Palladium-catalyzed desulfitative cross-coupling reaction of sodium arylsulfinates with H-phosphonate diesters

Article abstract of DOI:10.1002/adsc.201300983

A novel and convenient palladium-catalyzed cross-coupling reaction of H-phosphonate diesters with sodium arylsulfinates was developed via desulfitation in the presence of silver carbonate and tetra-butylammonium chloride. This method is highly efficient and provides a rapid access to a broad spectrum of arylphosphonate diesters in good to excellent yields.

Full text of DOI:10.1002/adsc.201300983

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DOI: 10.1002/adsc.201300983
Palladium-Catalyzed Desulfitative Cross-Coupling Reaction of
Sodium Arylsulfinates with H-Phosphonate Diesters
Tao Miaoa and Lei Wanga,b,*
a
Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, Peopleꢀs Republic of China
Fax : (+86)-561-309-0518; phone: (+86)-561-380-2069; e-mail: leiwang@chnu.edu.cn
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, Peopleꢀs
b
Republic of China
Received: November 5, 2013; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300983.
Abstract: A novel and convenient palladium-cata-
lyzed cross-coupling reaction of H-phosphonate di-
ACHTUNGTRENNUNGesters with sodium arylsulfinates was developed via
desulfitation in the presence of silver carbonate and
tetra-butylammonium chloride. This method is
highly efficient and provides a rapid access to
a broad spectrum of arylphosphonate diesters in
good to excellent yields.
availability. Although arylsulfinic acids (or salts) are
generally used as sulfonylation reagents,[9] they have
shown great potential as ideal aryl sources via release
of SO2 under transition metal catalysis. Recently, tran-
sition metal-catalyzed desulfitative coupling reactions
ꢀ
have emerged as powerful alternatives for C C bond
formation, thus providing new protocols for Heck-
type reactions,[10] formation of biaryls,[11] synthesis of
[13]
aryl ketones,[12] direct C H arylations. However, to
ꢀ
Keywords: arylphosphonates; desulfitative cross-
coupling reaction; H-phosphonate diesters; palladi-
um; sodium arylsulfinates
the best of our knowledge, this promising, attractive
coupling remains totally unexplored in the field of C
P bond formation. Stimulated by the advancement of
a cross-coupling reaction of H-phosphonate diesters
and our interest in the coupling of sodium arylsulfi-
nates, herein we wish to report the first example of
ꢀ
ꢀ
palladium-catalyzed desulfitative C P cross-coupling
Arylphosphonates are valuable structural components of sodium sulfinates with H-phosphonate diesters
in a number of biologically active compounds, phar- under mild conditions, providing arylphosphonates in
maceuticals and functional materials,[1] and act as the good to excellent yields.
key intermediates for the preparation of P ligands.[2]
Initially, sodium benzenesulfinate (1a) and diethyl
Among various methods for the synthesis of them, phosphonate (2a) was chosen as a model reaction to
the transition metal-catalyzed cross-coupling reactions optimize the reaction conditions with a number of ad-
of aryl electrophiles with dialkyl H-phosphonates or ditives, oxidants, and solvents in the presence of
trialkyl phosphites offer straightforward and conven- Pd
(PPh3)2Cl2 (5 mol%) at 808C for 9 h (Table 1). We
ꢀ
ient approaches for the formation of C P bonds. In were pleased to find that the desulfitative coupling re-
1981, Hirao and co-workers reported their pioneering action proceeded smoothly on using Ag2CO3 as oxi-
work on the palladium-catalyzed cross-coupling of di- dant and DMSO as solvent, providing the desired ar-
alkyl phosphonates with aryl halides, setting up ylphosphonate product 3a in 60% isolated yield
a stage for this territory of study.[3] Subsequently, sig- (Table 1, entry 1). Considering the promotion of qua-
nificant advances were made to assemble arylphos- ternary ammonium salts in the palladium-catalyzed P-
ACHTUNGTRENNUNG
phonates employing aryl halides,[4] sulfonic esters,[5] arylation reaction,[4c,d] we attempted this cross-cou-
diazonium salts,[6] boronic acids[7] and even arenes[8] as pling reaction using a quaternary ammonium salt as
the coupling partners with phosphorus nucleophiles. an additive to improve the yield of the desired prod-
Owing to the broad applications of arylphosphonates, uct. Then several quaternary ammonium salts were
the development of novel and efficient methods for added to the reaction system. To our delight, use of
their preparation from simple and readily available tetrabutylammonium chloride (TBAC) gave the de-
aryl sources is highly desirable in organic synthesis.
