Metal- and oxidant-free S-P(O) bond construction: Via direct coupling of P(O)H with sulfinic acids

Article abstract of DOI:10.1039/c6gc03285k

We have developed a simple and convenient method for S-P(O) bond formation between R₂P(O)H and sulfinic acids under metal-, oxidant-, and halogen-free conditions. The current method is compatible with a broad range of substituents on various substrates including halogens and heterocyclic moieties. The synthetic potential of this method was further highlighted by the expeditious synthesis of optically active P-chiral phosphorothioates via stereospecific coupling.

Full text of DOI:10.1039/c6gc03285k

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Metal- and Oxidant-Free S–P(O) Bond Construction via Direct
Coupling of P(O)H with Sulfinic Acids
Youngtaek Moon, a Yonghoon Moon,b,a Hangyeol Choi, b,a and Sungwoo Hong*,a,b
Received 00th January 20xx,
Accepted 00th January 20xx
We have developed a simple and convenient method for S–P(O) bond formation between R2P(O)H and sulfinic acids under
metal-, oxidant-, and halogen-free conditions. The current method is compatible with a broad range of substituents on
various substrates including halogens and heterocyclic moieties. The synthetic potential of this method was further
highlighted by the expeditious synthesis of optically active P-chiral phosphorothioates via stereospecific coupling.
DOI: 10.1039/x0xx00000x
www.rsc.org/
catalyzed desulfitative/crossꢀcoupling reactions using sulfinate
derivatives as coupling partners have been used for C–C bond
formation reactions.[9] On the other hand, reactions with
Introduction
The S–P(O) structural motif is a versatile and important
building block that is widely present in biologically active
molecules including pesticides, insecticides, enzyme inhibitors,
and pharmaceuticals.[1] Therefore, the significance of
thiophosphates has inspired chemists to develop efficient and
selective methods for S–P(O) bondꢀformation. The traditional
synthetic approach to S–P(O) bond formation is based on
nucleophilic substitution using R2P(O)X or RSX.[2] However,
extensive applications of traditional protocols often suffer from
limitations in the preparation of toxic and moistureꢀsensitive Pꢀ
or Sꢀreactants, poor functional group tolerance or harsh reaction
conditions. To overcome these challenges, considerable efforts
have been made in the direct crossꢀcoupling reactions of Hꢀ
phosphine oxides/H–phosphinates with thiols.[3ꢀ5] Recently,
sulfinyl cations from sulfinic acids have rarely been described
in the literature except for sulfenylation with indoles.[10] We
questioned whether the sulfinyl cations generated from sulfinic
acids could be suitable coupling partners for the P(O)H moiety
with high efficiency. We speculated that if sulfinylphosphine
oxide generated in situ as a result of cross coupling of a sulfinyl
cation and Hꢀphosphoryl compounds, it could be further
converted to the phosphorothioate moiety via concomitant
reduction (Scheme 1c). Notably, this new approach differs from
other S–P(O) bond formation methods in which thiols are
typically oxidized for the preparation of sulfide precursors
peroxide or
Nꢀchlorosuccinimideꢀmediated reactions have been
successfully applied to activate thiols for S–P(O) bond
formation.[4] Furthermore, impressive results were obtained by
using Pdꢀcatalyzed coupling reactions[3a] or photocatalysis[5] to
produce phosphorothioate derivatives. As these methods
require expensive transition metal catalysts, oxidants, or foul
smelling thiols, an alternative strategy to generate this moiety
via a simple and environmentally benign protocol is still in
great demand.
In this context, we were intrigued by developing a new
method for S–P(O) bond formation without using any metals or
oxidants in the reaction. It is well known that sulfinic acids are
versatile compounds that are widely used in a variety of
reactions via the formation of either sulfonyl anion[6,7] or
radical reactive species[8] (Scheme 1a). In addition, Pdꢀ
a.Center for Catalytic Hydrocarbon Functionalization, Institute for Basic Science
(IBS), Daejeon, 34141, Korea.
b.Department of Chemistry, Korea Advanced Institute of Science and Technology,
Daejeon, 34141, Korea, hongorg@kaist.ac.kr
† Electronic Supplementary Informaꢀon (ESI) available: See
DOI: 10.1039/x0xx00000x
Scheme 1 Synthetic application of sulfinic acids and strategies for S-
P(O) bond formation.
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11[d]
Ph3P
i-PrOAc
trace
during the coupling reaction process. Herein, we present a
novel and powerful strategy for S–P(O) bond formation that is
enabled by the direct cross coupling of Hꢀphosphoryl
compounds and sulfinic acids under metalꢀ and oxidantꢀfree
conditions.
a
Reaction conditions: 1a (0.17 mmol), 2a (2.0 equiv), additive (1.0 equiv), and
b
c
solvent (1.0 mL) under N2 at room temperature for 24 h. isolation yield.
Reacted at 40 oC. d Sodium sulfinate was used instead of 2a
.
With the optimized reaction conditions in hand, the scope of
the reaction was studied with respect to both sulfinic acids and
Hꢀphosphoryl compounds (Table 2). The substituted
arylsulfinic acids bearing methyl, tertꢀbutyl, and methoxy on
the aryl ring reacted well with Hꢀphosphine oxide to afford the
desired coupling products in good yields (3a-3d, 3k). It is
important to note that the halo substituents including I, Br, Cl,
and F on the phenyl ring of the substrates (3e-3h) were well
tolerated under the reaction conditions, enabling further
functionalization at these positions. These results are significant
because iodide and bromide groups on aromatic rings are
typically difficult to retain in transition metalꢀcatalyzed
reactions. In a similar fashion, substrates with trifluoromethyl (ꢀ
CF3) or trifluoromethoxy (ꢀOCF3) groups, which are useful
structural motifs in many biologically active molecules, can be
employed to afford the corresponding products (3i and 3j) in
excellent yield. A bulkier 2ꢀnaphthylsulfinic acid substrate is
also effective to afford the desired product 3l in 86% yield. In
addition, aliphatic sulfinic acids, such as isopropylꢀ, benzylꢀ,
phenylethylꢀ, and cyclopropyl sulfinic acids, were also effective
producing the desired products (3m-3p) in good yield. Further
exploration demonstrated that heterocyclic sulfinic acids that
are typically incompatible with strong oxidative conditions, as
exemplified by thiophene and dihydrobenzofuran could also be
used as coupling partners (3q-3r). Next, the scope of this
transformation with respect to the P(O)ꢀH compounds was
evaluated. A range of Hꢀphosphonates, Hꢀphosphinates, and
phosphine oxide substrates (4a-4r) was determined to be
suitable reaction partners for this transformation. Therefore, the
current protocol can be used to synthesize phosphorothioate
derivatives with substituents at various positions, providing
considerable advantages in both simplicity and efficiency. In
case of Hꢀphosphonates, the addition of DBU improved the
reactivity probably because the equilibrium in phosphiteꢀ
phosphonate tautomerism shifts toward the reactive phosphite
form under basic conditions.[12]
Results and discussion
In line with our hypothesis, the feasibility of this strategy relies
on the initial coupling process of two reactants, and we
explored the coupling reaction of Hꢀphosphine oxide 1a with
sulfinic acid 2a (Table 1). To our delight, our initial
investigations revealed that 1a and 2a reacted smoothly to
afford desired product 3a in 44% yield in toluene at room
temperature, thus demonstrating that the overall process
occurred spontaneously (Table 1, entry 1). The intermediate
sulfinylphosphine oxide was not detected during the reactions,
and a significant amount of diphenylphosphinic acid was
isolated, which was likely due to diphenylphosphine oxide 1a
also acting as a reductant during the process. Therefore, we
sought an alternative set of reaction conditions that would be
capable of overcoming this problem. The experiments indicated
that the reaction efficacy was promoted by addition of
arylphosphine,[11] and the yield improved to 72% using
triphenylphosphine with only
a
negligible amount of
diphenylphosphinic acid byꢀproduct (entry 6). An excess of
sulfinic acid (2 equiv) was needed to ensure complete
conversion of 1a. After extensive screenings, the optimal
parameters were determined and involved additive free
conditions at room temperature for 24 h. Interestingly, less
toxic isopropyl acetate and tꢀbutyl acetate exhibited the best
reactivity in the solvent screening (entries 7 and 10). Notably,
further increasing the reaction temperature to 40 °C did not
provide any significant changes in the yield of the product
(Table 1, entry 8). The use of the preformed sodium sulfinate
salt of 2a as a starting material did not react with Hꢀphosphine
oxide 1a (Table 1, entry 11).
Table 1 Optimization of coupling of diphenylphosphine oxide
1a with 4-methylbenzene sulfinic acid 2a a
.
