Pd-Catalyzed Synthesis of α-Aryl Vinylphosphonates via Suzuki Arylation of α-Phosphonovinyl Nonaflates

Article abstract of DOI:10.1002/cjoc.201500414

The first palladium-catalyzed method for the arylation of α-phosphonovinyl nonaflates is described. Using a catalyst comprised of Pd(OAc)₂ and SPhos, terminal and internal α-aryl vinylphosphonates could be efficiently accessed under mild condit

Full text of DOI:10.1002/cjoc.201500414

COMMUNICATION
DOI: 10.1002/cjoc.201500414
Pd-Catalyzed Synthesis of α-Aryl Vinylphosphonates via
Suzuki Arylation of α-Phosphonovinyl Nonaflates
Meijuan Yuan,a Yewen Fang,*,c Li Zhang,a Xiaoping Jin,*,b Minjia Tao,c Qilin Ye,c Ruifeng Li,*,a
Jinjian Li,c Hui Zheng,c and Juejun Guc
a College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan,
Shanxi 030024, China
b Department of Biology and Pharmaceutical Sciences, Zhejiang Pharmaceutical College, Ningbo,
Zhejiang 315100, China
c School of Chemical Engineering, Ningbo University of Technology, Ningbo, Zhejiang 315016, China
The first palladium-catalyzed method for the arylation of α-phosphonovinyl nonaflates is described. Using a
catalyst comprised of Pd(OAc)2 and SPhos, terminal and internal α-aryl vinylphosphonates could be efficiently ac-
cessed under mild conditions. The reaction features a broad coupling partner scope and tolerates many functional
groups.
Keywords phosphonate, cross-coupling, palladium, catalysis, arylation
Introduction
interest in cross-coupling reactions,[11,12] we hypothe-
sized that the use of readily available α-phosphonovinyl
nonaflates 1a－1c[13] (Figure 1) as the electrophilic cou-
pling partners would allow access to a broad range of
terminal and internal α-aryl vinylphosphonates via Su-
zuki cross-coupling reactions.[14] Moreover, compared to
the arylsulfonyl group, the strong electron-withdrawing
nature of nonafluorobutanesulfonyl group would greatly
facilitate the oxidative addition of a metal into the vinyl
C－O bond. Herein, as a part of our program aiming at
establishing practical methods for the synthesis of vi-
nylphosphoates,[7a,10] we describe a straightforward and
modular approach to the α-aryl vinylphosphonates using
α-phosphonovinyl nonaflate as a simple and readily
available electrophilic coupling partner.
α-Aryl vinylphosphonates represent ubiquitous
structural motifs among biologically active molecules[1]
and organic synthesis.[2] Given the importance of α-aryl
vinylphosphonates, numerous methods have been de-
veloped for the synthesis of this motif.[2,3] In particular,
many efforts have been devoted to the development of
the metal-catalyzed synthetic protocols. In addition to
transition-metal-catalyzed C－P bond formation reac-
tions,[4-6] C－C cross-coupling reactions employing al-
kenyl or aryl halides as the electrophilic coupling part-
ners have become an alternative and/or complementary
route.[7] However, the difficult preparation and purifica-
tion of α-bromoalkenylphosphonates and alkenyl bo-
ronophosphonates with well-defined stereochemistry
make these procedures less attractive. Moreover, there is
no general protocol for the preparation of β-disubstituted
α-aryl vinylphosphonates.[6d]
ONf
PO(OEt)2
ONf
PO(OEt)2
ONf
PO(OEt)2
Me
H
Me
During the past three decades, the transition-metal-
catalyzed cross-coupling of O-based electrophiles has
emerged as an extremely valuable method for the for-
mation of carbon-carbon and carbon-heteroatom
bonds.[8] Among the enol-derived electrophiles, alkenyl
sulfonates have been widely employed in the vinylation
reactions of various carbon nucleophiles.[9] Recently, we
reported for the first time that the O-based electrophiles,
α-phosphonovinyl arylsulfonates, could efficiently cou-
ple with arylboronic acids to synthesize α-arylethenyl-
