Synthesis of S-Aryl Phosphorothioates by Copper-Catalyzed Phosphorothiolation of Diaryliodonium and Arenediazonium Salts

Article abstract of DOI:10.1021/acs.joc.6b00925

Green methods for the synthesis of S-aryl phosphorothioates have been developed based on copper-catalyzed multicomponent reactions involving diaryliodonium/arenediazonium salts, elemental sulfur, and R₂P(O)H compounds. Most target products are obtained with these two methods in good to high yields at room temperature. These transformations allow the direct formation P-S and C-S bonds in one reaction.

Full text of DOI:10.1021/acs.joc.6b00925

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Article
Synthesis of S-Arylphosphorothioates by Copper-Catalyzed
Phosphorothiolation of Diaryliodonium and Arenediazonium Salts
Liangliang Zhang, Pengbo Zhang, Xueqin Li, Jian Xu, Guo Tang, and Yufen Zhao
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b00925 • Publication Date (Web): 31 May 2016
Downloaded from http://pubs.acs.org on June 1, 2016
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Synthesis of SꢀArylphosphorothioates by CopperꢀCatalyzed
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Phosphorothiolation of Diaryliodonium and Arenediazonium Salts
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Liangliang Zhang,† Pengbo Zhang,† Xueqin Li,† Jian Xu,*,‡ Guo Tang,*,† and Yufen Zhao†
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†Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory
for Chemical Biology of Fujian Province, Xiamen University, Xiamen 361005, China
Fax: (86)592ꢀ2185780; t12g21@xmu.edu.cn
‡Institute of Next Generation Matter Transformation, College of Chemical Engineering, Huaqiao
University, Xiamen 361021, China
xujian2024@qq.com
RECEIVED DATE (will be automatically inserted after manuscript is accepted).
Green methods for the synthesis of Sꢀarylphosphorothioates have been developed based on copper
catalyzed multicomponent reactions involving diaryliodonium/arenediazonium salts, elemental sulfur,
and R2P(O)H compounds. Most target products are obtained with these two methods in good to high
yields at room temperature. These transformations allow the direct formation P−S and C−S bonds in
one reaction.
INTRODUCTION
Compounds incorporating phosphorus−sulfur bond are versatile reagents in both organic and
inorganic synthesis. The best known example, Lawesson’s reagent [(4ꢀMeOC6H4)P=S (ꢁꢀS)]2, is
widely used in organic chemistry, for example, for the conversion of C=O to C=S groups.1
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Phosphate esters have broad applications in the fields of pharmaceuticals and agrochemicals
owing to its unique properties. Among the phosphate esters, phosphorothioates have received
considerable attention for more than 60 years because of their biological properties, for example,
as pesticides, insecticides, enzyme modifiers, and potential HIVꢀ1 and ACHE inhibitors.2
Additionally, Sꢀaryl phosphorothioates are also key synthetic intermediates for a variety of
complex molecules.3
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In contrast to the P=S functionality, the synthesis of analogues bearing sulfur atom at the
bridging position of a phosphate group as in a C–S–P(O) functionality, is usually a more
complicated task. Traditional synthesis work of Sꢀaryl phosphorothioates often proceeds via the
reaction between arylthiols and phosphorylation reagents (phosphorochloridates and
phosphorobromidates), however, chlorine and bromine are both toxic and difficult to control,
besides the preparation of phosphorochloridates and phosphorobromidates is required (Scheme
1a).4 As we know, thiols emit a pungent odour during and after use. Various substituted
arylsulfides (disulfides, sulfuryl chloride, and sulfonylhydrazides) instead of thiophenol were well
developed to construct C–S–P(O) bonds (Scheme 1b).5 In 2009, our group reported the direct
coupling of readily available R2P(O)H compounds with diaryl disulfides in the presence of
catalytic amounts of copper iodide.5b Recently, we successfully developed a facile catalytic
method for the preparation of Sꢀaryl phosphorothioates via phosphorothiolation of aryl boronic
acids with R2P(O)H compounds and sulfur powder (Scheme 1c).6 Hence, there is still great need
for the development of a convenient protocol to produce various phosphorothioate derivatives.
Scheme 1. C(aryl)−S−P BondꢀForming Reactions
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previous work
O
O
RO
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ArSH
+
Ar S P OR
(a)
P X
RO
OR
X = Cl, Br
O
O
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RO
Ar S P OR
Ar-X
+
or (RO) P
P H
(b)
(c)
(d)
3
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RO
OR
X = SH, SCl, SPh, SO2NHNH2, SO2Cl
our previous work
O
Ar S P OR
OR
O
RO
Ar
B(OH)2 +
S8
+
+
P H
RO
this work
OTf
Ar2
O
Ar1 S P OR
OR
I
Ar1
O
RO
RO
+ S8
P H
or
Ar1 N2BF4
Diaryliodonium salts, as important and valuable electrophilic arylation reagents, have recently
received considerable attention due to their high reactivity and nontoxicity.7 The regioselective
preparation of arylphosphonates using unsymmetrical diaryliodonium salts was discovered by our
group in 2013.8 Moreover, owing to the efforts of Beringer, Olofsson, and others, symmetrical and
unsymmetrical diaryliodonium triflates can now be easily synthesized from both electronꢀdeficient
and electronꢀrich arenes and aryl iodides with mCPBA and triflic acid in one pot.9 Furthermore,
diaryliodonium salts are stable and can be stored for one year or more at room temperature.
On the other hand, in comparison with those aforementioned sulfur species, sulfur powder (S8)
is cheap and more abundant in nature.10 Utilization of common and readily available chemicals as
the components and involvement of selective formation of C(aryl)–S–P bond should make this
reaction much more attractive. Herein we report a novel and efficient oneꢀstep synthesis of Sꢀaryl
phosphorothioates via multicomponent coupling of diaryliodonium salts, elemental sulfur (S8),
and R2P(O)H compounds (Scheme 1d).