Table 2 Scope of the coupling reactions.a
Entry
Additive [1 equiv]
Solvent
Yield [%][b]
1
ꢀ
PhMe
44
42
trace
51
69
72
86
83
62
82
2
pyridine
Cy3P
PhMe
3
PhMe
4
(C6F5)3P
(4ꢀMeOPh)3P
Ph3P
PhMe
5
PhMe
6
PhMe
7
8[c]
Ph3P
i-PrOAc
i-PrOAc
MeCN
t-BuOAc
Ph3P
9
Ph3P
10
Ph3P
2 | J. Name., 2012, 00, 1-3
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O
O
O
S
O
Ph
S
Ph
S
Ph
S
O
P
O
P
P
Ph3P (1 equiv)
(-)MenO
OH
(-)MenO
P
S
R
Ph
P
H
Ph
+
Ph
i-PrOAc, 80 o
C
Br
I
Ph
CF3
Ph
(R)-1b
(Rp/Sp>99:1)
3g, 75%[c]
R
3i, 77%[c]
3h, 86%
24 h
2 (2 equiv)
(S)-5a, R = Me, 80% (Rp/Sp>99:1)
(S)-5b, R = tBu, 84% (Rp/Sp>99:1)
(S)-5c, R = OMe, 78% (Rp/Sp>99:1)
O
P
O
O
Ph
S
Ph
S
Ph
S
P
P
Ph
Ph
Ph
OMe
OCF3
3k, 94%[b]
3j, 81%[b]
3l, 86%[b]
O
S
P
O
O
Ph
Ph
S
Me
Ph
S
Ph
Ph
P
P
Ph
Ph Me
Ph
3o, 85%[b]
Scheme 2 Stereospecific coupling reaction for the formation of
P-chiral phosphorothioates.
3m, 77%[c]
3n, 86%[c]
O
P
O
O
Ph
S
Ph
S
Ph
S
S
P
P
To fully evaluate this method, different Hꢀphosphoryl
compounds were investigated. Impressively, expanding the
scope to various phosphite reactants was also possible,
Ph
3r
Ph
Ph
O
3p, 87%[c]
[c]
3q, 75%[c]
, 95%
producing the coupling product
comparable reaction conditions (Scheme 3).
(
4b-d
,
4f) under the
Scope of P(O)-H reactants:
O
4b, R = Me, 52%[e]
4c, R = Et, 65%[e]
4d, R = iPr, 67%[f]
4e, R = nBu, 61%[f]
4f, R = Ph, 61%[e]
4g, R=
O
S
P
Ph
S
RO
P
OEt
OR
Me
Me
4a, 75%[d]
O
O
O
, 60%[e]
P
S
Me
tBu
P
S
Me
tBu
4i, 84%[d]
Scheme
3
Reaction
of
phosphites
with
4-
4h, 90%[c]
4k, R = Me, 94%
4l, R = F, 96%
methylbenzenesulfinic acid.
O
P
O
4m, R = OMe, 75%
Ph
S
Me
R
P
S
Me
To obtain mechanistic information of the reaction process,
radical trapping experiments were conducted by employing 2,6ꢀ
Diꢀtertꢀbutylꢀ4ꢀmethylphenol (BHT) whether the reaction
involves radical species. In addition, a model reaction was
performed under an O2 atmosphere because O2 was used as a
radical initiator.[8] No influence of this transformation was
found, providing 3a in 71% and 77% yields, respectively,
indicating that a radical process may not be involved in the
coupling reaction (scheme 4).
4n, R = CF3, 94%
4o, R = Cl, 93%[b]
4p, R = NMe2, 82%[d]
iPr
4j, 83%[c]
2
Me
O
P
O
P
S
Me
S
Me
2
2
Me
4q, 87%[b]
4r, 88%
a Reaction conditions: 1 (1.0 equiv), 2 (2.0 equiv), and Ph3P (1.0 equiv) under N2 (1 atm)
in i-PrOAc (0.17 M) at room temperature for 24 h. Isolated yields. b Reacted at 40 oC.
c
Reacted at 60 oC. d Reacted at 80 oC. DBU (1.0 equiv) in MeCN (0.10 M) at 60 oC.
e
f
DBU (1.0 equiv) in MeCN (0.10 M) at 80 oC.
Due to the importance of optically active organophosphorus
compounds as biological active compounds and chiral
auxiliaries,[13] the stereochemistry on the reactions of
menthyl phenyl Hꢀphosphinate (Rpꢀ1b, Rp/S
R
pꢀ(–)ꢀ
p > 99/1) with aryl
sulfinic acids was investigated. To our delight, the
corresponding ꢀchiral phosphorothioates were prepared
P
Scheme 4 Control experiments.
stereospecifically with retention of configuration at the
phosphorus centers (Scheme 2). The other diastereomer was not
detected from the crude products using 1H and 31P NMR
spectroscopy. Moreover, when a diastereomeric mixture of 1c
Based on the above observations and previous reports, a
plausible mechanism is shown in Scheme 5. Initially,
tautomerization of diphenylphosphine oxide 1a, which is a soꢀ
called P(V) form, exists in equilibrium with the P(III) form
(
Rp/Sp = 52/48) was employed, 6a was obtained as a mixture of
diastereomers with the same ratio, thus demonstrating the
1a’ [12b]
formation of a sulfinyl cation, which is generated in situ by
dehydration of sulfinic acid. Then, intermediate may be
.
The reaction pathway is likely to be triggered by the
efficiency of this method for preparing optically active
phosphorothioates derivatives.
Pꢀchiral
I
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formed by nucleophilic attack of the P(III) form 1a’ on the MHz and was fully decoupled by broad band proton
sulfinyl cation. In the process, other mechanistic possibility decoupling. Mass spectral data were obtained from the KAIST
involving reactive sulfur species such as such as sulfonothioate, Basic Science Institute by using ESI method. Commercial
sulfinothioate, or disulfide, can also be conceived.[14] Finally, grade reagents and solvents were used without further
intermediate
I
undergoes subsequent reduction by purification except as indicated below.
triphenylphosphine to afford the desired product
3.
General procedure
R1R2P(O)H (1 equiv), sulfinic acid (2 equiv), and Ph3P (1
equiv) were combined in iPrOAc (1.0 mL) under nitrogen
condition in a seal tube. The reaction was stirred at room
temperature for 24 h. The mixture was monitored by TLC using
MeOH and CH2Cl2 = 1 : 20 as the mobile phase and stirred
until starting material disappeared. The mixture solvent was
removed under reduced pressure. The reaction mixture was
diluted with CH2Cl2 and the residue was extracted with aqueous
NH4Cl (3 × 30 mL). The organic layer was dried over MgSO4.
After removal of solvent, the residue was purified by flash
chromatography on silica gel to give desired product.
Scheme 5 Proposed reaction pathway.
S-p-tolyl
diphenylphosphinothioate
(3a).[4c]
From
diphenylphosphine oxide (34.2 mg, 0.169 mol), compound 3a
(
Conclusions
o
1
47.2 mg, 86%) was obtained. White solid. mp 116ꢀ118 C. H
NMR (400 MHz, Chloroformꢀ ) δ 7.90 – 7.74 (m, 4H), 7.54 –
7.36 (m, 6H), 7.30 (dd, = 8.1, 1.8 Hz, 2H), 6.98 (d, = 7.8
Hz, 2H), 2.23 (s, 3H). 13C NMR (100 MHz, Chloroformꢀ
) δ
139.1 (d, = 2.4 Hz), 135.3 (d, = 3.8 Hz), 132.7 (d, = 106.7
Hz), 132.2 (d, = 3.0 Hz), 131.6 (d, = 10.3 Hz), 129.9 (d,
1.9 Hz), 128.5 (d, = 13.1 Hz), 122.2 (d,
= 5.3 Hz), 21.1. 31
NMR (162 MHz, Chloroformꢀ
calcd. C19H17NaOPS+ [M+Na]+: 347.0630, found: 347.0637.
S-o-tolyl diphenylphosphinothioate From
(3b).[5]
diphenylphosphine oxide (34.0 mg, 0.168 mol), compound 3b
52.9 mg, 97%) was obtained. White solid. mp 72ꢀ74 oC. 1H
NMR (400 MHz, Chloroformꢀ ) δ 7.85 – 7.74 (m, 4H), 7.52 –
7.32 (m, 7H), 7.16 – 7.05 (m, 2H), 6.97 (td, = 7.4, 2.1 Hz,
1H), 2.32 (s, 3H). 13C NMR (100 MHz, Chloroformꢀ
) δ 142.7
= 3.7 Hz), 133.2, 132.1 (d, = 3.2
= 2.2 Hz), 129.1 (d,
= 2.0 Hz), 125.3 (d,
) δ 41.6.
In summary, we have developed an operationally simple
method for S–P(O) bond formation metalꢀ, oxidantꢀ, and
halogenꢀfree conditions. The high reaction efficacy was
realized by the addition of PPh3 as a reductant. The current
method is compatible with a broad range of substituents on
various substrates including halogens and heterocyclic
moieties, which are difficult to retain in transition metalꢀ or
peroxideꢀmediated reactions. The synthetic potential of this
method was further highlighted by the expeditious synthesis of
d
J
J
d
J
J
J
J
J
J
=
P
J
J
d
) δ 42.0. HRMS (ESI+) m/z
optically pure
Pꢀchiral phosphorothioates via simple
stereospecific coupling reactions. Further studies on the
application of this method to conjugation in chemical biology
are currently underway.
