0.00006
Conclusions
In conclusion, we have developed a mild and electrochemical
oxidative reaction for the oxysulfuration of olefins. This
method enables the difunctionalization of olefins via cascade
two oxidations at anode under catalyst- and oxidant-free
conditions. The reaction shows good substrate generality, and
several types of nucleophilic oxygen sources are suitable for
this transformation. Most importantly, this reaction can be
conducted on a gram scale with good reaction efficiency, and
such electrochemical system has been successfully applied in
the synthesis thio-substituted γ-lactones with high yield. This
34
-2
-1
0
1
2
Potential/V
Figure 1. Cyclic voltammetry of 34 (10-4 M) in CH3CN with n-Bu4NPF6 (0.2 M).
Conditions: glassy carbon working electrode, Pt wire counter electrode, SCE reference
work represents
a new and green strategy for the
electrode, scan rate = 0.2 V∙ s−1
.
difunctionalization of olefins, and also provides
a
complementary and highly valuable vista for the current
methodologies of thio-substituted compounds synthesis.
We gratefully acknowledge the financial support from the
National Natural Science Foundation of China (Nos. 21472082,
21772085 and 21761132021).
Based on the previous reports9,10,22,28 and the above
experimental results, a possible electrochemical oxidative
radical reaction mechanism is shown in Scheme 4.
Notes and references
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Green Chemistry
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DOI: 10.1039/C8GC01337C
The first example of the electrochemical oxysulfuration reaction of alkenes with thiols and
nucleophilic oxygen sources has been reported.