Dimethyl sulfoxide as a mild oxidant in S-P(O) bond construction: Simple and metal-free approaches to phosphinothioates

Article abstract of DOI:10.1039/c6gc03115c

In the presence of dimethyl sulfoxide (DMSO) as a mild oxidant and reaction medium, a simple and efficient protocol has been developed for the preparation of phosphinothioates via oxidative dehydrogenative phosphorylation of thiols with P(O)H compounds. Additionally, a DMSO-mediated oxidative phosphorylation of disulfides is also demonstrated. Notably, these transformations occur efficiently without the help of any transition metal or additive. These reactions are easy to conduct and can be scaled-up, and various phosphinothioates are readily obtained in moderate to excellent yields with excellent chemoselectivity and good functional-group tolerance.

Full text of DOI:10.1039/c6gc03115c

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Dimethyl sulfoxide as a mild oxidant in S-P(O) bond construction:
simple and metal-free approaches to phosphinothioates
Jian-Guo Sun, Wei-Zhi Weng, Ping Li* and Bo Zhang*
Received 00th January 20xx,
Accepted 00th January 20xx
In the presence of dimethyl sulfoxide (DMSO) as the mild oxidant and reaction medium, a simple and efficient protocol has
been developed for the preparation of phosphinothioates via oxidative dehydrogenative phosphorylation of thiols with
P(O)H compounds. Additionally, a DMSO-mediated oxidative phosphorylation of disulfides is also demonstrated. Notably,
these transformations occur efficiently without the help of any transition metal or additive. These reactions are easy to
conduct and can be scaled-up, and various phosphinothioates are readily obtained in moderate to excellent yields with
DOI: 10.1039/x0xx00000x
www.rsc.org/
excellent
chemoselectivity
and
good
functional-group
tolerance.
DTBP) and DDQ have been made by Pan et al.,10 Wu et al.,11
and others12 (Scheme 1, d).
Introduction
O
O
X
H
P
R2
R1
S
X
H
P
R2
R1
S
+
+
Phosphinothioate has proved to be important and valuable
structural unit in organic synthesis, agrochemistry, and
medicinal chemistry due to its unique chemical and biological
R3
R3
X = Cl, Br
X = SPh, SO2NHNH2, SO2Cl
(b)
(c)
R2
[Cu], base
properties.1
Studies
have
revealed
that
many
O
O
O
(d) peroxides or DDQ
(a)
R1
S
H
X
P
R2
R1
S
P
H
H
P
R2
+
R1
S
+
organophosphorus compounds containing an S-P(O) bond
show prominent bioactivities, for example, as pesticides,
fungicides, and anticholinesterases.2 In light of the importance
of this structural unit, there is continuing interest in the
development of synthetic methods for S-P(O) bond
construction. Conventional approaches for the preparation of
phosphinothioates depend on nucleophilic substitution
reactions of the moisture-sensitive and toxic halides RSX or
R2P(O)X3 and on base-promoted Atherton-Todd type S-P(O)
formation4 (Scheme 1, a and b).
(e) [Pd]/dppf, styrene
(f) organic dyes, rt, air
visible light
R3
R3
R3
phosphinothioates
X = Cl, Br
(g)
only DMSO
R1
S
H
O
P
or
H
R2
+
R1
S
R3
S
R1
this work
Scheme 1 Strategies for the preparation of phosphinothioates.
Since the pioneering work of Zhao and co-workers in 2009,5
Very recently, Han and co-workers reported an oxidant-free
palladium-catalyzed dehydrogenative phosphorylation of
thiols with P(O)H compounds (Scheme 1, e).13 Shortly
thereafter, our group developed a novel, metal-free visible-
light-mediated oxidative cross-coupling of thiols with P(O)H
compounds using air as the oxidant (Scheme 1, f).14 Although
various approaches for the preparation of phosphinothioates
by direct S-P(O) bond coupling have been established, the
development of simple and complementary methods for a
facile access to phosphinothioates is still highly desirable due
to the importance of the S-P(O) structural moiety in various
fields as mentioned above.