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RESULTS AND DISCUSSION
Table 1. Optimization of Reaction Conditionsa
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entry
1
catalyst
Cu(OAc)2
Cu(OTf)2
Cu(acac)2
CuCl
base
Et3N
solvent
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
THF
yield (%)
92
2
Et3N
75
3
Et3N
Et3N
100a,b (95)a,c
4
70
44
5
CuI
Et3N
6
Cu2O
Et3N
66
7
ꢀ
Et3N
0
8
Cu(acac)2
Cu(acac)2
Cu(acac)2
Cu(acac)2
Cu(acac)2
Cu(acac)2
Cu(acac)2
K2CO3
Cs2CO3
NaOAc
K3PO4
Et3N
86
9
85
10
11
12
13
14
38
70
89
Et3N
DMF
80
Et3N
toluene
95a, 35d
aReaction conditions: diphenyliodonium triflate (0.30 mmol), diethyl
Hꢀphosphonate (0.30 mmol), elemental sulfur (0.45 mmol, 14.4 mg), catalyst
(0.03 mmol), base (0.45 mmol), solvent (1.5 mL) in a 10 mL tube at room
temperature for 20 h in air. Yield determinined by 31P NMR. Values in
b
parentheses indicate yield after purification. 1.0 equivalents of TEMPO was
added. c2,2’ꢀbipyridine (0.06 mmol) was added as ligand, reaction time: 5 h.
d
under a nitrogen atmosphere.
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As an initial attempt, reacting diphenyliodonium triflate (1a, 0.30 mmol) with elemental sulfur
(2, 0.45 mmol, 14.4 mg) and diethyl Hꢀphosphonate (3a, 0.30 mmol) in the presence of Cu(OAc)2
as catalyst and Et3N as base under air in CH3CN at room temperature were investigated.
Pleasingly, the reaction provided the product 4a in 92% yield (Table 1, entry 1). Without sulfur
powder, Pꢀarylation product could be obtained in 70% yield within 10 min.8 Once sulfur powder
was added, Pꢀarylation could be completely suppressed. Subsequently, various Cu(II) and Cu(I)
salts were further checked and the results showed that Cu(II) salts were more effective to give the
desired product (entries 1ꢀ6). Cu(acac)2 showed the highest activity and gave 4a in almost
quantitative yield within 20 hours (entry 3a). When 2,2’ꢀbipyridine was added as ligand, the
reaction could be completed in 5 h (entry 3b). No desired product was afforded without copper
salt (entry 7). Other inorganic bases, such as K2CO3, Cs2CO3, NaOAc and K3PO4 , could also
execute this reaction but with lower efficiency (entries 8ꢀ11). In addition to CH3CN, other tested
solvents, such as THF, DMF, and toluene, all gave good yields. Other inorganic sulfides such as
Na2S2O3, K2S2O8, K2S instead of elemental sulfur were investigated. K2S was also effective,
giving the product 4a in 50% yield. The same yield was obtained when 1.0 equiv of TEMPO was
added in the reaction under the optimal conditions (entry 3c). Reactions performed under a
nitrogen atmosphere led to a 35% yield (entry 14d). These results suggest that the mechanism is
like the wellꢀknown Chan−Evans−Lam coupling reaction.6
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With the optimized conditions in hand, the generality of the method was explored under the
optimized conditions (Table 1, entry 3a), and the results are summarized in Scheme 2. First,
symmetrical iodonium salts with electronꢀdonating groups such as methyl, tertꢀbutyl and methoxy
all afforded the desired products (4bꢀ4e) in good yields. Gratefully, steric bulk posed no problem
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in this reaction, as exemplified by 2,5ꢀdimethyl product 4d. In regard to the Hꢀphosphonates, in
addition to diethyl Hꢀphosphonate, dibenzyl, dimethyl, and diisopropyl all could be used as the
substrates, generating the corresponding Sꢀaryl phosphorothioates in 71ꢀ85% yields (4fꢀ4h). When
ethyl phenylphosphinate was used, 4i was obtained in 74% yield. Diphenylphosphine oxide was
used in the phosphorothiolation of iodonium salt, and led to the formation of product 4j in 65%
yield indicating that the reactivities of these P(O)–H compounds are almost independent of the
alkoxy and alkyl moieties. Symmetrical iodonium salts with electronꢀwithdrawing groups were
less effective, giving the corresponding products 4kꢀ4o in 10ꢀ 40% yields. Raising temperature to
60 oC slightly increase the yield.
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We then designed unsymmetrical diaryliodonium salts with one mesityl group and one
electronꢀdeficient aryl group. 4ꢀFluoroꢀ, 4ꢀchloroꢀ and 4ꢀbromophenyliodonium triflates were
examined for the reactivity with diethyl Hꢀphosphonate and sulfur powder under the same reaction
conditions to give the expected products 4kꢀ4m in excellent yields. Unsymmetrical iodonium salts
with electronꢀwithdrawing groups such as 4ꢀacyl and 3ꢀtrifluoromethyl afforded 4n and 4o with
satisfactory results. Substituted phenyl ring with electronꢀdonating oꢀmethyl, pꢀmethyl and
pꢀphenyl groups of the salts reacted with diethyl Hꢀphosphonate and sulfur powder to result in the
corresponding Sꢀaryl phosphorothioates (4pꢀ4r) in 70ꢀ84% yields. Unsymmetrical iodonium
salts with pyridine group didn’t work in this method.
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Scheme 2. Scope of Phosphorothiolation of Iodonium Salts.