(
d
J
d
(d,
J
= 3.9 Hz), 136.6 (d,
J
J
Experimental
Hz), 131.3 (d,
2.6 Hz), 128.3 (d,
J
= 10.2 Hz), 130.5 (d,
J
J =
General information
J = 13.0 Hz), 126.3 (d, J
Unless stated otherwise, reactions were performed in flameꢀ
dried glassware. Analytical thin layer chromatography (TLC)
was performed on precoated silica gel 60 F254 plates and
visualization on TLC was achieved by UV light (254 and 365
nm). Flash column chromatography was undertaken on silica
J
= 5.3 Hz), 21.3. 31P NMR (162 MHz, Chloroformꢀ
d
HRMS (ESI+) m/z calcd. C19H17NaOPS+ [M+Na]+: 347.0630,
found: 347.0625.
S-phenyl
diphenylphosphine oxide (33.9 mg, 0.168 mol), compound 3c
50.1 mg, 96%) was obtained. White solid. mp 92ꢀ94 oC. 1H
NMR (400 MHz, Chloroformꢀ ) δ 7.88 – 7.76 (m, 4H), 7.54 –
7.34 (m, 8H), 7.22 – 7.11 (m, 3H). 13C NMR (100 MHz,
Chloroformꢀ ) δ 135.2 (d, = 3.9 Hz), 132.5 (d, = 107.0 Hz),
132.2 (d, = 3.0 Hz), 131.5 (d, = 10.2 Hz), 129.0 (d, = 1.8
Hz), 128.8 (d, = 2.2 Hz), 128.4 (d, = 13.2 Hz), 126.0 (d,
) δ 42.1. HRMS
diphenylphosphinothioate
(3c).[4c]
From
1
gel (400ꢀ630 mesh). H NMR was recorded on 400 MHz and
(
chemical shifts were quoted in parts per million (ppm)
referenced to the appropriate solvent peak or 0.0 ppm for
tetramethylsilane. The following abbreviations were used to
describe peak splitting patterns when appropriate: br = broad, s
= singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd
= doublet of doublet, td = doublet of triplet, ddd = doublet of
d
d
J
J
J
J
J
J
J
J =
5.2 Hz). 31P NMR (162 MHz, Chloroformꢀ
d
(ESI+) m/z calcd. C18H15NaOPS+ [M+Na]+: 333.0473, found:
333.0479.
S-(4-(tert-butyl)phenyl) diphenylphosphinothioate (3d).[5]
doublet of doublet. Coupling constants, J, were reported in
hertz unit (Hz). 13C NMR was recorded on 100 MHz and was
fully decoupled by broad band proton decoupling. Signals of
13C spectra of carbon atom adjacent to phosphorus atom of
organophosphorus compounds appeared as a doublet with
From diphenylphosphine oxide (34.0 mg,
0.168 mol),
compound 3d (59.8 mg, 97%) was obtained. White solid. mp
o
126ꢀ128 C. 1H NMR (400 MHz, Chloroformꢀ
d) δ 7.81 (ddd,
J
varied coupling constants between C and P (JCP). Chemical
shifts were reported in ppm referenced to the center line of a
triplet at 77.0 ppm of CDCl3. 31P NMR was recorded on 162
= 12.9, 8.4, 1.4 Hz, 4H), 7.49 – 7.29 (m, 8H), 7.18 (d,
J
= 8.4
Hz, 2H), 1.19 (s, 9H). 13C NMR (100 MHz, Chloroformꢀ
d) δ
4 | J. Name., 2012, 00, 1-3
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152.1 (d,
Hz), 132.1 (d,
13.1 Hz), 126.1 (d,
31.0. 31P NMR (162 MHz, Chloroformꢀ
J
= 2.5 Hz), 135.1 (d,
= 3.0 Hz), 131.5 (d,
= 1.9 Hz), 122.2 (d,
J
= 3.7 Hz), 132.7 (d,
J
= 106.7 2H), 7.47 – 7.38 (m, 6H). 13C NMR (100 MHz, Chloroformꢀ
δ 135.2 (d, = 4.0 Hz), 132.6 (d, = 3.2 Hz), 132.6, 131.6 (d,
= 32.8, 2.1 Hz), 128.7 (d, = 13.3 Hz),
= 4.1, 2.0 Hz), 125.1, 122.4. 31P NMR (162 MHz,
d)
J
J
J
= 10.3 Hz), 128.3 (d,
J
=
J
J
J
J
= 5.3 Hz), 34.4, = 10.4 Hz), 130.8 (dd,
J
J
d
) δ 42.2. HRMS (ESI+) 125.8 (dt,
J
m/z calcd. C22H23NaOPS+ [M+Na]+: 389.1099, found: Chloroformꢀ
d)
δ
42.3. HRMS (ESI+) m/z calcd.
389.1097.
C19H14F3NaOPS+ [M+Na]+: 401.0347, found: 401.0346.
S-(4-fluorophenyl) diphenylphosphinothioate (3e).[5] From
S-(4-(trifluoromethoxy)phenyl) diphenylphosphinothioate
diphenylphosphine oxide (33.6 mg, 0.166 mol), compound 3e (3j). From diphenylphosphine oxide (34.3 mg, 0.170 mol),
o
(
49.7 mg, 91%) was obtained. White solid. mp 111ꢀ113 C. 1H compound 3j (54.2 mg, 81%) was obtained. White solid. mp
NMR (400 MHz, Chloroformꢀ ) δ 7.81 (ddd, ) δ 7.84 – 7.76 (m,
= 12.9, 8.4, 1.5 69ꢀ71 oC. 1H NMR (400 MHz, Chloroformꢀ
Hz, 4H), 7.53 – 7.31 (m, 8H), 6.86 (t,
= 8.6 Hz, 2H). 13C 4H), 7.52 – 7.37 (m, 8H), 7.01 (dt, = 7.9, 1.1 Hz, 2H). 13
NMR (100 MHz, Chloroformꢀ ) δ 163.3 (dd, = 249.8, 2.5 NMR (100 MHz, Chloroformꢀ ) δ 149.8 (t, = 2.2 Hz), 136.8
Hz), 137.3 (dd, = 8.6, 3.7 Hz), 132.4 (d, = 3.1 Hz), 132.3 (d, (d, = 3.7 Hz), 132.5 (d, = 3.1 Hz), 132.0 (d, = 107.1 Hz),
= 106.9 Hz), 131.5 (d, = 10.3 Hz), 128.5 (d, = 13.2 Hz), 131.5 (d, = 10.4 Hz), 128.6 (d, = 13.2 Hz), 124.8 (d, = 5.1
= 21.9, 2.0 Hz). 31 = 258.0 Hz). 31P NMR (162 MHz,
Hz), 121.3, 120.2 (q,
= 4.5 Hz). HRMS Chloroformꢀ
42.3. HRMS (ESI+) m/z calcd.
d
J
d
J
J
C
d
J
d
J
J
J
J
J
J
J
J
J
J
J
J
121.1 (dd,
NMR (162 MHz, Chloroformꢀ
J
= 5.2, 3.4 Hz), 116.3 (dd,
J
P
J
d
) δ 42.1 (d,
J
d)
δ
(ESI+) m/z calcd. C18H14FNaOPS+ [M+Na]+: 351.0379, found: C19H14F3NaO2PS+ [M+Na]+: 417.0296, found: 417.0298.
351.0382.
S-(4-chlorophenyl) diphenylphosphinothioate (3f).[4c] From From diphenylphosphine oxide (31.7 mg,
diphenylphosphine oxide (33.8 mg, 0.167 mol), compound 3f compound 3k (50.1 mg, 94%) was obtained. White solid. mp
S-(4-methoxyphenyl) diphenylphosphinothioate (3k).[4c]
0.157 mol),
o
o
(
47.2 mg, 82%) was obtained. White solid. mp 114ꢀ116 C. 1H 150ꢀ152 C. 1H NMR (400 MHz, Chloroformꢀ
NMR (400 MHz, Chloroformꢀ ) δ 7.82 (ddd, = 12.9, 8.4, 1.4 = 12.8, 8.2, 1.4 Hz, 4H), 7.49 – 7.36 (m, 6H), 7.30 (dd,
Hz, 4H), 7.54 – 7.47 (m, 2H), 7.43 (ddd,
= 8.5, 6.5, 3.7 Hz, 1.8 Hz, 2H), 6.72 – 6.66 (m, 2H), 3.68 (s, 3H). 13C NMR (100
4H), 7.35 (dd, = 8.5, 1.7 Hz, 2H), 7.15 (d, = 8.5 Hz, 2H). MHz, Chloroformꢀ ) δ 160.3 (d, = 2.2 Hz), 136.9 (d, = 3.5
13C NMR (100 MHz, Chloroformꢀ
) δ 136.5 (d, = 3.9 Hz), Hz), 132.5 (d, = 106.2 Hz), 132.1 (d, = 3.0 Hz), 131.5 (d,
135.5 (d, = 2.7 Hz), 132.5 (d, = 3.0 Hz), 132.2 (d, = 107.2 = 10.1 Hz), 128.4 (d, = 13.1 Hz), 115.9 (d,
Hz), 131.6 (d, = 10.3 Hz), 129.3 (d, = 1.8 Hz), 128.6 (d, (d,
= 1.9 Hz), 55.1. 31P NMR (162 MHz, Chloroformꢀ
13.2 Hz), 124.7 (d,
Chloroformꢀ
C18H14ClNaOPS+ [M+Na]+: 367.0084, found: 367.0091.