a
copper-catalyzed cross-coupling reaction of diaryl
disulfides,5,6 sulfonyl hydrazines,7 and sulfonyl chlorides8 with
P(O)H compounds has become a valuable and practical
alternative for S-P(O) bond formation (Scheme 1, c).9 In recent
years, the cross-dehydrogenative coupling (CDC) reactions
between an S-H bond and an P(O)-H bond, which provide a
straightforward
and
atom-economic
approach
to
phosphinothioates, have attracted considerable attention
from the synthetic community. Impressive achievements in the
CDC reactions of thiols with P(O)H compounds in the presence
of a stoichiometric strong oxidant such as peroxides (TBPB or
Dimethyl sulfoxide (DMSO), which is a commonly used high-
boiling polar aprotic solvent, is utilized as
a mild and
inexpensive oxidant in synthetic chemistry.15 A variety of
DMSO-mediated oxidation reactions for the conversion of
alcohols, halides, epoxides, alkenes, alkynes, and thiols to their
corresponding products such as aldehydes, ketones, acids, and
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disulfides have been well developed.15 However, S-P(O) bond diphenylphosphine oxide 2a. In general, the reaction was not
construction by DMSO-based oxidation has not been sensitive to the electronic properties of substitutions on
investigated to date. In comparison with those thiophenol derivatives. As illustrated in Table 3, thiophenol
aforementioned oxidants (e.g., TBPB, DTBP, and DDQ), DMSO derivatives bearing electron-donating substituents at their
is more mild, cheap, and readily accessible. Utilization of para-position produced the
simple and common DMSO as the oxidant and involvement of
the construction of S-P(O) bonds should make this procedure
Table 2 Optimization of reaction conditionsa
much more attractive synthetically. Herein, we report a simple
and efficient oxidative cross-coupling reaction between thiols
(or disulfides) and P(O)H compounds using DMSO as the mild
oxidant, providing various phosphinothioates in moderate to
Entry
Amount of 1a (equiv)
Yieldb (%)
excellent yields under metal-and additive-free conditions.
1
1.5
2.0
2.5
3.0
2.0
2.0
2.0
73
94
92
93
81
83
93
2
3
Results and discussion
4
5c
6d
7e
We initiated our study by investigating oxidative
dehydrogenative phosphorylation of 4-methylbenzenethiol 1a
(1.5 equiv) with diphenylphosphine oxide 2a in the presence of
DMSO as the solvent and oxidant at room temperature under
a nitrogen atmosphere for 12 h. Pleasingly, the targeted
product 3aa was isolated in 73% yield (Table 1, entry 1). To
demonstrate the role of DMSO as an oxidant, we next
examined a variety of solvents under the same conditions
(Table 1, entries 2-14). However, these reactions did not
proceed well in these solvents, which confirmed the oxidative
effect of DMSO.
a
Reaction conditions: 1a and 2a (0.30 mmol) in DMSO (1.5 mL) at room
temperature under N2 for 12 h.
conducted under air. The reaction was conducted under O2 (1 atm). The
reaction was carried out in the dark.
b
c
Isolated Yields. The reaction was
d
e
desired phosphinothioates 3da (4-Et), 3ea (4-tBu), and 3fa (4-
OMe) in good to excellent yields (83-90%). The substituent
positions did not affect the efficiency of the transformation to
a large extent (see 3aa
, 3ba, and 3ca). Thiophenol derivatives
containing halogen groups such as F, Cl, and Br were
Table 1 Oxidative dehydrogenative phosphorylation of 4-methylbenzenethiol
1a with diphenylphosphine oxide 2a under various solventsa
successfully transformed into the corresponding products 3ia
3ka in good yields (60-82%). It is important to note that the
-
Table 3 Reaction scope of thiolsa,b
O
P
O
P
H
+
H
Ph
RS
Ph
RS
Entry
Solvent
DMSO
DCM
Yieldb (%)
Entry
8
Solvent
CH3CN
EtOAc
toluene
CH3NO2
DMF
Yieldb (%)
DMSO, rt, 12
h
Ph
Ph
1
2
3
4
5
6
7
73
0
0
1
2a
3
Me
Me
9
0
O
O
O
DCE
0
10
11
12
13
14
0
Me
S
P
Ph
S
P
Ph
S
P
Ph
Acetone
MeOH
THF
0
trace
trace
trace
trace
Ph
Ph
Ph
3aa, 94% (77%)c
3ba, 83%
3ca, 85%
0
O
O
O
0
DMA
Et
S
S
S
P
Ph
tBu
S
P
Ph MeO
S
P
Ph
Ph
Ph
Ph
1,4-dioxane
0
NMP
3da, 85%
3ga, 96%
3ja, 74%
3ea, 83%
3fa, 90%
a
Reaction conditions: 1a (0.45 mmol) and 2a (0.30 mmol) in solvent (1.5
O
O
P
O
P
mL) at room temperature under N2 for 12 h. b Isolated yields.