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OTf
R1
O
O
I
R3
R4
Cu(acac)2 (10 mol %) , Et3N
CH3CN, rt, 20 h
P R4
R3
S
R1
R2
+
S8
+
PH
4a-4r
1
2
3
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O
O
P
O
O
S
P OEt
OEt
S
t-Bu
S
P
OEt
OEt
S
P OEt
OEt
OEt
OEt
70%
4c
81%
4a
95%
4b
85%
4d
OTf
O
O
I
S
P
OBn
MeO
S
P OEt
OEt
R1
R1
OBn
4e
70%
4f
85%
1a-1e
symmetrical iodonium salts
as starting materials for 4a-4j
O
O
O
O
S
P OMe
S
P Ph
Ph
P O-i-Pr
O-i-Pr
S
P Ph
OEt
S
OMe
80%
4j 65%
4h
71%
4g
4i
74%
O
O
O
P
F
S
P OEt
OEt
Br
S
P
OEt
Cl
S
OEt
OEt
OEt
4m
88%
4k
4l
90%
87%
OTf
I
CH3
O
O
EtO2C
4n
S
P OEt
OEt
F3C
S
P OEt
R1
OEt
H3C
CH3
94%
4o
87%
unsymmetrical iodonium salts 1f-1n
as starting materials for
O
4k-4r
O
O
S
P OEt
OEt
S
P OEt
OEt
S
P OEt
OEt
73%
4q
4r 70%
84%
4p
Encouraged by the findings described above, we continued to explore the synthesis of Sꢀaryl
phosphorothioates from diazonium salts. As we know, diazonium compounds are standard
reagents used in synthesis of organic compounds, especially aryl derivatives.11 Arenediazonium
cations are very versatile and useful synthons and show the several reactions in which the N2
group is replaced by another group or ion.12 Furthermore, the preparation of arenediazonium
tetrafluoroborate salts is treatment of cheap aromatic amines with sodium nitrite in the presence of
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tetrafluoroboric acid. The pure arenediazonium tetrafluoroborate salts are stable at room
temperature and can be stored below 8 °C for several months. To our delight, when diazonium
tetrafluoroborates was employed as the aryl source, the reaction took place under slightly modified
conditions. The optimal reaction conditions are: 1) Cu(OTf)2 (0.06 mmol), R2P(O)H (0.30 mmol),
elemental sulfur (0.45 mmol), Et3N (0.45 mmol), in CH3CN (1.0 mL) for 20 min; 2) adding
arenediazonium salt (0.36 mmol, in CH3CN 0.5 mL) into the above reaction mixture and stirring
at room temperature for 12 h. No 4a was obtained when 1.0 equiv of TEMPO was added. The
yield of 4a was decreased to 10% when the reaction was performed in the open air. Although the
detailed mechanism remains ambiguous at present, we reasoned that directly generating
Sꢀhydrogen phosphorothioate by reaction of R2P(O)H and elemental sulfur would react with
arenediazonium salt leading to the formation of Sꢀaryl phosphorothioates via a radical pathway in
the presence of copper catalyst.6,13
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We next examined the reactions of various substituted arenediazonium tetrafluoroborates 5
with sulfur powder and R2P(O)H compounds to probe the scope of the reaction (Scheme 3). It was
found that a wide range of arenediazonium tetrafluoroborates proceeded efficiently. With methyl
substituted on benzene, such as paraꢀ, metaꢀ, and orthoꢀmethyl groups (5bꢀ5d), these compounds
reacted efficiently to give the desired products in good yields. Halogen atoms such as fluorine,
chlorine, bromine, and iodine (5eꢀ5k) have little influence under the optimized reaction conditions
to afford the corresponding products in moderate to good yields. The orthoꢀsubstituted diazonium
salts gave much lower yields because of the steric effect (5c, 5hꢀ5j).
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Scheme 3. Scope of Phosphorothiolation of Diazonium Salts.
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Diazonium salts with electrondonating (methoxy) or electronꢀwithdrawing (CN, CH3CO, CF3,
NO2, COOEt, and CONH2) groups all produced the desired products in good yields, suggesting
that the substituted groups did not have a significant influence on the reaction (5lꢀ5r). In regard to
the Hꢀphosphonates, in addition to 3a, dibenzyl (3b), dimethyl (3c), and diisopropyl (3d) all could
be used as the substrates, generating the corresponding Sꢀaryl phosphorothioates (4f–4h) in
70–81% yields. When ethyl phenylphosphinate (3e) was used, 4i was obtained in good yield.
Diphenylphosphine oxide was also examined. Unfortunately, only 22% yield of the desired PꢀSꢀC
bondꢀforming product was obtained.
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In order to demonstrate the practical application of these methods, phosphorothiolation of
diaryliodonium (5 mmol) and arenediazonium(6 mmol) salts were conducted and afforded 4a in
good yields (Scheme 4).
Scheme 4. Scaleꢀup Preparation of 4a.
CONCLUSION
In conclusion, we have developed two novel copperꢀcatalyzed phosphorusꢀsulfurꢀcarbon(aryl)
bondꢀforming reactions which proceeds in good yield via phosphorothiolation of diaryliodonium
or diazonium salts with R2P(O)H compounds and sulfur powder. The reactions described provide
novel accesses to Sꢀaryl phosphorothioates and cover a broad scope of substrates. Importantly, this
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transformation would provide a new pathway for the formation of P−S and C−S bonds in one
reaction. Moreover, the diaryliodonium salts and diazonium salts can be readily prepared from the
corresponding cheap arene compounds. In addition, the use of an inexpensive Cu(II) catalyst
without any ligands, using readily available sulfur powder (S8) and R2P(O)H compounds, means
that this facile protocol will have wide application for the construction of biologically active Sꢀaryl
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phosphorothioates.
EXPERIMENTAL SECTION
General. All reagents were purchased and used without further purification. The solvent was
freshly distilled. All new compounds were further characterized by HRMS (FTꢀICRꢀMS) and
electrospray ionization source in positive ion mode.
1. General Procedure for the Phosphorothiolation of Diaryliodonium Salts (Method A)
A 10 mL tube was charged with Cu(acac)2 (0.03 mmol, 7.8 mg), R2P(O)H (0.30 mmol),
elemental sulfur (0.45 mmol, 14.4 mg), diaryliodonium triflate (0.30 mmol), Et3N (0.45 mmol,
45.5 mg), and CH3CN (1.5 mL), and the reaction mixture was stirred at room temperature open to
air for 20 h. After completion, the crude reaction mixture was purified by flash chromatography
using petroleum−AcOEt (3:1, v/v) as the eluent to give Sꢀaryl phosphorothioates.
The preparations of symmetrical and unsymmetrical iodonium salts are shown in refs 9dꢀ9g.