S-(4-bromophenyl) diphenylphosphinothioate
From diphenylphosphine oxide (33.5 mg,
compound 3g (48.2 mg, 75%) was obtained. White solid. mp NMR (400 MHz, Chloroformꢀ
d) δ 7.81 (ddd,
J
d
J
J
= 8.8,
J
J
J
d
J
J
d
J
J
J
J
J
J
J
J
J = 5.2 Hz), 114.7
J
J
J
=
J
d
) δ
J
= 5.1 Hz). 31P NMR (162 MHz, 41.9. HRMS (ESI+) m/z calcd. C19H17NaO2PS+ [M+Na]+:
d
)
δ
42.1. HRMS (ESI+) m/z calcd. 363.0579, found: 363.0585.
S-(naphthalen-2-yl) diphenylphosphinothioate (3l).[5] From
(3g).[5] diphenylphosphine oxide (33.8 mg, 0.167 mol), compound 3l
o
0.166 mol),
(
51.9 mg, 86%) was obtained. White solid. mp 128ꢀ130 C. 1H
d
) δ 7.98 (t,
= 12.9, 8.3, 1.4 Hz, 4H), 7.74 – 7.63 (m, 2H), 7.63 (d,
= 7.2, 1.6 Hz, 2H), 7.43 = 8.6 Hz, 1H), 7.51 – 7.34 (m, 9H). 13C NMR (100 MHz,
= 8.6, 6.7, 3.8 Hz, 4H), 7.29 (d, Chloroformꢀ ) δ 135.3 (d, = 5.0 Hz), 133.4 (d, = 1.8 Hz),
= 1.3 Hz, 4H). 13
NMR (100 MHz, Chloroformꢀ ) δ 136.7 (d, = 3.9 Hz), 132.7, 132.9 (d, = 1.6 Hz), 132.5 (d, = 106.8 Hz), 132.2 (d, = 3.0
132.5 (d, = 3.0 Hz), 132.2 (d, = 1.9 Hz), 131.5 (d, = 10.3 Hz), 131.5 (d, = 3.1 Hz), 128.6 (d,
Hz), 128.6 (d, = 13.2 Hz), 125.3 (d, = 5.2 Hz), 123.7 (d,
2.8 Hz). 31P NMR (162 MHz, Chloroformꢀ
) δ 42.1. HRMS 123.4 (d,
(ESI+) m/z calcd. C18H14BrNaOPS+ [M+Na]+: 410.9579, found: 42.1. HRMS (ESI+) m/z calcd. C22H17NaOPS+ [M+Na]+:
J = 2.1 Hz, 1H), 7.86
106ꢀ108 C. 1H NMR (400 MHz, Chloroformꢀ
= 13.0, 8.3, 1.4 Hz, 4H), 7.50 (td,
(ddd,
d
) δ 7.81 (ddd,
J
(ddd,
J
J
o
J
J
J
C
d
J
J
d
J
J
J
J
J
J
J
J
= 10.3 Hz), 131.4 (d,
J
J =
J
J
J
=
1.4 Hz), 128.4 (d,
J
= 13.2 Hz), 127.7, 127.5, 126.8, 126.3,
) δ
d
J
= 5.5 Hz). 31P NMR (162 MHz, Chloroformꢀ
d
410.9567.
383.0630, found: 383.0636.
S-isopropyl diphenylphosphinothioate (3m).[4c] From
S-(4-iodophenyl) diphenylphosphinothioate (3h). From
diphenylphosphine oxide (34.0 mg, 0.168 mol), compound 3h diphenylphosphine oxide (33.8 mg, 0.167 mol), compound 3m
o
o
(
63.1 mg, 86%) was obtained. White solid. mp 102ꢀ104 C. 1H
NMR (400 MHz, Chloroformꢀ ) δ 7.86 – 7.73 (m, 4H), 7.52 – NMR (400 MHz, Chloroformꢀ
7.35 (m, 8H), 7.14 (dd,
= 8.4, 1.7 Hz, 2H). 13C NMR (100 Hz, 4H), 7.52 – 7.40 (m, 6H), 3.40 (dhept,
MHz, Chloroformꢀ ) δ 138.1 (d, = 1.7 Hz), 136.7 (d, = 3.9 1.32 (d,
= 6.8 Hz, 6H). 13C NMR (100 MHz, Chloroformꢀ
Hz), 132.6, 132.4 (d, = 3.1 Hz), 131.5 (d, = 10.2 Hz), 128.5 133.9 (d,
(d, = 13.2 Hz), 126.2 (d, = 5.2 Hz), 95.5 (d, 10.3 Hz), 128.5 (d,
= 2.9 Hz). 31
NMR (162 MHz, Chloroformꢀ
calcd. C18H14INaOPS+ [M+Na]+: 458.9440, found: 458.9449.
S-(4-(trifluoromethyl)phenyl) diphenylphosphinothioate 299.0629.
(3i). From diphenylphosphine oxide (32.2 mg, 0.159 mol), S-benzyl
compound 3i (46.3 mg, 77%) was obtained. White solid. mp diphenylphosphine oxide (33.9 mg, 0.168 mol), compound 3n
98ꢀ100 oC. 1H NMR (400 MHz, Chloroformꢀ 46.8 mg, 86%) was obtained. White solid. mp 87ꢀ89 oC. 1H
) δ 7.83 (ddd,
13.0, 8.3, 1.4 Hz, 4H), 7.57 (d, = 8.1 Hz, 2H), 7.54 – 7.48 (m, NMR (400 MHz, Chloroformꢀ
(
35.6 mg, 77%) was obtained. White solid. mp 106ꢀ108 C. 1H
) δ 7.85 (ddd, = 12.9, 8.2, 1.5
= 9.8, 6.8 Hz, 1H),
) δ
d
d
J
J
J
d
J
J
J
d
J
J
J
= 107.0 Hz), 132.1 (d,
J
= 3.0 Hz), 131.4 (d,
= 13.1 Hz), 36.9 (d, J = 2.5 Hz), 25.8 (d,
) δ 42.3. HRMS
(ESI+) m/z calcd. C15H17NaOPS+ [M+Na]+: 299.0630, found:
J
=
J
J
J
J
P
J
d
) δ 42.0. HRMS (ESI+) m/z = 4.6 Hz). 31P NMR (162 MHz, Chloroformꢀ
d
diphenylphosphinothioate
(3n).[4c]
From
d
J
=
(
J
d
) δ 7.88 – 7.81 (m, 4H), 7.53 –
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ARTICLE
Journal Name
7.47 (m, 2H), 7.46 – 7.40 (m, 4H), 7.21 – 7.13 (m, 5H), 4.00 (d, MHz, Chloroformꢀ
= 9.1 Hz, 2H). 13C NMR (100 MHz, Chloroformꢀ
(d, = 5.5 Hz), 133.0 (d, = 106.9 Hz), 132.3 (d,
131.5 (d, = 10.5 Hz), 129.0, 128.7, 128.5 (d,
127.4, 33.1 (d,
= 2.2 Hz). 31P NMR (162 MHz, Chloroformꢀ
δ 43.4. HRMS (ESI+) m/z calcd. C19H17NaOPS+ [M+Na]+: 3.1 Hz), 131.4 (d,
347.0630, found: 347.0633. 128.1 (d, = 14.9 Hz), 122.8 (d,
S-phenethyl diphenylphosphinothioate From Hz), 21.1, 16.3 (d,
= 6.7 Hz). 31P NMR (162 MHz,
diphenylphosphine oxide (33.9 mg, 0.168 mol), compound 3o Chloroformꢀ
42.4. HRMS (ESI+) m/z calcd.
48.2 mg, 85%) was obtained. Colorless oil. H NMR (400 C15H17NaO2PS+ [M+Na]+: 315.0579, found: 315.0581.
MHz, Chloroformꢀ ) δ 7.94 – 7.86 (m, 4H), 7.58 – 7.45 (m,
O,O-dimethyl S-p-tolyl phosphorothioate (4b).[3c] From
6H), 7.31 – 7.25 (m, 2H), 7.24 – 7.19 (m, 1H), 7.15 – 7.10 (m, dimethyl phosphonate (10.9 mg, 0.0986 mol), compound 4b
2H), 3.11 – 3.03 (m, 2H), 2.98 – 2.92 (m, 2H). 13C NMR (100
11.9 mg, 52%) was obtained. From trimethyl phosphite (21.0
MHz, Chloroformꢀ ) δ 139.3, 133.2 (d, = 107.1 Hz), 132.2 (d, mg, 0.169 mol), compound 4b (21.6 mg, 55%) was obtained.