HO
P
Ph H2
N
S
Ph
F
S
Ph
Ph
Ph
Ph
Motivated by the above results, we further optimized the
reaction conditions. The yield of 3aa was further increased to
94% by using 2.0 equiv of 1a (Table 2, entry 2). When the
reaction was performed with 2.5 or 3.0 equiv of 1a, a similar
yield was obtained (Table 2, entries 3 and 4). The reaction
conducted under air or 1 atm of O2 provided slightly lower but
still good yield due to the formation of byproducts (Table 2,
entries 5 and 6). P(O)H compounds are prone to autoxidation
under an oxygen atmosphere. These byproducts probably
were derived from the autoxidation of the P(O)H
compounds.16 The yield was not affected when the reaction
was performed in the absence of light, implying that light did
not have any effect on the DMSO oxidation process.
3ha, 72%
3ia, 82%
O
O
O
Cl
P
Ph
Br
S
P
Ph
S
P
Ph
Ph
Ph
Ph
3ka, 60%d
3la, 79%
O
O
O
S
P
Ph
S
P
Ph
S
P
Ph
Ph
Ph
Ph
3oa, 55%e
3ma, 80%
3na, 60%
O
O
P
Me
S
P
Ph
S
Ph
Ph
Ph
3pa, 45%e
3qa, 65%f
a Reaction conditions: 1 (0.60 mmol) and 2a (0.30 mmol) in DMSO (1.5 mL)
b
c
at room temperature under N2 for 12 h. Isolated yields. 1.25g of 3aa
prepared. d The reaction was conducted for 6 h. e The reaction was conducted
With the optimized reaction conditions in hand, we
at 120 oC for 24 h in a sealed tube. The reaction was conducted at 100 oC for
f
examined
the
scope
of
thiol
substrates
with
12 h in a sealed tube.
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current method exhibits excellent chemoselectivity. For groups were all well tolerated in the reaction, leading to the
example, reactions with sensitive functional groups such as OH desired coupling products 3fa 3ma in good to excellent yields
-
and NH2 exclusively provided the S-P(O) coupling products in (58-95%). Aliphatic disulfides 4o-4q also proved to be suitable
good to excellent yields (3ga: 96%, 3ha: 72%). Thiophenol and substrates for this transformation, producing the
naphthalene-derivated substrates coupled readily with corresponding products 3oa-3qa in 42-78% yields.
diphenylphosphine oxide 2a to give the corresponding
Table 5 Reaction scope of disulfidesa,b
products 3la
such as
-
3na in good yields (60-80%). When aliphatic thiols
cyclohexanethiol, propane-1-thiol, and
phenylmethanethiol were employed for the transformation,
the corresponding products 3oa-3qa were obtained in
moderate to good yields. To show the practicality of this
method, we performed a preparative scale reaction of 1a with
2a to give 3aa in 77% yield (1.25 g).
Table
4 Oxidative phosphorylation of 1,2-di-p-tolyldisulfide 4a with
diphenylphosphine oxide 2a under various conditionsa
Entry
Amount of 4a (equiv)
Solvent
DMSO
DMSO
DMSO
CH3CN
DMF
Yieldb (%)
1
2c
3
4
5
6
7
0.5
0.5
0.6
0.6
0.6
0.6
0.6
73
70
80
62
62
60
61
a Reaction conditions: 4 (0.18 mmol) and 2a (0.30 mmol) in DMSO (1.5 mL)
b
c
at room temperature under N2 for 12 h. Isolated yields. 1.33g of 3aa
prepared. d The reaction was conducted at 120 oC for 24 h in a sealed tube.
DCE
We next turned our attention to the scope of P(O)H
1,4-dioxane
compounds (Table 6). Diarylphosphine oxides bearing methyl
or
a
Reaction conditions: 4a and 2a (0.30 mmol) in solvent (1.5 mL) at room
temperature under N2 for 12 h. b Isolated yields. c The reaction was conducted
for 24 h.