2. General Procedure for the Phosphorothiolation of Arenediazonium Salts (Method B)
An ovenꢀdried Schlenk tube with a magnetic stir bar containing Cu(OTf)2 (0.06 mmol, 21.7 mg),
R2P(O)H (0.30 mmol), elemental sulfur (0.45 mmol, 14.4 mg) was evacuated and purged with
nitrogen three times. Et3N (0.45 mmol, 45.5 mg) and CH3CN (1.0 mL) were added to the system
at room temperature and the reaction mixture was stirred at room temperature for 20 min. Then,
arenediazonium salt (0.36 mmol) in CH3CN (0.5 mL) was added to the system at room
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temperature. The resulting mixture was stirred at room temperature for 12 h. After completion, the
crude reaction mixture was purified by flash chromatography using petroleum−AcOEt (3:1, v/v)
as the eluent to give Sꢀaryl phosphorothioates.
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The preparations of arenediazonium salts are shown in ref 11f.
O,OꢀDiethyl SꢀPhenyl Phosphorothioate (4a) (CAS Registry No. 1889ꢀ58ꢀ3).6 Yield: 69.8 mg, 95%
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(Method A); 70.1 mg, 95% (Method B). Yellow oil. H NMR (400 MHz, CDCl3, ppm) (Method B) δ
7.58 – 7.55 (m, 2 H), 7.35 – 7.31 (m, 3 H), 4.26 – 4.11 (m, 4 H), 1.32 – 1.28 (m, 6 H). 13C{1H} NMR
(100 MHz, CDCl3, ppm) δ 134.6 (d, J = 5.2 Hz), 129.4 (d, J = 2.0 Hz), 129.0 (d, J = 2.6 Hz), 126.6 (d,
J = 7.2 Hz), 64.1 (d, J = 6.3 Hz), 16.0 (d, J = 7.1 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 22.8.
MSꢀESI: m/z 268.8, [M + Na]+.
O,OꢀDiethyl SꢀpꢀTolyl Phosphorothioate (4b) (CAS Registry No. 4143ꢀ38ꢀ8).6 Yield: 66.0 mg, 85%
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(Method A); 66.3 mg, 85% (Method B). Yellow oil. H NMR (400 MHz, CDCl3, ppm) (Method B) δ
7.45 – 7.43 (m, 2 H), 7.15 (d, J = 8.1 Hz, 2 H), 4.26 – 4.11 (m, 4 H), 2.34 (d, J = 1.8 Hz, 3 H), 1.32 –
1.29 (m, 6 H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 139.3 (d, J = 3.0 Hz), 134.6 (d, J = 5.0 Hz),
130.1 (d, J = 2.3 Hz), 122.8 (d, J = 7.3 Hz), 64.0 (d, J = 6.1 Hz), 21.2, 16.0 (d, J = 7.3 Hz). 31P{1H}
NMR (162 MHz, CDCl3, ppm) δ 23.3. MSꢀESI: m/z 282.8, [M + Na]+.
Sꢀ(4ꢀ(Tertꢀbutyl)phenyl) O,OꢀDiethyl Phosphorothioate (4c). Yield: 73.4 mg, 81% (Method A). Yellow
oil. 1H NMR (400 MHz, CDCl3, ppm) δ 7.48 – 7.46 (m, 2 H), 7.35 (d, J = 8.3 Hz, 2 H), 4.26 – 4.13 (m,
4 H), 1.32 – 1.30 (m, 15 H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 152.5 (d, J = 3.1 Hz), 134.5 (d,
J = 4.9 Hz), 126.6 (d, J = 2.3 Hz), 122.9 (d, J = 7.2 Hz), 64.1 (d, J = 6.1 Hz), 34.8, 31.3, 21.1, 16.1 (d,
J = 7.3 Hz). 31P{1H}NMR (162 MHz, CDCl3, ppm) δ 23.4. HRMS (ESI) m/z: [M + Na]+ Calcd for
C14H23NaO3PS+, 325.0998; Found: 325.0988).
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Sꢀ(2,5ꢀDimethylphenyl) O,OꢀDiethyl Phosphorothioate (4d) (CAS Registry No. 1628447ꢀ77ꢀ7).5i Yield:
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57.6 mg, 70% (Method A). Yellow oil. H NMR (400 MHz, CDCl3, ppm) δ 7.41 (s, 1 H), 7.12 (d, J =
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7.9 Hz, 1 H), 7.06 (d, J = 7.9 Hz, 1 H), 4.22 – 4.09 (m, 4 H), 2.47 (s, 3H), 2.30 (s, 3 H), 1.31 – 1.28 (m,
6 H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 139.2 (d, J = 5.6 Hz), 136.9 (d, J = 3.9 Hz), 136.4 (d, J
= 2.6 Hz), 130.7 (d, J = 2.6 Hz), 130.4 (d, J = 3.3 Hz), 125.3 (d, J = 7.3 Hz), 64.2 (d, J = 6.7 Hz), 21.0,
20.9, 16.1 (d, J = 7.2 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 23.4. MSꢀESI: m/z 296.9, [M +
Na]+.
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O,OꢀDiethyl Sꢀ(4ꢀMethoxyphenyl) Phosphorothioate (4e) (CAS Registry No. 56806ꢀ76ꢀ9).5j Yield: 58.0
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mg, 70% (Method A); 79.5 mg, 96% (Method B). Yellow oil. H NMR (400 MHz, CDCl3, ppm)
(Method B) δ 7.48 – 7.46 (m, 2 H), 6.88 (d, J = 8.7 Hz, 2 H), 4.25 – 4.10 (m, 4 H), 3.80 (s, 3 H), 1.33 –
1.29 (m, 6 H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 160.5 (d, J = 2.9 Hz), 136.3 (d, J = 4.7 Hz),
116.6 (d, J = 7.5 Hz), 115.0 (d, J = 2.6 Hz), 64.0 (d, J = 6.3 Hz), 55.4, 16.0 (d, J = 7.1 Hz). 31P{1H}
NMR (162 MHz, CDCl3, ppm) δ 23.5. MSꢀESI: m/z 298.9, [M + Na]+.