sired product (3a) in 89% yield (Table 1, entry 2).
Arylsulfinic acids (or salts), as important starting Meanwhile, the desulfitative coupling reaction also
materials in organic synthesis, have attracted much at- proceeded in comparable efficiency and yield in the
tention due to their low cost, high stability, and ready presence of tetramethylammonium chloride (TMAC)
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Tao Miao and Lei Wang
Table 1. Palladium-catalyzed desulfitative cross-coupling re-
action of sodium benzenesulfinate (1a) with diethyl phos-
phonate (2a) under various conditions.[a]
hand, organic oxidants, such as BQ (1,4-benzoqui-
none), TBHP (tert-butyl hydroperoxide) were also ex-
amined and were found to be harmful in this transfor-
mation (Table 1, entries 18 and 19). Furthermore, no
desired product was obtained when oxygen was used
as oxidant (Table 1, entry 20).
Optimizations of Pd sources are summarized in
Table 2. By contrast, Pd
est reactivity and the desired product 3a was obtained
in excellent yield (Table 2, entry 1). Pd(CH3CN)2Cl2,
PdCl2, Pd(PPh3)4, Pd(OAc)2 and Pd(OCOCF3)2 were
less effective and afforded 3a in 41–70% yields
(Table 2, entries 2–6).
ACHTUGNTRENUN(GN PPh3)2Cl2 exhibited the high-
Entry
Oxidant
Additive
Solvent
Yield[b] [%]
AHCTUNGTRENNUNG
1
2
3
4
5
6
7
8
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2O
–
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
60
89
81
39
66
45
58
75
57
36
11
0
35
14
0
0
0
G
R
ACHTUNGTRENNUNG
TBAC
TMAC
TBAF
TBAB
TBAI
TBAC
TBAC
TBAC
TBAC
TBAC
TBAC
TBAC
TBAC
TBAC
TBAC
TBAC
TBAC
TBAC
TBAC
With the optimized reaction conditions (5 mol% of
PdACHTNURTGNE(UNG PPh3)2Cl2, 1.6 equiv. of Ag2CO3, 1.5 equiv. of
TBAC, DMSO, 808C, 9 h) in our hands, the scope and
limitation of the Pd-catalyzed desulfitative cross-cou-
pling of sodium arylsulfinates with H-phosphonate
diesters was examined. As can be seen from Table 3,
sodium benzenesulfinates bearing substituents includ-
ing methyl, tert-butyl, methoxy and acetylamino react-
ed with diethyl phosphonate (2a) effectively and af-
forded the desired products 3b–3f in 80–88% yields
(Table 3, entries 2–6). Meanwhile, this reaction was
also tolerant of halogen substituents, such as fluoro,
chloro and bromo groups on the aromatic ring of
sodium benzenesulfinate and the corresponding prod-
ucts 3g–3i were obtained in excellent yields (Table 3,
entries 7–9). Sodium 1,1’-biphenylsulfinate, 1-naph-
thylsulfinate and 2-naphthylsulfinate were also tested
for their reactions with 2a under the present condi-
tions, and the desired desulfitative cross-coupling
products 3j, 3k and 3l were isolated in 81, 92, and
95% yields, respectively (Table 3, entries 10–12).