= 3.0 Hz), 131.4 (d, = 10.4 Hz), 128.7, 128.5 (d,
Hz), 128.4, 126.5, 36.9 (d, = 4.7 Hz), 30.3 (d,
= 2.2 Hz). 31
NMR (162 MHz, Chloroformꢀ
) δ 43.8. HRMS (ESI+) m/z Hz, 6H), 2.33 (d,
calcd. C20H19NaOPS+ [M+Na]+: 361.0786, found: 361.0789.
Chloroformꢀ ) δ 139.5 (d,
S-cyclopropyl diphenylphosphinothioate (3p). From 130.3 (d, = 2.7 Hz), 122.3 (d,
diphenylphosphine oxide (33.7 mg, 0.167 mol), compound 3p Hz), 21.2. 31P NMR (243 MHz, Chloroformꢀ
39.8 mg, 87%) was obtained. White solid. mp 78ꢀ80 oC. 1H (ESI+) m/z calcd. C9H13NaO3PS+ [M+Na]+: 255.0215, found:
NMR (400 MHz, Chloroformꢀ ) δ 7.90 – 7.82 (m, 4H), 7.54 – 255.0217.
7.41 (m, 6H), 1.92 (ttd, = 7.6, 4.4, 2.1 Hz, 1H), 0.81 – 0.72
O,O-diethyl S-(p-tolyl) phosphorothioate (4c).[3c] From
(m, 2H), 0.68 – 0.60 (m, 2H). 13C NMR (100 MHz, dimethyl phosphonate (13.7 mg, 0.0994 mol), compound 4c
Chloroformꢀ ) δ 133.4 (d, = 105.7 Hz), 132.2 (d, = 3.0 Hz), 16.8 mg, 65%) was obtained. From triethyl phosphite (28.8
131.4 (d, = 10.3 Hz), 128.5 (d, = 12.9 Hz), 9.3 (d, = 2.9 mg, 0.173 mol), compound 4c (27.5 mg, 61%) was obtained.
Hz), 7.6 (d, ) δ 7.40 (dd,
= 5.3 Hz). 31P NMR (162 MHz, Chloroformꢀ ) δ Colorless oil. 1H NMR (600 MHz, Chloroformꢀ
43.1. HRMS (ESI+) m/z calcd. C15H15NaOPS+ [M+Na]+: = 8.2, 2.1 Hz, 2H), 7.12 (d,
= 7.8 Hz, 2H), 4.21 – 4.09 (m,
297.0473, found: 297.0475. 4H), 2.30 (d, = 2.1 Hz, 3H), 1.27 (dd, = 7.4, 6.5 Hz, 6H).
S-(thiophen-2-yl) diphenylphosphinothioate (3q). From 13C NMR (150 MHz, Chloroformꢀ
) δ 139.2 (d, = 3.2 Hz),
diphenylphosphine oxide (33.7 mg, 0.167 mol), compound 3q 134.5 (d, = 4.9 Hz), 130.1 (d, = 2.3 Hz), 122.7 (d, = 7.3
39.5 mg, 75%) was obtained. White solid. mp 86ꢀ88 oC. 1H Hz), 63.9 (d, = 7.1 Hz). 31P NMR
= 6.0 Hz), 21.1, 15.9 (d,
d) δ 7.67 – 7.59 (m, 2H), 7.50 – 7.43 (m,
J
d
) δ 136.8 1H), 7.38 – 7.30 (m, 2H), 7.13 (dd,
= 3.0 Hz), (d, = 7.6 Hz, 2H), 4.40 – 4.22 (m, 2H), 2.26 (d,
= 2.7 Hz), 3H), 1.36 (t,
= 7.1 Hz, 3H). 13C NMR (100 MHz, Chloroformꢀ
) δ 139.1 (d, = 3.1 Hz), 135.3 (d, = 4.1 Hz), 132.3 (d,
= 10.5 Hz), 130.8, 129.9 (d, = 2.4 Hz),
= 5.8 Hz), 62.3 (d, = 6.9
J
= 8.2, 2.0 Hz, 2H), 6.98
J
J
J
J
J
J
= 1.9 Hz,
J
J
J
d)
d
J
J
J =
J
J
J
J
J
(3o).
J
d)
δ
1
(
d
(
d
J
J
J
J
= 1.5 Colorless oil. 1H NMR (600 MHz, Chloroformꢀ
= 8.3, 2.1 Hz, 2H), 7.14 (d, = 8.1 Hz, 2H), 3.79 (d,
d
) δ 7.42 (dd,
J
J
J
P
J
J
= 12.6
d
J
= 2.1 Hz, 3H). 13C NMR (150 MHz,
d
J
= 3.2 Hz), 134.6 (d,
= 7.5 Hz), 54.2 (d,
) δ 26.6. HRMS
J
= 5.1 Hz),
J
J
J
= 6.2
d
(
d
J
d
J
J
(
J
J
J
J
d
d
J
J
J
J
d
J
J
J
J
(
J
J
NMR (400 MHz, Chloroformꢀ
d
) δ 7.89 – 7.80 (m, 4H), 7.56 – (243 MHz, Chloroformꢀ
d
) δ 23.3. HRMS (ESI+) m/z calcd.
7.50 (m, 2H), 7.45 (tdd,
5.4, 2.1, 1.2 Hz, 1H), 7.11 (ddd,
(dd,
= 5.4, 3.6 Hz, 1H). 13C NMR (100 MHz, Chloroformꢀ
136.9 (d, = 4.7 Hz), 132.5 (d, = 3.1 Hz), 131.8 (d, = 10.3
Hz), 131.7 (d, = 105.9 Hz), 131.3 (d, = 3.2 Hz), 128.6 (d,
= 13.2 Hz), 127.8 (d, = 2.5 Hz), 122.0 (d,
= 5.8 Hz). 31
J
= 8.3, 3.3, 1.3 Hz, 4H), 7.28 (ddd,
J
=
C11H17NaO3PS+ [M+Na]+: 283.0528, found: 283.0528.
J
= 3.8, 2.6, 1.3 Hz, 1H), 6.89
O,O-diisopropyl S-p-tolyl phosphorothioate (4d).[3c] From
J
d
) δ diisopropyl phosphonate (17.1 mg, 0.103 mol), compound 4d
19.8 mg, 67%) was obtained. From triisopropyl phosphite
(36.0 mg, 0.173 mol), compound 4d (33.4 mg, 67%) was
obtained. Colorless oil. 1H NMR (400 MHz, Chloroformꢀ
) δ
= 7.9, 0.7 Hz, 2H),
= 1.7 Hz, 3H), 1.27
J
J
J
(
J
J
J
P
J
J
d
NMR (162 MHz, Chloroformꢀ
calcd. C16H13NaOPS2+ [M+Na]+: 339.0038, found: 339.0039.