O,OꢀDibenzyl SꢀPhenyl Phosphorothioate (4f) (CAS Registry No. 1608108ꢀ22ꢀ0).5c Yield: 94.3 mg,
85% (Method A); 85.5 mg, 77% (Method B). Yellow oil. 1H NMR (400 MHz, CDCl3, ppm) (Method B)
δ 7.48 – 7.46 (m, 2 H), 7.30 – 7.23 (m, 13 H), 5.14 – 5.05 (m, 4 H). 13C{1H} NMR (100 MHz, CDCl3,
ppm) δ 135.3 (d, J = 7.6 Hz), 134.8 (d, J = 5.3 Hz), 129.4 (d, J = 2.2 Hz), 129.1 (d, J = 2.8 Hz), 128.6,
128.5, 128.0, 125.9 (d, J = 7.3 Hz), 69.4 (d, J = 6.4 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 23.9.
MSꢀESI: m/z 370.9, [M + H]+.
O,OꢀDimethyl SꢀPhenyl Phosphorothioate (4g) (CAS Registry No. 4237ꢀ00ꢀ7). 5j Yield: 52.3 mg, 80%
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(Method A); 53.0 mg, 81% (Method B). Yellow oil. H NMR (400 MHz, CDCl3, ppm) (Method B) δ
7.56 – 7.54 (m, 2 H), 7.38 – 7.32 (m, 3 H), 3.82 (s, 3 H), 3.79 (s, 3 H). 13C{1H} NMR (100 MHz,
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CDCl3, ppm) δ 134.7 (d, J = 5.4 Hz), 129.6 (d, J = 1.9 Hz), 129.3 (d, J = 3.2 Hz), 126.1 (d, J = 7.4 Hz),
54.3 (d, J = 6.4 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 26.2. MSꢀESI: m/z 240.8, [M +Na]+.
O,OꢀDiisopropyl SꢀPhenyl Phosphorothioate (4h) (CAS Registry No. 15267ꢀ38ꢀ6).6 Yield: 58.4 mg,
71% (Method A); 57.4 mg, 70% (Method B). Yellow oil. 1H NMR (400 MHz, CDCl3, ppm) (Method B)
δ 7.61 – 7.58 (m, 2 H), 7.35 – 7.32 (m, 3 H), 4.80 – 4.72 (m, 2 H), 1.32 (d, J = 6.2 Hz, 6 H), 1.25 (d, J
= 6.2 Hz, 6 H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 134.3 (d, J = 5.3 Hz), 129.2 (d, J = 1.8 Hz),
128.7 (d, J = 2.4 Hz), 127.4 (d, J = 7.0 Hz), 73.4 (d, J = 6.8 Hz), 23.9 (d, J = 4.2 Hz), 23.6 (d, J = 5.7
Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 20.4. MSꢀESI: m/z 297.0, [M + Na]+.
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OꢀEthyl SꢀPhenyl Phenylphosphonothioate (4i) (CAS Registry No. 1629085ꢀ78ꢀ4).6 Yield: 61.7 mg,
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74% (Method A); 55.9 mg, 67%, (Method B). Yellow oil. H NMR (400 MHz, CDCl3, ppm) (Method
B) δ 7.67 – 7.62 (m, 2 H), 7.50 – 7.46 (m, 1 H), 7.38 – 7.33 (m, 2 H), 7.30 – 7.26 (m, 3 H), 7.19 (t, J =
7.7 Hz, 2 H), 4.42 – 4.22 (m, 2 H), 1.41 – 1.38 (m, 3 H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ
135.5 (d, J = 4.2 Hz), 132.5 (d, J = 3.1 Hz), 131.5 (d, J = 10.6 Hz), 131.6 (d, J = 151.3 Hz), 129.2 (d, J
= 2.1 Hz), 129.0 (d, J = 2.7 Hz), 128.3 (d, J = 15.0 Hz), 126.7 (d, J = 5.6 Hz), 62.5 (d, J = 6.9 Hz), 16.4
(d, J = 6.8 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 41.7. MSꢀESI: m/z 278.8, [M + H]+.
SꢀPhenyl Diphenylphosphinothioate (4j) (CAS Registry No. 5510ꢀ78ꢀ1).5g Yield: 60.4 mg, 65%
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(Method A); 20.5 mg, 22% (Method B). White solid. H NMR (400 MHz, CDCl3, ppm) (Method B)
δ 7.87 – 7.82 (m, 4 H), 7.56 – 7.38 (m, 8 H), 7.26 – 7.17 (m, 3 H). 13C{1H} NMR (100 MHz, CDCl3,
ppm) δ 135.5 (d, J = 4.0 Hz), 132.7 (d, J = 106.8 Hz), 132.4 (d, J = 2.9 Hz), 131.7 (d, J = 10.2 Hz),
129.2 (d, J = 1.2 Hz), 129.0 (d, J = 1.8 Hz), 128.6 (d, J = 13.2 Hz), 126.3 (d, J = 5.3 Hz). 31P{1H}
NMR (162 MHz, CDCl3, ppm) δ 41.4. MSꢀESI: m/z 333.1, [M + Na]+.
O,OꢀDiethyl Sꢀ(4ꢀFluorophenyl)phosphorothioate (4k) (CAS Registry No. 333ꢀ42ꢀ6).6 Yield: 71.2 mg,
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90% (Method A); 74.4 mg, 94% (method B). Yellow oil. 1H NMR (400 MHz, CDCl3, ppm) (Method B)
δ 7.54 – 7.50 (m, 2 H), 7.03 (t, J = 8.5 Hz, 2 H), 4.23 – 4.10 (m, 4 H), 1.30 – 1.27 (m, 6 H). 13C{1H}
NMR (100 MHz, CDCl3, ppm) δ 163.4 (dd, J = 250.0 Hz, J = 2.7 HZ), 136.8 (dd, J = 8.4 Hz, J = 4.9
Hz), 121.8 (dd, J = 7.3 Hz, J = 3.0 Hz), 116.7 (dd, J = 22.1 Hz, J = 1.9 Hz), 64.3 (d, J = 6.3 Hz), 16.1
(d, J = 7.1 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 22.6. 19F{1H} NMR (377 MHz, CDCl3, ppm)
δ ꢀ111.6 (d, J = 4.9 Hz). MSꢀESI: m/z 286.8, [M + Na]+.