Table 6 Reaction scope of P(O)H compoundsa,b
It is well known that disulfides are important sulfur source in
organic synthesis. In comparison with thiols, disulfides are
more stable and bearing less odor. Along this line, we
conducted a coupling reaction of 1,2-di-p-tolyldisulfide 4a (0.5
equiv) with diphenylphosphine oxide 2a in DMSO at room
temperature under
a nitrogen atmosphere for 12 h.
Interestingly, the targeted product 3aa was obtained in 73%
yield without any additive (Table 4, entry 1). The yield of 3aa
was not improved when the reaction was run for 24 h (Table 4,
entry 2). A yield of 80% was achieved upon increasing the
amount of 4a to 0.6 equiv (Table 4, entry 3). Other solvents,
such as CH3CN, DMF, DCE, and 1,4-dioxane were also
investigated, which gave 3aa in 60-62% yields (Table 4, entries
4-7). The above results showed that 1,2-di-p-tolyldisulfide 4a
can directly react with diphenylphosphine oxide 2a by
nucleophilic substitution to give the product 3aa 17
In this
.
process, a molecule of 4-methylbenzenethiol 1a is released,
which is further oxidized by DMSO to regenerate 1,2-di-p-
tolyldisulfide 4a
.
With the optimal system in hand, we next investigated the
scope of disulfides as revealed in Table 5. All disulfides coupled
readily with diphenylphosphine oxide 2a to give the
corresponding products in good to excellent yields. Diaryl
disulfides with a methyl substituent at the meta- and ortho-
position of the aromatic ring worked well with good yields
a Reaction conditions: 1a (0.60 mmol) and 2 (0.30 mmol) in DMSO (1.5 mL)
at room temperature under N2 for 12 h. Reaction conditions in parentheses:
4a (0.18 mmol) and 2 (0.30 mmol) in DMSO (1.5 mL) at room temperature
under N2 for 12 h. b Isolated yields. c Using DMSO (1.3 mL) and DCM (0.2
mL). d The reaction was conducted for 36 h.
(
3ba and 3ca). A variety of functional groups, such as
methoxyl, hydroxyl, halide (F and Cl), phenyl, and naphthyl
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tert-butyl groups at the para- or meta-position of the aromatic be involved in these reaction processes [Scheme 2, eqn (1) and
rings gave the corresponding phosphinothioates in good yields eqn (2)]. To completely exclude the radical mechanism, we
(
3ab, 3ac, and 3ae). A moderate yield was obtained for the next performed EPR experiments and radical capture
ortho-substituted systems likely due to the steric hindrance experiments. We employed DMPO (5,5-dimethyl-1-pyrroline-
effect (3ad). With substrates carrying halogen substituents N-oxide) as the radical trapping agent, and no radical signal
such as F, Cl, and Br on the benzene rings, the desired products was observed by EPR spectra. Moreover, radical capture
3af
functional groups, such as phenyl and naphthyl were tolerated, diphenylphosphine oxide 2a did not give radical adducts
affording the products in good yields (3ai and 3aj). When one [Scheme 2, eqn (3) and eqn (5)]. Finally, we conducted
arene ring was replaced by alkyl or alkoxy groups, the products radical clock experiments. Starting with olefin containing a
were obtained in good yields (3ak 3am). All experiments were typical radical clock cyclopropane moiety, no desired ring-
-
3ah were obtained in moderate to good yields. Other experiments with styrene
4
on 4-methylbenzenethiol 1a and
5
and
8
-
then repeated by using 1,2-di-p-tolyldisulfide 4a as the opening product was obtained [Scheme 2, eqn (4) and eqn
substrate (see yields in parentheses). As illustrated in Table 6, (6)]. All of these observations support the hypothesis that P-
various diarylphosphine oxides did smoothly react with 1,2-di- centered radicals and S-centered radicals are not likely
p-tolyldisulfide 4a to produce the corresponding involved in the current reaction. Furthermore, in thiol-
phosphinothioates 3ab
However, diethyl phosphonates failed to give the targeted are produced in all cases. Further investigation showed that
products under the current reaction conditions. 1,2-di-p-tolyldisulfide 4a could be formed from 4-
-3am in moderate to good yields. mediated S-P(O) formation reaction, we found that disulfides
To gain insight into the possible mechanism of the DMSO- methylbenzenethiol 1a in 85% yield under the standard
mediated S-P(O) coupling, some control experiments were conditions [Scheme 2, eqn (7)]. However, the homocoupling
performed (Scheme 2). The phosphorylation of both 1a and 4a product 10 from diphenylphosphine oxide 2a could not be
with diphenylphosphine oxide 2a in the presence of 2,6-di- observed [Scheme 2, eqn (8)]. These results indicated that 1,2-
tert-butyl-4-methylphenol (BHT) or 2,2,6,6-tetramethyl-1- di-p-tolyldisulfide 4a may be the key intermediate of this
piperidinyloxy (TEMPO) as a radical scavenger gave the transformation.