d
) δ 42.3. HRMS (ESI+) m/z 7.45 (dd,
J
= 8.2, 2.1 Hz, 2H), 7.11 (dq,
J
J
4.73 (dhept, = 8.7, 6.2 Hz, 2H), 2.31 (d,
J
S-(2,3-dihydrobenzofuran-5-yl) diphenylphosphinothioate (dd,
J
= 26.0, 6.1 Hz, 12H). 13C NMR (150 MHz, Chloroformꢀ
(3r). From diphenylphosphine oxide (35.3 mg, 0.174 mol),
d
) δ 138.9 (d,
J
= 2.9 Hz), 134.3 (d,
= 7.1 Hz), 73.2 (d,
) δ 7.86 – 7.77 = 50.6, 4.9 Hz), 21.2. 31P NMR (243 MHz, Chloroformꢀ
(m, 4H), 7.53 – 7.45 (m, 2H), 7.45 – 7.38 (m, 4H), 7.27 (t,
1.6 Hz, 1H), 7.08 – 7.02 (m, 1H), 6.55 (d, = 8.3 Hz, 1H), 4.49 311.0841, found: 311.0847.
(t, = 8.7 Hz, 2H), 3.08 (t,
= 8.7 Hz, 2H). 13C NMR (100 O,O-dibutyl S-p-tolyl phosphorothioate (4e).[3c] From
MHz, Chloroformꢀ ) δ 161.2 (d, = 2.3 Hz), 135.8 (d, = 3.8 diphenylphosphine oxide (19.3 mg, 0.0996 mol), compound 4e
Hz), 133.2, 132.6 (d, = 3.2 Hz), 132.2 (d, = 3.2 Hz), 131.6
(d, = 10.2 Hz), 128.5 (d, = 13.1 Hz), 128.4 (d, = 1.8 Hz), MHz, Chloroformꢀ
115.1 (d, = 5.3 Hz), 110.0 (d, = 7.9, 0.7 Hz, 2H), 4.16 – 4.01 (m, 4H), 2.32 (d,
= 2.0 Hz), 71.6, 29.4. 31
NMR (162 MHz, Chloroformꢀ
) δ 41.9. HRMS (ESI+) m/z 3H), 1.65 – 1.56 (m, 4H), 1.39 – 1.28 (m, 4H), 0.88 (t,
calcd. C20H17NaO2PS+ [M+Na]+: 375.0579, found: 375.0579. Hz, 6H). 13C NMR (150 MHz, Chloroformꢀ
) δ 139.2 (d,
O-ethyl S-(p-tolyl) phenylphosphonothioate (4a).[3b] From 3.0 Hz), 134.6 (d,
= 2.4 Hz), 122.9 (d,
ethyl phenylphosphinate (23.0 mg, 0.136 mol), compound 3e = 7.4 Hz), 67.7 (d,
J
= 5.3 Hz), 130.0 (d,
J
=
J
compound 3r (56.1 mg, 91%) was obtained. White solid. mp 2.2 Hz), 123.5 (d,
J
J
= 6.8 Hz), 23.7 (dd,
o
137ꢀ139 C. 1H NMR (400 MHz, Chloroformꢀ
d
d
) δ
J
=
20.8. HRMS (ESI+) m/z calcd. C13H21NaO3PS+ [M+Na]+:
J
J
J
d
J
J
1
J
J
(
19.2 mg, 61%) was obtained. Colorless oil. H NMR (400
) δ 7.42 (dd, = 8.3, 2.1 Hz, 2H), 7.12 (dq,
= 2.1 Hz,
= 7.4
J
J
J
d
J
J
J
P
J
J
d
J
d
J
=
J
J
J
= 4.9 Hz), 130.1 (d,
= 6.5 Hz), 32.1 (d,
29.7 mg, 75%.) was obtained. Colorless oil. H NMR (400 13.6. 31P NMR (162 MHz, Chloroformꢀ
J
J
= 7.0 Hz), 21.2, 18.7,
1
(
d
) δ 24.0. HRMS (ESI+)
6 | J. Name., 2012, 00, 1-3
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m/z calcd. C15H25NaO3PS+ [M+Na]+: 339.1154, found: NMR (400 MHz, Chloroformꢀ
339.1159.
O,O-diphenyl S-p-tolyl phosphorothioate (4f).[4a] From 2.35 – 2.18 (m, 4H), 1.18 (dddd,
diphenyl phosphonate (24.5 mg, 0.105 mol), compound 4f 6H). 13C NMR (100 MHz, Chloroformꢀ
22.7 mg, 61%) was obtained. From triphenyl phosphite (47.9 Hz), 135.3 (d, = 3.5 Hz), 131.9 (d, = 9.3 Hz), 131.9 (d,
mg, 0.155 mol), compound 4f (35.8 mg, 65%) was obtained. 2.9 Hz), 130.9 (d, = 95.2 Hz), 129.8 (d, = 1.7 Hz), 128.2 (d,
= 12.2 Hz), 121.9 (d, = 5.2 Hz), 32.1 (d, = 71.1 Hz), 21.1,
= 74.2, 2.8 Hz). 31P NMR (162 MHz, Chloroformꢀ
d
) δ 7.78 – 7.68 (m, 2H), 7.50 –
7.34 (m, 3H), 7.32 – 7.25 (m, 2H), 6.98 (d,
= 60.4, 19.1, 7.1, 1.5 Hz,
) δ 138.9 (d, = 2.2
J = 7.8 Hz, 2H),
J
d
J
(
J
J
J =
J
J
Colorless oil. 1H NMR (400 MHz, Chloroformꢀ
(m, 6H), 7.22 – 7.16 (m, 6H), 7.15 – 7.10 (m, 2H), 2.34 (d,
2.3 Hz, 3H). 13C NMR (100 MHz, Chloroformꢀ
) δ 150.4 (d,
= 8.3 Hz), 140.0 (d, = 3.4 Hz), 135.3 (d,
= 2.9 Hz), 129.7, 125.5 (d, = 1.5 Hz), 121.2 (d,
d
) δ 7.38 – 7.29
J
J
J
J
=
16.1 (dd,
J
d
)
d
J
δ 59.3. HRMS (ESI+) m/z calcd. C16H19NaOPS+ [M+Na]+:
J
J = 5.3 Hz), 130.3 (d, 313.0786, found: 313.0788.
J
J
J
= 7.8 Hz),
S-(p-tolyl) di-p-tolylphosphinothioate (4k).[5] From diꢀpꢀ
120.5 (d,
Chloroformꢀ
J
= 5.1 Hz), 21.2 (d,
J
= 1.3 Hz). 31P NMR (243 MHz, tolylphosphine oxide (38.8 mg, 0.169 mol), compound 4k
1
d
)
δ
15.2. HRMS (ESI+) m/z calcd.
(
55.8 mg, 94%) was obtained. Colorless oil. H NMR (400
C19H17NaO3PS+ [M+Na]+: 379.0528, found: 379.0524.
MHz, Chloroformꢀ
d
) δ 7.73 – 7.66 (m, 4H), 7.31 (dd,
= 8.1, 3.4 Hz, 4H), 6.97 (d, = 7.9 Hz,
= 1.4 Hz, 3H). 13C NMR (100
) δ 142.6 (d, = 3.1 Hz), 138.8 (d, = 2.3
= 3.8 Hz), 131.5 (d, = 10.6 Hz), 130.2, 129.8
J = 8.2,
5,5-dimethyl-2-(p-tolylthio)-1,3,2-dioxaphosphinane
2- 1.7 Hz, 2H), 7.20 (dd,
J
J
oxide (4g). From 5,5ꢀdimethylꢀ1,3,2ꢀdioxaphosphinane 2ꢀoxide 2H), 2.34 (s, 6H), 2.22 (d,
(15.4 mg, 0.103 mol), compound 4g (16.8 mg, 60%) was MHz, Chloroformꢀ
J
d
J
J
obtained. White solid. mp 103ꢀ105 oC. H NMR (600 MHz, Hz), 135.1 (d,
Chloroformꢀ ) δ 7.49 (dd, = 8.3, 2.1 Hz, 2H), 7.14 (d, = 7.9 (d, = 1.8 Hz), 129.1 (d,
Hz, 2H), 4.18 (dd, = 10.8, 3.7 Hz, 2H), 3.90 (ddt, = 23.8, 21.5 (d,
11.3, 1.6 Hz, 2H), 2.32 (d,
= 2.0 Hz, 3H), 1.25 (s, 3H), 0.85 δ 42.3. HRMS (ESI+) m/z calcd. C21H21NaOPS+ [M+Na]+:
(s, 3H). 13C NMR (150 MHz, Chloroformꢀ
) δ 139.3 (d, = 2.9 375.0943, found: 375.0948.
Hz), 134.5 (d, = 5.1 Hz), 130.1 (d, = 2.6 Hz), 120.8 (d,
S-(p-tolyl) bis(4-fluorophenyl)phosphinothioate (4l).[5]
6.5 Hz), 78.0 (d, = 7.1 Hz), 32.3 (d,
20.2. 31P NMR (243 MHz, Chloroformꢀ
J
J
1
d
J
J
J
J
= 13.5 Hz), 122.7 (d, J = 5.2 Hz),
J
J
J d)
= 1.4 Hz), 21.1. 31P NMR (162 MHz, Chloroformꢀ
J
d
J
J
J
J =
J
J
= 6.9 Hz), 21.8, 21.0, From bis(4ꢀfluorophenyl)phosphine oxide (39.8 mg, 0.167
d
) δ 15.2. HRMS (ESI+) mol), compound 4l (57.7 mg, 96%) was obtained. White solid.
m/z calcd. C12H17NaO3PS+ [M+Na]+: 295.0528, found: mp 102ꢀ104 C. 1H NMR (400 MHz, Chloroformꢀ
d
) δ 7.84 –
= 8.2, 1.8 Hz, 2H), 7.09 (ddd, = 8.7,
= 7.9 Hz, 2H), 2.22 (d, = 1.5 Hz,
) δ 165.1 (dd,
= 2.5 Hz), 135.2 (d, = 3.9 Hz),
= 11.8, 8.9 Hz), 130.0 (d, = 2.0 Hz), 128.4 (dd,
= 7.9, = 110.8, 3.3 Hz), 121.8 (d, = 5.3 Hz), 115.9 (dd, = 21.6,
= 8.4, 7.5, 1.4 Hz, 1H), 7.43 (tdd, ) δ 39.7.
14.4 Hz), 21.1. 31P NMR (162 MHz, Chloroformꢀ
7.5, 3.6, 1.0 Hz, 1H), 7.31 – 7.26 (m, 1H), 7.16 – 7.09 (m, 2H), HRMS (ESI+) m/z calcd. C19H15F2NaOPS+ [M+Na]+: 383.0441,
7.05 (dd, = 8.2, 2.2 Hz, 2H), 6.82 (d, = 8.0 Hz, 2H), 2.17 (d, found: 383.0444.
= 2.1 Hz, 3H). 13C NMR (100 MHz, Chloroformꢀ
) δ 150.4 S-(p-tolyl) bis(4-methoxyphenyl)phosphinothioate (4m).
(d, = 9.6 Hz), 139.6 (d, = 3.3 Hz), 136.2 (d, = 7.3 Hz), From bis(4ꢀmethoxyphenyl)phosphine oxide (28.7 mg, 0.109
135.8 (d, = 4.2 Hz), 133.6 (d, = 2.6 Hz), 130.6 (d, = 10.2 mol), compound 4m (31.5 mg, 75%) was obtained. White solid.