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Sꢀ(4ꢀChlorophenyl) O,OꢀDiethyl Phosphorothioate (4l) (CAS Registry No. 4524ꢀ70ꢀ3).6 Yield: 73.1 mg,
87% (Method A); 78.1 mg, 93% (Method B). Yellow oil. 1H NMR (400 MHz, CDCl3, ppm) (Method B)
δ 7.52 – 7.49 (m, 2 H), 7.32 (d, J = 8.4 Hz, 2 H), 4.27 – 4.11 (m, 4 H), 1.34 – 1.30 (m, 6 H). 13C{1H}
NMR (100 MHz, CDCl3, ppm) δ 135.8 (d, J = 5.2 Hz), 135.5 (d, J = 3.5 Hz), 129.6 (d, J = 2.2 Hz),
125.2 (d, J = 7.3 Hz), 64.3 (d, J = 6.3 Hz), 16.0 (d, J = 7.1 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm)
δ 22.1. MSꢀESI: m/z 302.9, [M + Na]+.
Sꢀ(4ꢀBromophenyl) O,OꢀDiethyl Phosphorothioate (4m) (CAS Registry No. 15224ꢀ36ꢀ9).6 Yield: 85.8
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mg, 88% (Method A); 87.5 mg, 90% (Method B). Yellow oil. H NMR (400 MHz, CDCl3, ppm)
(Method B) δ 7.49 – 7.42 (m, 4 H), 4.27 – 4.11 (m, 4 H), 1.33 – 1.30 (m, 6 H). 13C{1H} NMR (100
MHz, CDCl3, ppm) δ 136.0 (d, J = 5.3 Hz), 132.5 (d, J = 2.0 Hz), 125.8 (d, J = 7.3 Hz), 123.6 (d, J =
3.6 Hz), 64.3 (d, J = 6.4 Hz), 16.0 (d, J = 7.0 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 21.9.
MSꢀESI: m/z 346.9, [M + Na]+.
Ethyl 4ꢀ((Diethoxyphosphoryl)thio)benzoate (4n) . Yield: 89.6 mg, 94% (Method A); 83.0 mg, 87%
(Method B). Yellow oil. 1H NMR (400 MHz, CDCl3, ppm) (Method B) δ 8.01 (d, J = 8.2 Hz, 2 H), 7.66
– 7.64 (m, 2 H), 4.41 – 4.36 (m, 2 H), 4.29 – 4.13 (m, 4 H), 1.39 (t, J = 7.1 Hz, 3 H), 1.34 – 1.30 (m, 6
H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 165.8, 133.7 (d, J = 5.7 Hz), 132.8 (d, J = 7.0 Hz), 130.8
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(d, J = 3.0 Hz), 130.2 (d, J = 1.6 Hz), 64.4 (d, J = 6.4 Hz), 61.3, 16.0 (d, J = 7.2 Hz), 14.3. 31P{1H}
NMR (162 MHz, CDCl3, ppm) δ 21.4. HRMS (ESI) m/z: [M + Na]+ Calcd for C13H19NaO5PS+,
341.0583; Found: 341.0575).
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O,OꢀDiethyl Sꢀ(3ꢀ(Trifluoromethyl)phenyl) Phosphorothioate(4o) (CAS Registry No. 38726ꢀ06ꢀ6).6
Yield: 82.0 mg, 87% (Method A). Yellow oil. 1H NMR (400 MHz, CDCl3, ppm) δ 7.81(s, 1 H), 7.47 (d,
J = 7.9 Hz, 1 H), 7.76 (d, J = 7.8 Hz, 1 H), 7.60 (t, J = 7.8 Hz, 1 H), 4.25 – 4.13 (m, 4 H), 1.31 – 1.28
(m, 6 H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 137.9 (d, J = 5.2 Hz), 131.8 (dd, J = 32.8 Hz, J =
1.8 Hz), 131.4 – 131.2 (m), 129.88 (d, J = 2.7 Hz), 128.4 (d, J = 7.1 Hz), 125.8 (q, J = 3.28 Hz), 123.6
(d, J = 272.5 Hz), 64.5 (d, J = 6.4 Hz), 16.0 (d, J = 7.2 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ
21.6. 19F NMR (377 MHz, CDCl3, ppm) δ ꢀ62.9. MSꢀESI: m/z 337.0, [M + Na]+.
O,OꢀDiethyl SꢀoꢀTolyl Phosphorothioate (4p) (CAS Registry No. 94583ꢀ02ꢀ5).6 Yield: 56.9 mg, 73%
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(Method A); 57.7 mg, 74% (Method B). Yellow oil. H NMR (400 MHz, CDCl3, ppm) (Method B) δ
7.60 (d, J = 8.2 Hz, 1 H), 7.26 – 7.24 (m, 2 H), 7.20 – 7.15 (m, 1 H), 4.23 – 4.08 (m, 4 H), 2.52 (d, J =
1.0 Hz, 3 H), 1.31 – 1.27 (m, 6 H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 142.2 (d, J = 5.4 Hz),
136.2 (d, J = 4.0 Hz), 130.9 (d, J = 2.6 Hz), 129.5 (d, J = 2.9 Hz), 126.8 (d, J = 2.5 Hz), 125.8 (d, J =
7.4 Hz), 64.2 (d, J = 6.7 Hz), 21.4, 16.1 (d, J = 7.1 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 23.0.
MSꢀESI: m/z 283.0, [M + Na]+.
O,OꢀDiethyl SꢀmꢀTolyl Phosphorothioate (4q) (CAS Registry No. 108481ꢀ79ꢀ4).6 Yield: 65.5mg, 84%
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(Method A); 59.3 mg, 76% (Method B). Yellow oil. H NMR (400 MHz, CDCl3, ppm) (Method B) δ
7.37 (d, J = 10.3 Hz, 2 H), 7.22 (d, J = 7.6 Hz, 1 H), 7.16 (d, J = 7.6 Hz, 1 H), 4.28 – 4.11 (m, 4 H),
2.34 (s, 3 H), 1.33 – 1.29 (m, 6 H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 139.3 (d, J = 2.2 Hz),
135.2 (d, J = 5.2 Hz), 131.6 (d, J = 5.2 Hz), 129.9 (d, J = 2.8 Hz), 129.2 (d, J = 2.1 Hz), 126.2 (d, J =
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7.2 Hz), 64.1 (d, J = 6.1 Hz), 21.3, 16.0 (d, J = 7.2 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 23.1.