However, these reaction conditions are not suitable
DMA
9
toluene
CH3CN
EtOH
10
11
12
13
14
15
16
17
18
19
20[c]
dioxane
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
CuACHTUNGTRENNUNG(OAc)2
AgOAc
AgSbF6
K2S2O8
BQ
TBHP
O2
0
0
0
[a]
Reaction conditions: 1a (0.40 mmol), 2a (0.25 mmol), and
Pd(PPh3)2Cl2 (5 mol%), oxidant (0.40 mmol), additive
ACHTUNGTRENNUNG
(0.375 mmol), solvent (2.0 mL), 808C for 9 h.
Isolated yield.
O2 balloon.
[b]
[c]
(Table 1, entry 3 vs. entry 2). However, tetrabutylam- for 4-nitrophenylsulfinate, only a trace of product 3m
monium fluoride (TBAF), tetrabutylammonium bro-
mide (TBAB), and tetrabutylammonium iodide
Table 2. Effect of the Pd source on the coupling reaction of
sodium benzenesulfinate (1a) with diethyl phosphonate
(2a).[a]
(TBAI) were inferior and led to the formation of 3a
in 39–66% yields (Table 1, entries 4–6). Next, the
effect of the solvent on the model reaction was exam-
ined. Among the solvents screened, DMSO exhibited
the highest reactivity. When the model reaction was
carried out in DMA, DMF or toluene, 57–75% yields
of 3a were obtained (Table 1, entries 7–9). Using
CH3CN or EtOH instead of DMSO as solvent,
CH3CN gave 3a in 36% yield, and EtOH generated
3a only in 11% yield (Table 1, entries 10 and 11).
However, dioxane was not suitable and the reaction
was prevented (Table 1, entry 12). Further exploration
of a variety of commercially available oxidants indi-
cated that Ag2CO3 was superior to the others. Ag2O
Entry
Pd source
Yield[b] [%]
1
2
3
4
5
6
Pd
Pd
PdCl2
Pd
Pd
Pd
N
89
70
63
60
50
41
and CuACHTUNGTRENNUNG(OAc)2 were less effective and produced de-
[a]
sired 3a in 35% and 14% yields, respectively (Table 1,
entries 13 and 14). The other inorganic oxidants in-
cluding AgOAc, AgSbF6 and K2S2O8 did not work in
the reaction (Table 1, entries 15–17). On the other
Reaction conditions: 1a (0.40 mmol), 2a (0.25 mmol), Pd
catalyst (5 mol%), Ag2CO3 (0.40 mmol), TBAC
(0.375 mmol), DMSO (2.0 mL), 808C, 9 h.
Isolated yield.
[b]
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Palladium-Catalyzed Desulfitative Cross-Coupling Reaction
Table 3. Palladium-catalyzed desulfitative cross-coupling re-
action of various sodium arylsulfinates with diethyl phos-
phonate (2a).[a]
[a]
[b]
Reaction conditions:
1 (0.40 mmol), 2a (0.25 mmol),
Pd(PPh3)2Cl2 (5 mol%), Ag2CO3 (0.40 mmol), TBAC
AHCTUNGTRENNUNG
(0.375 mmol), DMSO (2.0 mL), 808C, 9 h.
Isolated yields.
was observed when 4-nitrophenylsulfinate participat-
ed in the reaction with diethyl phosphonate (2a)
(Table 3, entry 13).
The substrate scope with respect to H-phosphonate
diesters was also investigated (Scheme 1). Under the
standard reaction conditions, dimethyl, di(isopropyl),
di(tert-butyl), diACTHNUTRGNE(NUG n-butyl) and dibenzyl phosphonates
all reacted with sodium arylsulfinates smoothly, gener-
ating the corresponding arylphosphonates 3n–3ae in
70–95% yields. The reactivity of dialkyl phosphonates
in the reaction indicated that dimethyl phosphonate
was comparable with diethyl phosphonate; diACTHNUTRGENUG(N n-butyl)
phosphonate displayed higher activity than did di(iso-
propyl) phosphonate and di(tert-butyl) phosphonate
using sodium arylsulfinates as coupling partners under
the optimal reaction conditions. It should be noted
that dibenzyl phosphonate with a bulky aliphatic
chain also underwent the desulfitative cross-coupling
reaction and gave the desired products (3ac–3ae) in
good yields.