Hz), 130.3, 129.7 (d, ) δ 7.76 – 7.69
= 14.9 Hz), 124.8 mp 87ꢀ89 oC. 1H NMR (400 MHz, Chloroformꢀ
= 11.4 Hz), 121.7 (m, 4H), 7.29 (dd, = 8.2, 1.7 Hz, 2H), 6.97 (d, = 7.9 Hz,
= 6.3 Hz), 119.9 (d, = 7.1 Hz), 2H), 6.90 (dd, = 8.9, 2.7 Hz, 4H), 3.79 (s, 6H), 2.22 (s, 3H).
) δ 35.0. HRMS (ESI+) 13C NMR (100 MHz, Chloroformꢀ
) δ 162.6 (d, = 3.1 Hz),
= 2.4 Hz), 135.1 (d, = 3.8 Hz), 133.5 (d, = 11.8
Hz), 129.8 (d, = 1.8 Hz), 124.1 (d, = 114.4 Hz), 123.0 (d,
S-(p-tolyl) di-tert-butylphosphinothioate (4i). From diꢀtertꢀ = 5.2 Hz), 113.9 (d,
= 14.3 Hz), 55.3, 21.1. 31P NMR (162
butylphosphine oxide (27.7 mg, 0.171 mol), compound 4i MHz, Chloroformꢀ
42.0. HRMS (ESI+) m/z calcd.
40.7 mg, 84%) was obtained. White solid. mp 55ꢀ57 oC. 1H C21H21NaO3PS+ [M+Na]+: 407.0841, found: 407.0841.
o
295.0527.
7.76 (m, 4H), 7.27 (dd,
J
J
6-(p-tolylthio)dibenzo[c,e][1,2]oxaphosphinine
6-oxide 6.7, 2.6 Hz, 4H), 6.99 (d,
J
J
(4h). From dibenzo[c,e][1,2]oxaphosphinine 6ꢀoxide (36.8 mg, 3H). 13C NMR (100 MHz, Chloroformꢀ
d
J =
0.170 mol), compound 4h (51.9 mg, 90%) was obtained. 254.4, 3.5 Hz), 139.4 (d,
Colorless oil. 1H NMR (400 MHz, Chloroformꢀ
) δ 7.87 (ddd, 134.1 (dd,
= 14.6, 7.6, 1.4 Hz, 1H), 7.79 – 7.74 (m, 1H), 7.66 (dd,
1.6 Hz, 1H), 7.61 (ddt,
J
J
d
J
J
J
J
J
J
J
J
J
=
d
J
J
J
d
J
J
J
J
J
J
J
= 2.7 Hz), 128.3 (d,
J
d
(d,
(d,
J
J
= 133.8 Hz), 124.8, 124.3, 123.1 (d,
= 11.5 Hz), 120.3 (d,
J
J
J
J
J
J
21.0. 31P NMR (162 MHz, Chloroformꢀ
d
d
J
m/z calcd. C19H15NaO2PS+ [M+Na]+: 361.0423, found: 138.8 (d,
361.0424.
J
J
J
J
J
J
J
d) δ
(
NMR (400 MHz, Chloroformꢀ
2H), 7.08 (d, = 8.0 Hz, 2H), 2.29 (s, 3H), 1.31 (d,
18H). 13C NMR (100 MHz, Chloroformꢀ
) δ 138.1 (d,
Hz), 135.4 (d, = 2.9 Hz), 129.6, 124.7 (d,
= 5.0 Hz), 41.1 (d, obtained. White solid. mp 139ꢀ141 oC. H NMR (400 MHz,
= 54.8 Hz), 26.9, 21.1. 31P NMR (162 MHz, Chloroformꢀ
) δ Chloroformꢀ ) δ 7.99 – 7.92 (m, 4H), 7.70 (dd, = 8.3, 2.9 Hz,
81.0. HRMS (ESI+) m/z calcd. C15H25NaOPS+ [M+Na]+: 4H), 7.30 (dd,
= 8.2, 1.8 Hz, 2H), 7.02 (d, = 8.0 Hz, 2H),
307.1256, found: 307.1253. 2.26 (d, ) δ
= 1.6 Hz, 3H). 13C NMR (100 MHz, Chloroformꢀ
S-(p-tolyl) isopropyl(phenyl)phosphinothioate (4j). From 140.0 (d, = 2.6 Hz), 136.4 (d, = 104.6 Hz), 135.4 (d, = 4.0
= 32.9, 3.1 Hz), 132.0 (d, = 10.4 Hz), 130.3
= 2.1 Hz), 125.6 (dq, = 13.3, 3.7 Hz), 123.4 (q, = 272.9
d
) δ 7.45 (dd,
J
= 8.2, 1.2 Hz,
S-(p-tolyl) bis(4-(trifluoromethyl)phenyl)phosphinothioate
J
J
= 15.5 Hz, (4n). From bis(4ꢀ(trifluoromethyl)phenyl)phosphine oxide
d
J = 1.6 (34.5 mg, 0.102 mol), compound 4n (44.1 mg, 94%) was
1
J
J
J
d
d
J
J
J
J
d
J
J
J
isopropyl(phenyl)phosphine oxide (27.8 mg, 0.163 mol), Hz), 134.3 (dd,
J
J
compound 4j (39.8 mg, 83%) was obtained. Colorless oil. 1H (d,
J
J
J
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Hz), 120.6 (d,
J
δ
= 5.4 Hz), 21.1. 31P NMR (162 MHz, 7.42 (m, 1H), 7.39 – 7.31 (m, 2H), 7.22 (dd,
38.3. HRMS (ESI+) m/z calcd. 2H), 7.00 – 6.96 (m, 2H), 4.48 (tdd,
= 10.7, 8.5, 4.5 Hz, 1H),
2.25 (d, = 1.9 Hz, 3H), 2.23 – 2.08 (m, 2H), 1.69 – 1.59 (m,
S-(p-tolyl) bis(4-chlorophenyl)phosphinothioate (4o).[5] 2H), 1.41 (dddd,
= 14.7, 10.6, 6.0, 3.2 Hz, 2H), 1.14 (td,
From bis(4ꢀchlorophenyl)phosphine oxide (46.0 mg, 0.170 12.2, 10.8 Hz, 1H), 1.08 – 0.96 (m, 1H), 0.92 (d, = 7.0 Hz,
mol), compound 4o (62.2 mg, 93%) was obtained. White solid. 3H), 0.84 (dd,
= 13.2, 6.7 Hz, 7H). 13C NMR (100 MHz,
mp 125ꢀ127 oC. 1H NMR (400 MHz, Chloroformꢀ
) δ 7.72 (dd, Chloroformꢀ ) δ 138.9 (d, = 2.9 Hz), 135.3 (d, = 4.1 Hz),
= 12.3, 8.1 Hz, 4H), 7.43 – 7.34 (m, 4H), 7.28 (d, = 7.8 Hz, 133.3 (d, = 149.2 Hz), 132.1 (d, = 3.2 Hz), 131.4 (d,
= 7.8 Hz, 2H), 2.23 (s, 3H). 13C NMR (100 10.6 Hz), 129.8 (d,
= 2.4 Hz), 128.0 (d, = 14.9 Hz), 122.8
) δ 139.5 (d, = 2.5 Hz), 139.0 (d, = 3.7 (d, = 5.1 Hz), 79.6 (d, = 8.4 Hz), 48.7 (d, = 6.9 Hz), 43.4,
= 3.8 Hz), 132.8 (d, = 11.1 Hz), 130.8 (d, 34.0, 31.6, 25.6, 22.9, 21.8, 21.1 (d,
= 3.3 Hz), 15.9. 31P NMR
= 13.8 Hz), 121.4 (162 MHz, Chloroformꢀ
) δ 40.5. HRMS (ESI+) m/z calcd.
) δ C23H31NaO2PS+ [M+Na]+: 425.1675, found: 425.1671.
S-(4-(tert-butyl)phenyl) O-((1R,2S,5R)-2-isopropyl-5-
methylcyclohexyl) (S)-phenylphosphonothioate (5b).[3a]
J = 8.2, 2.0 Hz,
Chloroformꢀ
d
)
J
C21H15F6NaOPS+ [M+Na]+: 483.0378, found: 483.0379.
J
J
J =
J
J
d
d
J
J
J
J
J
J
J =
2H), 7.00 (d,
J
J
J
MHz, Chloroformꢀ
Hz), 135.2 (d,
108.9 Hz), 130.1 (d,
(d,
d
J
J
J
J
J
J
J
J
=
J
J
= 2.0 Hz), 128.9 (d,
J
d
J
= 5.2 Hz), 21.1. 31P NMR (162 MHz, Chloroformꢀ
d
39.6. HRMS (ESI+) m/z calcd. C19H15Cl2NaOPS+ [M+Na]+:
414.9850, found: 414.9854.