corresponding products in good yields , thus suggesting that a
radical mechanism or single-electron-transfer (SET) might not
On the basis of the above experiments and previous
literatures,14,18 a plausible reaction mechanism is proposed in
Scheme 3. Initially, DMSO gets protonated by thiol
produce the thiol anion and the protonated sulfoxide
Subsequently, nucleophilic attack of the thiol anion onto the
protonated sulfoxide forms the thiol-sulfoxide adduct
which then reacts further with another molecule of thiol
afford the disulfide along with dimethylsulfane (DMS) and
H2O.18,19 Finally, the product
is generated by nucleophilic
attack of the P(O)H compounds with the disulfide 4 17
This
, which is further
1 to
O
O
A
B.
+
H
P
Ph
Me
S
P
Ph (1)
Me
S
H
DMSO, rt, 12 h
Ph
2a
Ph
A
1a
3aa
B
C,
no additive
BHT (2.0 equiv)
94%
85%
TEMPO (2.0 equiv) 70%
1
to
Me
O
O
4
S
(2)
Ph
+
H
P
Ph
Me
S
P
S
DMSO, rt, 12 h
3
Ph
2a
Ph
Me
4a
3aa
.
no additive
BHT (2.0 equiv)
80%
82%
TEMPO (2.0 equiv) 68%
process allows the regeneration of thiol
oxidized by DMSO to provide the disulfide
1
S
4.
Ph
+
(3)
Me
Me
S
S
H
H
Ph
DMSO, rt, 12 h
Me
1a
4
5 (0%)
S
+
(4)
Ph
Me
DMSO, rt, 12 h
1a
6
7 (0%)
O
O
P
Ph
Ph
+
(5)
H
H
P
Ph
Ph
DMSO, rt, 12 h
Ph
O
Ph
2a
4
8 (0%)
P
O
Ph
Ph
P
Ph
+
(6)
Ph
DMSO, rt, 12 h
Ph
2a
6
9 (0%)
Me
Scheme 3 Proposed reaction mechanism.
S
(7)
Me
S
H
S
DMSO, rt, 12 h
Me
4a (85%)
1a
Conclusions
O
O
O
P
O
P
(8)
H
P
Ph
Ph
+
H
P
Ph
Ph
In summary, we have presented a simple and direct oxidative
S-P(O) coupling method for the efficient preparation of
phosphinothioates starting with readily available thiols (or
disulfides) and P(O)H compounds using common and cheap
DMSO, rt, 12 h
Ph
2a
Ph
Ph Ph
10 (0%)
2a (95%)
Scheme 2 Mechanistic studies.
4 | J. Name., 2012, 00, 1-3
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Disulfide
4 (0.18 mmol, 0.6 equiv) and P(O)H compound 2
DMSO as the mild oxidant. Reactions that are easy to conduct
and can be scaled-up occur with excellent chemoselectivity
and good functional-group tolerance. Importantly, these
transformations occur without the help of any transition metal
and additive, and a wide array of phosphinothioates can be
readily obtained in moderate to excellent yields. These
advantages make this protocol very practical. Further studies
on the mechanism and the synthetic applications are ongoing
in our laboratory.
(0.30 mmol, 1.0 equiv) were placed in a 10 mL Schlenk tube.
Then DMSO (1.5 mL) was added. The reaction mixture was
stirred at room temperature under N2 for 12 h, and the
reaction was monitored with TLC. After the reaction was
completed, H2O (10.0 mL) was added, and the mixture was
extracted by EtOAc (3x10.0 mL). The combined organic layer
was dried over anhydrous Na2SO4, filtered, and concentrated
by rotary evaporation. The crude reaction mixture was purified
by flash column chromatography on silica gel to afford the
corresponding product.
