Palladium-catalyzed desulfitative C-P coupling of arylsulfinate metal salts and H-phosphonates

Article abstract of DOI:10.1039/c4ra01270d

Catalyzed by palladium(ii) chloride, a diverse range of arylsulfinate sodium, potassium, lithium, silver, zinc, and copper salts undergo desulfination/C-P coupling with H-phosphonates, in the presence of silver(i) carbonate as oxidant, to produce useful arylphosphonates under microwave irradiation. the Partner Organisations 2014.

Full text of DOI:10.1039/c4ra01270d

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Palladium-catalyzed desulfitative C–P coupling of
arylsulfinate metal salts and H-phosphonates†
Cite this: RSC Adv., 2014, 4, 19214
*
Junchen Li, Xiaojing Bi, Hongmei Wang and Junhua Xiao
Received 13th February 2014
Accepted 14th April 2014
DOI: 10.1039/c4ra01270d
www.rsc.org/advances
Catalyzed by palladium(II) chloride, a diverse range of arylsulfinate compounds, we wish to develop an efficient desultative C–P
sodium, potassium, lithium, silver, zinc, and copper salts undergo coupling reaction of arylsulnate metal salts and H-phospho-
desulfination/C–P coupling with H-phosphonates, in the presence of nates, and have achieved the preliminary results.16 While this
silver(I) carbonate as oxidant, to produce useful arylphosphonates manuscript was under review, a similar work has been pub-
under microwave irradiation.
lished focusing on desultative C–P coupling of sodium aryl-
sulnates by Wang group.17 Differing from Wang's work, a
microwave-promoted method was applied to our desultative
C–P coupling, and the scope of arylsulnate metal salts was also
investigated.
The synthesis of organophosphorus compounds has received
signicant interest due to their widespread applications in
catalysis,1 synthesis,2 medicinal chemistry,3 and materials
chemistry.4 Among the manifold reported methods, the transi-
tion-metal-catalyzed cross-coupling reaction has been one of
the most powerful carbon–phosphorus bond-forming strate-
gies.5 Since the seminal work reported by Tavs and Hirao
independently,6 versatile efficient catalytic systems have been
developed for the preparation of arylphosphonates. In this
context, the aryl substrate scope has been expanded from aryl
halides to triates, mesylates, tosylates, phenols, diazonium
salts, boronic acids, and cyano compounds.7
Recently, increasing attention has been attracted to desul-
tative coupling via releasing SO2 from sulnate metal salts,
RSO2Na8 or (RSO2)2Zn.9 In contrast to current research in which
sulnates are mainly used to participate in sulfonylation reac-
tions,10 desultative coupling reactions have been well
demonstrated in desultative Heck reactions,8d tandem desul-
nation/C–H activations,8e,9,11 biaryls synthesis,11c,12 aryl ketones
synthesis,8f,g additions,13 and diarylmethanes synthesis.14
However, until now, this type of reaction is limited to the C–C
bond formations. As similar with the decarboxylative
couplings,15 we envisioned that the resulting aryl metallic
intermediate from arylsulnate metal salt generated in the
presence of palladium catalyst might also react with nucleo-
philes. Considering the great importance of organophosphorus
Our initial investigations focused on the PdCl2-catalyzed
desultative phosphonation of sodium p-toluenesulnate 1a
with diethyl phosphite 2a under microwave irradiation. AgI salts
are known as efficient oxidants in the Pd-catalyzed oxidative
couplings,18 thus we chose silver salts as oxidants to take part in
this reaction. As shown in Table 1, we were gratied to nd that
the use of 20 mol% of PdCl2 and 1 equivalent of Ag2CO3 in
toluene at 120 ꢀC provided a 8% yield of the desired product 3a
(Table 1, entry 1). Besides the desultative homocoupling
product 4,11a,12a the reduction/arylation product 5 and reduc-
tion/phosphorylation product 619 were also generated because
of the reductive properties of phosphites.20 Similar product
distribution was obtained when xylene was used as the solvent
(entry 2). When the reaction in other common solvents (e.g.,
EtOAc, THF, DCE, and DMF) was carried out, 3a was produced
in moderate yield, and the phosphorothioate ester 6 was effec-
tively controlled (entries 3–6). By employing Myers' solvent
system,21 the reaction yield was slightly improved to 68% (entry
7). Due to the competing reduction reactions, we anticipated
that the yield might be mended through increasing the amount
of the oxidant. To our delight, the augment of the dose of