Based on the previous literature and the above ob-
servations, a plausible mechanism to realize the desu-
fitative cross-coupling is shown in Scheme 2. The first
step is the reaction of Pd(II)Cl
arylsulfinate, providing palladium salt A. Elimination
of SO2 from A generates ArPd(II)Cl(PPh3)2, which
2ACHTUNGTRENN(NUG PPh3)2 with sodium
AHCTUNGTRENNUNG
differs from the classic formation of the aryl-palladi-
um species through oxidative addition and transme-
tallation. Then nucleophilic coordination of the phos-
phonate to ArPd(II)ClACHTNUGTRNEGNU(PPh3)2, affords the intermedi-
ate B in the presence of a base, which is probably ac-
celerated by Clꢀ from TBAC.[4c,d] Subsquently, reduc-
tive elimination from B produces arylphosphonate
and Pd(0) species. Finally, Pd(0) is oxidized by Ag(I)
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Tao Miao and Lei Wang
Scheme 1. Palladium-catalyzed desulfitative cross-coupling reaction of sodium arylsulfinates with dialkyl phosphonates. Re-
action conditions: 1 (0.40 mmol), 2 (0.25 mmol) and Pd
DMSO (2.0 mL), 808C, 9 h. Isolated yields are reported.
AHCTUNGTRENNUNG
Experimental Section
Typical Procedure for the Desulfitative Cross-
Coupling Reaction
The Schlenk tube equipped with a stir bar was charged with
sodium
arylsulfinate
(0.40 mmol),
PdACHTGNUETRNNU(G PPh3)2Cl2
(0.0125 mmol), Ag2CO3 (0.40 mmol), TBAC (0.375 mmol),
DMSO (2.0 mL) and H-phosphonate diester (0.25 mmol)
was added by syringe. The reaction mixture was stirred at
808C for 9 h. Then it was cooled to room temperature, the
reaction mixture was diluted with 5.0 mL of ethyl acetate,
filtered through a pad of silica gel, followed by washing the
pad of the silica gel with the same solvent (10.0 mL). The fil-
trate was washed with water (3ꢂ5.0 mL). The organic phase
was dried over MgSO4, filtered, and concentrated under re-
duced pressure to yield the crude product, which was further
purified by flash chromatography on silica gel with ethyl
acetate-petroleum ether (1:2!2:1) to provide the corre-
sponding product.
Scheme 2. The proposed reaction mechanism.
to regenerate the catalytically active Pd(II) complex
and finishes the catalytic cycle.
In summary, we have developed a novel and con-
venient palladium-catalyzed cross-coupling reaction
of H-phosphonate diesters with sodium arylsulfinates
via desulfitation in the presence of Ag2CO3 and
TBAC. To the best of our knowledge, this is the first
Acknowledgements
This work was financially supported by the National Science
Foundation of China (Nos. 21372095, 21172092).
ꢀ
C P bond formation using sodium arylsufinates as
coupling species via a desufitative cross-coupling pro-
cess. This method is highly efficient and provides
rapid access to a broad spectrum of arylphosphonate
diesters in good to excellent yields. An investigation
on the detailed reaction mechanism and use of
sodium arylsulfinates as aryl source in other coupling
reactions is underway.
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6 Palladium-Catalyzed Desulfitative Cross-Coupling Reaction
of Sodium Arylsulfinates with H-Phosphonate Diesters
Adv. Synth. Catal. 2014, 356, 1 – 6
Tao Miao, Lei Wang*
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