S-(p-tolyl) bis(4-(dimethylamino)phenyl)phosphinothioate From 2ꢀisopropylꢀ5ꢀmethylcyclohexyl phenylphosphinate (42.5
(4p). From bis(4ꢀ(dimethylamino)phenyl)phosphine oxide (28.8 mg, 0.152 mol), compound 5b (56.7 mg, 84%) was obtained.
mg, 0.0999 mol), compound 4p (33.6 mg, 82%) was obtained. Yield 84%. mg. Colorless oil. 1H NMR (400 MHz, Chloroformꢀ
o
White solid. mp 181ꢀ183 C. 1H NMR (400 MHz, Chloroformꢀ
d
) δ 7.68 (ddd,
= 7.8 7.35 (ddd, = 8.5, 6.8, 4.5 Hz, 2H), 7.29 – 7.25 (m, 2H), 7.22 –
Hz, 2H), 6.68 – 6.60 (m, 4H), 2.97 (s, 12H), 2.23 (s, 3H). 13
7.18 (m, 2H), 4.48 (tdd, = 10.7, 8.4, 4.5 Hz, 1H), 2.24 – 2.08
= 2.7 Hz), 138.2, (m, 2H), 1.71 – 1.58 (m, 2H), 1.46 – 1.35 (m, 2H), 1.24 (s, 9H),
1.14 (td, = 12.2, 10.9 Hz, 1H), 1.02 (qd, = 14.1, 13.6, 3.8
= 14.0 Hz), 40.0, Hz, 1H), 0.91 (d,
= 7.0 Hz, 3H), 0.85 – 0.76 (m, 7H). 13
) δ 152.0 (d, = 2.9 Hz), 135.0
= 149.1 Hz), 132.1 (d, = 3.2 Hz),
= 10.6 Hz), 128.0 (d, = 14.8 Hz), 126.1 (d,
S-(p-tolyl) bis(3,5-dimethylphenyl)phosphinothioate (4q). Hz), 123.0 (d, = 5.2 Hz), 79.7 (d, = 8.5 Hz), 48.7 (d,
J = 13.7, 8.3, 1.4 Hz, 2H), 7.49 – 7.43 (m, 1H),
d
) δ 7.68 – 7.59 (m, 4H), 7.35 – 7.30 (m, 2H), 6.97 (d,
J
J
C
J
NMR (100 MHz, Chloroformꢀ
134.9 (d, = 3.8 Hz), 133.1 (d,
= 5.1 Hz), 118.2 (d, = 119.3 Hz), 111.0 (d,
21.1. 31P NMR (162 MHz, Chloroformꢀ
d
) δ 152.4 (d,
J
J
J
J
= 11.7 Hz), 129.7, 124.6 (d,
J
J
J
J
J
C
d
) δ 44.3. HRMS (ESI+) NMR (100 MHz, Chloroformꢀ
d
J
m/z calcd. C23H27N2NaOPS+ [M+Na]+: 433.1474, found: (d,
433.1475. 131.4 (d,
J
= 4.3 Hz), 133.4 (d,
J
J
J
J
J
J
= 2.2
= 6.9
J
J
From bis(3,5ꢀdimethylphenyl)phosphine oxide (43.9 mg, 0.170 Hz), 43.4, 34.6, 34.0, 31.6, 31.2, 25.6, 22.9, 21.9, 21.1, 15.9. 31
mol), compound 4p (56.3 mg, 87%) was obtained. White solid. NMR (162 MHz, Chloroformꢀ
P
d
) δ 40.5. HRMS (ESI+) m/z
d
) δ 7.47 – calcd. C26H37NaO2PS+ [M+Na]+: 467.2144, found: 467.2145.
mp 142ꢀ144 C. 1H NMR (400 MHz, Chloroformꢀ
7.38 (m, 4H), 7.31 (dd, = 8.2, 1.7 Hz, 2H), 7.12 – 7.05 (m,
2H), 6.99 (d,
= 7.9 Hz, 2H), 2.29 (s, 12H), 2.23 (s, 3H). 13
NMR (100 MHz, Chloroformꢀ ) δ 138.9 (d,
(d, = 13.8 Hz), 135.3 (d, = 3.6 Hz), 133.8 (d,
132.4 (d, = 105.3 Hz), 129.8 (d, = 1.9 Hz), 129.1 (d,
10.2 Hz), 122.7 (d,
= 5.2 Hz), 21.2, 21.1. 31P NMR (162 MHz, (m, 2H), 7.49 – 7.42 (m, 1H), 7.39 – 7.31 (m, 2H), 7.27 – 7.20
Chloroformꢀ = 10.7, 8.5, 4.5 Hz,
) δ 43.1. HRMS (ESI+) m/z calcd. C23H25NaOPS+ (m, 2H), 6.75 – 6.67 (m, 2H), 4.48 (tdd,
[M+Na]+: 403.1256, found: 403.1256.
1H), 3.73 (s, 3H), 2.24 – 2.10 (m, 2H), 1.71 – 1.58 (m, 2H),
S-(p-tolyl) di(naphthalen-2-yl)phosphinothioate (4r).[5] 1.40 (dddd,
= 13.9, 6.0, 4.5, 2.7 Hz, 2H), 1.13 (td, = 12.2,
From di(naphthalenꢀ2ꢀyl)phosphine oxide (30.7 mg, 0.102 10.9 Hz, 1H), 1.08 – 0.97 (m, 1H), 0.93 (d, = 7.0 Hz, 3H),
mol), compound 4p (37.9 mg, 88%) was obtained. Yield 88%. 0.89 – 0.79 (m, 7H). 13C NMR (100 MHz, Chloroformꢀ
) δ
mg. Colorless oil. 1H NMR (400 MHz, Chloroformꢀ
) δ 8.47 160.3 (d, = 2.7 Hz), 137.0 (d, = 4.0 Hz), 133.3 (d, = 148.6
(d, = 14.8 Hz, 2H), 7.95 – 7.79 (m, 8H), 7.58 – 7.47 (m, 4H), Hz), 132.1 (d, = 3.2 Hz), 131.4 (d, = 10.6 Hz), 128.1 (d,
7.38 (dd, = 8.1, 1.9 Hz, 2H), 6.94 (d, = 7.8 Hz, 2H), 2.17 (s, 14.8 Hz), 116.7 (d, = 5.2 Hz), 114.6 (d, = 2.2 Hz), 79.6 (d,
3H). 13C NMR (100 MHz, Chloroformꢀ
) δ 139.1 (d, = 2.6 = 8.4 Hz), 55.3, 48.7 (d,
Hz), 135.2 (d, = 3.8 Hz), 134.7 (d, = 2.6 Hz), 133.9 (d,
22.9, 21.9, 21.2, 16.0. 31P NMR (162 MHz, Chloroformꢀ
9.5 Hz), 132.3 (d, = 14.3 Hz), 129.9 (d,
= 2.0 Hz), 129.7 (d, 40.5. HRMS (ESI+) m/z calcd. C23H31NaO3PS+ [M+Na]+:
= 107.2 Hz), 128.9, 128.4 (d, = 13.0 Hz), 128.3, 127.7, 441.1624, found: 441.1625.
126.9, 126.2 (d, = 11.5 Hz), 122.1 (d,
= 5.2 Hz), 21.0. 31
NMR (162 MHz, Chloroformꢀ
) δ 42.0. HRMS (ESI+) m/z
o
J
(S)-O-((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl) S-(4-
J
C
methoxyphenyl) phenylphosphonothioate (5c).[3a] From 2ꢀ
d
J
= 2.5 Hz), 138.1 isopropylꢀ5ꢀmethylcyclohexyl phenylphosphinate (33.8 mg,
= 3.1 Hz), 0.120 mol), compound 5c (39.4 mg, 78%) was obtained.
Colorless oil. 1H NMR (400 MHz, Chloroformꢀ
) δ 7.71 – 7.61
J
J
J
J
J
J
=
d
J
d
J
J
J
J
d
d
J
J
J
J
J
J
J
=
J
J
J
J
J
d
J
J
= 6.8 Hz), 43.4, 34.0, 31.6, 25.6,
) δ
J
J
J
=
d
J
J
J
J
J
J
P
d
calcd. C27H21NaOPS+ [M+Na]+: 447.0943, found: 447.0941.
O-((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl) S-(p-tolyl)
(S)-phenylphosphonothioate (5a).[3a] From 2ꢀisopropylꢀ5ꢀ
methylcyclohexyl phenylphosphinate (27.6 mg, 0.0985 mol),
compound 5a (31.7 mg, 80%) was obtained. Colorless oil. 1H
Acknowledgements
This research was supported financially by Institute for Basic
Science (IBSꢀR010ꢀG1).
NMR (400 MHz, Chloroformꢀd) δ 7.72 – 7.64 (m, 2H), 7.48 –
Notes and references
8 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C6GC03285K
ARTICLE
1
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Green Chemistry
Page 10 of 10
View Article Online
DOI: 10.1039/C6GC03285K
Metal- and Oxidant-Free S–P(O) Bond Construction via Direct Coupling of P(O)H with
Sulfinic Acids
Youngtaek Moon, Yonghoon Moon, Hangyeol Choi, and Sungwoo Hong*
A method for S–P(O) bond formation between R2P(O)H and sulfinic acids was developed under metal-, oxidant-,
and halogen-free conditions.