Ag2CO3 to 2 equivalents gave 3a in 96% isolated yield (entry 8).
Moving to other silver salts (e.g., Ag2O, AgNO3, Ag2MoO4, and
AgOAc) resulted in lower yield (entries 9–12). Running the
reaction in DMSO afforded the coupled product in 80% yield
(entry 13). 20% yield of 3a was obtained in the absence of
Ag2CO3 whether or not the reaction was ran in air atmosphere
(entries 14–15), which indicating that the oxygen had no
effect on reaction. Absence of PdCl2 showed none of the
State Key Laboratory of NBC Protection for Civilian, Beijing 102205, P. R. China.
E-mail: xiao.junhua@pku.edu.cn
† Electronic supplementary information (ESI) available: Experimental procedures
and characterization data of all compounds and copies of NMR spectra. See DOI:
10.1039/c4ra01270d
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Table 1 Optimization of the reaction between 1a and 2aa
Table
2
Desulfitative phosphonation of 1a with various H-
phosphonatesa,b
Entry Ag salt (equiv.) Solvent
Yield of 3ab (%) 3a/4/5/6b,c (%)
1
2
3
4
5
6
Ag2CO3 (1)
Ag2CO3 (1)
Ag2CO3 (1)
Ag2CO3 (1)
Ag2CO3 (1)
Ag2CO3 (1)
Ag2CO3 (1)
Ag2CO3 (2)
Ag2O (2)
AgNO3 (2)
Ag2MoO4 (2)
AgOAc (2)
Ag2CO3 (2)
—
Toluene
Xylene
EtOAc
THF
DCE
DMF
DMF–DMSO 68
DMF–DMSO 99 (96e)
DMF–DMSO 81
DMF–DMSO 33
DMF–DMSO 43
DMF–DMSO
DMSO
DMF–DMSO 20
DMF–DMSO 21
DMF–DMSO ꢁ0
DMF–DMSO 40
8
14/0/3/83
16/4/6/74
84/4/11/1
80/0/16/4
57/13/22/8
77/2/17/4
82/0/10/8
94/5/1/0
10
63
66
44
64
7d
8d
9d
10d
11d
12d
13
14d
15d,f
a
Reaction conditions: 1a (0.36 mmol), 2 (0.3 mmol), PdCl2 (20 mol%),
90/8/0/0
Ag2CO3 (2 equiv.), DMF–DMSO (v/v ¼ 19/1, 2 mL), MW irradiation at
b
c
120 ꢀC for 10 min. Isolated yields. Only biaryl 4 was observed by
67/31/2/0
64/3/13/10
11/0/13/76
86/10/4/0
46/4/34/16
52/4/37/7
4/44/41/10
66/0/34/0
GC-MS.
4
80
moderate yields (3o, 3r and 3s). Sodium 2-naphthalenesulnate
provided the corresponding product in 58% yield (3t).
—
16d,g Ag2CO3 (2)
17d,h Ag2CO3 (2)
This catalytic system was also effective for other metal salts
of arylsulnate, including Li, K, Ag, Zn, and Cu. As depicted in
Table 4, the reaction of these arylsulnate metal salts with
diethyl phosphite gave the coupled product in moderate to
a
Reaction conditions: 1a (0.36 mmol), 2a (0.3 mmol), PdCl2 (20 mol%),
b
Ag salt, solvent (2 mL), MW irradiation at 120 ꢀC for 10 min. GC-MS
analysis of crude reaction mixture. Ratio of these four peaks was
c
d
determined by area normalization method. DMF–DMSO ¼ 19/1 (v/v).
e
f
g
Isolated yield in parentheses. Carried out in Ar. In the absence of
h
PdCl2. Carried out under conventional heating condition at 120 ꢀC
for 10 h.
Table 3 Desulfitative arylation of 2a with various arylsulfinate sodium
saltsa,b
phosphonation product 3a (entry 16), Therefore, PdCl2 and
Ag2CO3 might have a synergetic action in the desulnation.
When the reaction was operated under conventional heating
condition for 10 h, only 40% of 3a was generated (entry 17).
The scope of this desultative C–P coupling with respect to
the H-phosphonates has been investigated (Table 2). Moderate
to good yields could be obtained with various H-phosphonates
(3a–3f, 3h). The strong steric hindrance of the H-phosphonates
led to inhibition of the reaction (3g).
We have also explored functional group tolerance with
respect to the substituents on the sodium arylsulnate (Table
3). Both electron-rich groups and electron-withdrawing groups
performed well under our standard reaction conditions.
Sodium arylsulnates with a m-methyl substitution gave a yield
of 91% (3j). Versatile groups on the para-position of the aryl-
t
sulnates, such as Bu, AcNH, MeO, and halides, gave the
products in good yields (3l–3n, 3p and 3q). It was noteworthy
that the bromo substituent tolerated well in this reaction (3q).
However, much diethyl pyrophosphate was produced when p-
uoro, p-nitro, and p-triuoromethyl arylsulnate sodium salts
were employed as the substrates. Using DMSO as the solvent
could eliminate these disadvantages and gave the products in
a
Reaction conditions: 1a (0.36 mmol), 2 (0.3 mmol), PdCl2 (20 mol%),
Ag2CO3 (2 equiv.), DMF–DMSO (v/v ¼ 19/1, 2 mL), MW irradiation at
120 ꢀC for 10 min. b Isolated yields. c DMSO (2 mL).
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Entry
1
Arylsulnate
Product
Yieldb (%)
36
3a
2
3
3a
3a
86
44
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3b
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Reaction conditions: 1u–w (0.36 mmol) or 1x and 1y (0.18 mmol), 2a
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