MSꢀESI: m/z 282.9, [M + Na]+.
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Sꢀ[1,1'ꢀBiphenyl]ꢀ4ꢀyl O,OꢀDiethyl Phosphorothioate (4r). Yield: 67.6 mg, 70% (method A). Yellow oil.
1H NMR (400 MHz, CDCl3, ppm) δ 7.64 – 7.62 (m, 2 H), 7.57 (d, J = 7.8 Hz, 4 H), 7.44 (t, J = 7.6 Hz,
2 H), 7.38 – 7.35 (m, 1 H), 4.29 – 4.16 (m, 4 H), 1.35 – 1.32 (m, 6 H). 13C{1H} NMR (100 MHz,
CDCl3, ppm) δ 142.1 (d, J = 3.0 Hz), 140.0, 135.0 (d, J = 5.3 Hz), 129.0, 128.1 (d, J = 2.0 Hz), 127.9,
127.2, 125.4 (d, J = 7.3 Hz), 64.2 (d, J = 6.1 Hz), 16.2 (d, J = 7.2 Hz). 31P{1H} NMR (162 MHz,
CDCl3, ppm) δ 22.8. HRMS (ESI) m/z: [M + Na]+ Calcd for C16H19NaO3PS+, 345.0685; Found:
345.0669).
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O,OꢀDiethyl Sꢀ(2ꢀFluorophenyl) Phosphorothioate (4s) (CAS Registry No. 1883501ꢀ47ꢀ0).6 Yield: 61.0
mg, 77% (Method B). Yellow oil. 1H NMR (400 MHz, CDCl3, ppm) (Method A) δ 7.64 – 7.60 (m, 1 H),
7.41 – 7.35 (m, 1 H), 7.17 – 7.11 (m, 2 H), 4.30 – 4.16 (m, 4 H), 1.34 – 1.31 (m, 6 H). 13C{1H} NMR
(100 MHz, CDCl3, ppm) δ 162.7 (dd, J = 248.8 Hz, J = 5.6 Hz), 137.6 (d, J = 4.3 Hz), 131.7 (dd, J =
8.0 Hz, J = 2.76), 124.9ꢀ125.0 (m), 116.4 (dd, J = 22.9 Hz, J = 2.3 Hz), 113.9 (dd, J = 18.5 Hz, J = 7.5
Hz), 64.3 (d, J = 6.0 Hz), 16.0 (d, J = 7.0 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 21.3 (d, J =
2.8 Hz). 19F NMR (377 MHz, CDCl3, ppm) δ ꢀ106.2 (d, J = 4.0 Hz). MSꢀESI: m/z 286.8, [M + Na]+.
Sꢀ(2ꢀChlorophenyl) O,OꢀDiethyl Phosphorothioate (4t) (CAS Registry No. 15224ꢀ41ꢀ6).6 Yield: 62.2
mg, 74% (Method B). Yellow oil. 1H NMR (400 MHz, CDCl3, ppm) δ 7.76 (d, J = 7.5 Hz, 1 H), 7.46 (d,
J = 7.6 Hz, 1 H), 7.32 – 7.24 (m, 2 H), 4.30 – 4.16 (m, 4 H), 1.34 – 1.30 (m, 6 H). 13C{1H} NMR (100
MHz, CDCl3, ppm) δ 137.9 (d, J = 6.9 Hz), 136.8 (d, J = 4.0 Hz), 130.3 (d, J = 6.7 Hz), 127.5, 126.4 (d,
J = 6.8 Hz), 64.4 (d, J = 6.3 Hz), 16.0 (d, J = 7.3 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 21.2.
MSꢀESI: m/z 302.9, [M + Na]+.
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O,OꢀDiethyl Sꢀ(2ꢀIodophenyl) Phosphorothioate (4u). Yield: 87.0 mg, 78% (Method B). Yellow oil. 1H
NMR (400 MHz, CDCl3, ppm) δ 7.90 (d, J = 8.0 Hz, 1 H), 7.83 – 7.80 (m, 1 H), 7.37 – 7.33 (m, 1 H),
7.02 (t, J = 7.7 Hz, 1 H), 4.31 – 4.16 (m, 4 H), 1.34 – 1.30 (m, 6 H). 13C{1H} NMR (100 MHz, CDCl3,
ppm) δ 140.2 (d, J = 2.1 Hz), 135.3 (d, J = 4.0 Hz), 132.9 (d, J = 6.7 Hz), 130.2, 129.1 (d, J = 2.0 Hz),
105.6 (d, J = 8.1 Hz), 64.5 (d, J = 6.4 Hz), 16.1 (d, J = 7.2 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm)
δ 21.6. HRMS (ESI) m/z: [M + Na]+ Calcd for C10H15IO3PS+, 372.9519; Found: 372.9515).
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Sꢀ(2ꢀBromophenyl) O,OꢀDiethyl phosphorothioate (4v) (CAS Registry No. 1807788ꢀ31ꢀ3).5j Yield: 85.5
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mg, 88% (Method B). Yellow oil. H NMR (400 MHz, CDCl3, ppm) δ 7.71 – 7.69 (m, 1 H), 7.51 –
7.46 (m, 2 H), 7.21 (t, J = 7.9 Hz, 1 H), 4.26 – 4.11 (m, 4 H), 1.33 – 1.29 (m, 6 H). 13C{1H} NMR (100
MHz, CDCl3, ppm) δ 137.0 (d, J = 5.3 Hz), 133.0 (d, J = 5.3 Hz), 132.1 (d, J = 2.7 Hz), 130.6 (d, J =
2.1 Hz), 128.8 (d, J = 7.0 Hz), 122.7 (d, J = 2.7 Hz), 64.3 (d, J = 6.4 Hz), 16.0 (d, J = 7.1 Hz). 31P{1H}
NMR (162 MHz, CDCl3, ppm) δ 21.77. MSꢀESI: m/z 346.9, [M + Na]+.