Experimental
General information
Acknowledgements
All manipulations were conducted with a standard Schlenk
tube under N2. Unless otherwise noted, materials obtained
from commercial suppliers were used without further
This work is financially supported by the National Natural
Science Foundation of China (81421005), the Natural Science
Foundation of Jiangsu Province (BK20160743), the 111 Project
(B16046), and the Project Program of State Key Laboratory of
Natural Medicines, China Pharmaceutical University
(SKLNMZZYQ201602). We thank Meng-Ning Li in this group
for assistance with mass spectrometry.
purification. The P(O)H compounds 2b-2k were prepared
reported method.20 Flash column
according to
a
chromatography was carried out on silica gel (200-300 mesh).
Thin layer chromatography (TLC) was performed using silica
1
gel 60 F254 plates. H NMR spectra were recorded on a Bruker
AV-300 spectrometer or a Bruker AV-500 spectrometer at
room temperature. Chemical shifts (in ppm) were referenced
to tetramethylsilane (δ = 0 ppm) in CDCl3 as an internal
standard. 13C NMR spectra were obtained by the same NMR
spectrometer and were calibrated with CDCl3 (δ = 77.00 ppm).
Notes and references
1
(a) L. D. Quin, A Guide to Organophosphorus Chemistry,
Wiley Interscience, New York, 2000; (b) P. J. Murphy,
Organophosphorus Reagents, Oxford University Press,
Oxford, UK, 2004; (c) M. A. Gallo and N. J. Lawryk, Organic
Phosphorus Pesticides. The Handbook of Pesticide Toxicology,
Academic Press, San Diego, 1991; (d) N. N. Melnikov,
Chemistry of Pesticides, Springer-Verlag, New York, 1971; (e)
N.-S. Li, J. K. Frederiksen and J. A. Piccirilli, Acc. Chem. Res.,
2011, 44, 1257; (f) P. Carta, N. Puljic, C. Robert, A.-L.
Dhimane, L. Fensterbank, E. Lacôte and M. Malacria, Org.
31P NMR spectra were recorded on
a Bruker AV-300
spectrometer or a Bruker AV-500 spectrometer, and using 85%
1
H3PO4 as external standard. Data for H NMR are reported as
follows: chemical shifts (δ ppm), multiplicity (s = singlet, d =
doublet, t = triplet, q = quartet, m = multiplet or unresolved, br
s = broad singlet), coupling constant (Hz) and integration. Data
for 13C NMR are reported in terms of chemical shift and
multiplicity where appropriate. Mass spectra were performed
on an Aglient 6530 Q-TOF for HRMS. The yields were
determined on a METTLER TOLEDO ME 104 balance (accuracy:
0.1 mg). Melting points (Mp) were determined on a SGW X-4B
and are uncorrected.
Lett., 2007, 9, 1061; (g) N. Hoshi, T. Kashiwabara and M.
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General
procedure
for
DMSO-mediated
oxidative
dehydrogenative phosphorylation of thiols with P(O)H compounds
(GP1)
Thiol
1 (0.6 mmol, 2.0 equiv) and P(O)H compound 2 (0.3
mmol, 1.0 equiv) were placed in a 10 mL Schlenk tube. Then
DMSO (1.5 mL) was added. The reaction mixture was stirred at
room temperature under N2 for 12 h, and the reaction was
monitored with TLC. After the reaction was completed, H2O
(10.0 mL) was added, and the mixture was extracted by EtOAc
(3x10.0 mL). The combined organic layer was dried over
anhydrous Na2SO4, filtered, and concentrated by rotary
evaporation. The crude reaction mixture was purified by flash
column chromatography on silica gel to afford the
corresponding product.
General procedure for DMSO-mediated oxidative phosphorylation
of disulfides with P(O)H compounds (GP2)
B. Han, RSC Adv., 2015, 5, 71544.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2016, 00, 1-3 | 5
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Green Chemistry
Page 6 of 7
View Article Online
DOI: 10.1039/C6GC03115C
ARTICLE
Journal Name
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6 | J. Name., 2012, 00, 1-3
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Page 7 of 7
Green Chemistry
View Article Online
DOI: 10.1039/C6GC03115C
Dimethyl sulfoxide as a mild oxidant in S-P(O)
bond construction: simple and metal-free
approaches to phosphinothioates
Jian-Guo Sun, Wei-Zhi Weng, Ping Li*
and Bo Zhang*
A direct metal-free oxidative S-P(O) coupling reaction for the preparation
of phosphinothioates starting with readily available thiols (or disulfides)
and P(O)H compounds using DMSO as the mild oxidant is presented.