Sꢀ(4ꢀCyanophenyl) O,OꢀDiethyl Phosphorothioate (4w) (CAS Registry No. 179637ꢀ16ꢀ2).6 Yield: 75.5
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mg, 93% (Method B). Yellow oil. H NMR (400 MHz, CDCl3, ppm) δ 7.69 – 7.67 (m, 2 H), 7.61 (d, J
= 8.2 Hz, 2 H), 4.25 – 4.14 (m, 4 H), 1.32 – 1.30 (m, 6 H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ
134.2 (d, J = 6.0 Hz), 134.0 (d, J = 6.7 Hz), 132.7, 118.0, 112.5 (d, J = 2.3 Hz), 64.7 (d, J = 6.5 Hz),
16.0 (d, J = 6.9 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 20.3. MSꢀESI: m/z 294.0, [M + Na]+.
Sꢀ(4ꢀAcetylphenyl) O,OꢀDiethyl Phosphorothioate (4x) (CAS Registry No. 1883501ꢀ44ꢀ7).6 Yield: 78.6
mg, 91% (Method B). Yellow oil. 1H NMR (400 MHz, CDCl3, ppm) δ 7.88 (d, J = 8.3 Hz, 2 H), 7.65 –
7.63 (m, 2 H), 4.25 – 4.11 (m, 4 H), 2.56 (s, 3 H), 1.30 – 1.27 (m, 6 H). 13C{1H} NMR (100 MHz,
CDCl3, ppm) δ 197.2 (s), 137.0, 133.9 (d, J = 5.8 Hz), 133.2 (d, J = 6.9 Hz), 129.0 (d, J = 1.2 Hz), 64.4
(d, J = 6.4 Hz), 26.7, 16.0 (d, J = 7.0 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 21.2. MSꢀESI: m/z
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310.8, [M + Na]+.
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O,OꢀDiethyl Sꢀ(4ꢀ(Trifluoromethyl)phenyl) Phosphorothioate (4y) (CAS Registry No. 1883501ꢀ42ꢀ5).6
Yield: 84.8 mg, 90% (method B). Yellow oil. 1H NMR (400 MHz, CDCl3, ppm) δ 7.70 (d, J = 7.8 Hz, 2
H), 7.60 (d, J = 8.4 Hz, 2 H), 4.28 – 4.13 (m, 4 H), 1.34 – 1.30 (m, 6 H). 13C{1H} NMR (100 MHz,
CDCl3, ppm) δ 134.3 (d, J = 5.6 Hz), 132.0 (d, J = 6.6 Hz), 131.0 (m, J = 17.7.0 Hz), 126.2, 123.8 (d, J
= 272.1 Hz), 64.5 (d, J = 6.4 Hz), 16.0 (d, J = 7.1 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 21.3.
19F{1H} NMR (377 MHz, CDCl3, ppm) δ ꢀ62.9. MSꢀESI: m/z 336.9, [M + Na]+.
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O,OꢀDiethyl Sꢀ(4ꢀNitrophenyl) Phosphorothioate (4z). Yield: 71.6 mg, 82% (Method B). Yellow oil. 1H
NMR (400 MHz, CDCl3, ppm) δ 8.20 (d, J = 8.6 Hz, 2 H), 7.78 – 7.75 (m, 2 H), 4.32 – 4.15 (m, 4 H),
1.36 – 1.33 (m, 6 H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 147.9, 136.3 (d, J = 6.5 Hz), 134.2 (d, J
= 6.0 Hz), 124.2, 64.8 (d, J = 6.4 Hz), 16.1 (d, J = 7.0 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ
19.8. HRMS (ESI) m/z: [M + Na]+ Calcd for C10H14NaNO5PS+, 314.0223; Found: 314.0218).
Sꢀ(4ꢀCarbamoylphenyl) O,OꢀDiethyl Phosphorothioate (4aa). Yield: 57.2 mg, 66% (method B). Yellow
o
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solid, m.p. 144.5ꢀ146.8 C. H NMR (400 MHz, CDCl3, ppm) δ 7.78 (d, J = 8.0 Hz, 2 H), 7.64 (t, J =
4.1 Hz, 2 H), 6.33 (s, 1 H), 5.89 (s, 1 H), 4.26 – 4.13 (m, 4 H), 1.33 – 1.30 (m, 6 H); 13C{1H} NMR
(100 MHz, CDCl3, ppm) δ 168.6, 134.3 (d, J = 5.4 Hz), 133.9 (d, J = 2.6 Hz), 131.6 (d, J = 6.6 Hz),
128.3, 64.6 (d, J = 6.4 Hz), 16.1 (d, J = 7.0 Hz); 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 21.7.
HRMSꢀESI: m/z found: 312.0415 ([M + Na]+, C11H16NaNO4PS+ calcd. 312.0430).
Sꢀ(3,5ꢀDimethylphenyl) O,OꢀDiethyl Phosphorothioate (4ab) (CAS Registry No. 1883501ꢀ37ꢀ8).6 Yield:
51.8 mg, 63% (Method B). Yellow oil. 1H NMR (400 MHz, CDCl3, ppm) δ 7.17 (s, 2 H), 6.97 (s, 1 H),
4.24 – 4.12 (m, 4 H), 2.29 (s, 6 H), 1.32ꢀ1.29 (m, 6 H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 139.1
(d, J = 2.0 Hz), 132.3 (d, J = 5.2 Hz), 131.0 (d, J = 2.8 Hz), 125.8 (d, J = 7.1 Hz), 64.1 (d, J = 6.2 Hz),
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21.3, 16.1 (d, J = 7.3 Hz). 31P{1H} NMR (162 MHz, CDCl3, ppm) δ 23.4. MSꢀESI: m/z 296.8, [M +
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ASSOCIATED CONTENT
Acknowledgements We acknowledge financial support from the Chinese National Natural Science
Foundation (21232005, 21375113), the National Basic Research Program of China (2012CB821600),
and the Fundamental Research Funds for the Central Universities (20720160030).
Supporting Information.
Copies of 1H NMR, 13C NMR spectra of compounds 4aꢀ4z and 4aaꢀ4ab. The Supporting Information
is available free of charge on the ACS Publications website.
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