phosphonates.[10] Inspired by this report and our great
H
H
Me
1a
1b
1c
Figure 1 Readily available α-phosphonovinyl nonaflates.
Experimental
General procedure of the Suzuki arylation cross-
coupling reactions
A Schlenk flask was loaded with α-phosphonovinyl
nonaflates 1a (138.6 mg, 0.3 mmol), Pd(OAc)2 (3.4 mg),
*
E-mail: fang@nbut.edu.cn; rfli@tyut.edu.cn
Received June 1, 2015; accepted June 24, 2015; published online August 12, 2015.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201500414 or from the author.
Chin. J. Chem. 2015, 33, 1119—1123
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Yuan et al.
COMMUNICATION
SPhos (12.3 mg, 0.03 mmol), o-tolylboronic acid (61.2
mg, 0.45 mmol), Cs2CO3 (244.5 mg, 0.75 mmol) and
held under vacuum for 10 min and then filled with ni-
trogen. Then toluene (2.0 mL) was introduced and the
mixture was stirred at room temperature for 5 h. After
completion of the reaction, the mixture was diluted with
EtOAc (15.0 mL). The catalyst and inorganic base were
filtered off using a short pad of silica gel. The filtrate
was concentrated under reduced pressure and the residue
was purified by column chromatography on a silica gel
column using petroleum ether/EtOAc (2∶1, V∶V) as
eluent to give 74.7 mg (98% yield) of diethyl
(1-(o-tolyl)vinyl)phosphonate 3a as a pale yellow oil.
Table 1 Screening of ligands for arylation of α-phosphonovinyl
nonaflate 1aa
B(OH)2
Me
Pd(OAc)2 (5 mol%)
Ligand (10 mol%)
ONf
PO(OEt)2
PO(OEt)2
Me
+
Cs2CO3 (2.5 equiv)
toluene (0.15 mol/L)
r.t., 5 h
3a
1a
2a
Entry
1
Ligand
Yield/%
－
34
2
DPPF
＜10
3
XantPhos
rac-BINAP
DPEPhos
t-Bu3P•HBF4
t-Cy3P•HBF4
PPh3
14
4
16
Results and Discussion
5
78
39 (42d)
45 (＜10e)
6b,c
7b,c
8
For the optimization of reaction condition, various
commercially available bidentate and monophosphine
ligands were tested and the results were summarized in
Table 1. The Suzuki coupling reactions of the model
substrate 1a with 2-tolylboronic acid 2a were performed
in toluene under nitrogen atmosphere at room tempera-
ture for 5 h in the presence of 5 mol% Pd(OAc)2 and 10
mol% phosphorus ligand with Cs2CO3 (2.5 equiv.) as
the base. Interestingly, 34% isolated yield could be
achieved in the absence of external supporting ligand
(Entry 1). Several commercially available bisphos-
phanes, such as DPPF (1,1'-bis(diphenylphosphanyl)-
ferrocene), rac-BINAP (racemic-2,2'-bis(diphenylphos-
phanyl)-1,1'-binaphthyl), and XantPhos (4,5-bis-
(diphenylphosphanyl)-9,9-dimethylxanthene), all pro-
vided disappointing results (＜20%; Entries 2－4).
However, promising yield could be achieved with
DPEPhos [bis(2-diphenylphosphinophenyl)ether] as the
ligand (Entry 5). The bulky trialkylphosphanes such as
t-Bu3P•HBF4 and t-Cy3P•HBF4 were not very effective
for the expected coupling reaction (Entries 6 and 7) and
the mixtures of (Z)- and (E)-β-o-tolylvinylphos-
phonates[15] were also produced. The simple triaryl
phosphine ligands such as PPh3 and (2-MeC6H4)3P were
active and the yields were 78% and 70%, respectively
(Entries 8 and 9). With BrettPhos (2-(dicyclohexylpho-
sphino)-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-
biphenyl), efficient ligand for the coupling of vinyl to-
sylates and mesylates with boronic acids,[16] only 58%
of the desired product was isolated (Entry 10). Gratify-
ingly, the dialkylarylphosphine ligands, such as SPhos
(2-dicyclohexylphosphanyl-2',6'-dimethoxybiphenyl)[17]
and XPhos (2-dicyclohexylphosphanyl-2',4',6'-
triisopropylbiphenyl),[18] were very efficient ligands and
nearly quantitative yields were obtained (Entries 11 and
12). Consequently, SPhos was chosen as the optimal
ligand in the light of the isolated yield.
78
70
58
96
98
9
(2-MeC6H4)3P
BrettPhos
XPhos
10
11
12
SPhos
a
Reaction conditions: α-phosphonovinyl nonaflate (1a) (0.3
mmol), 2-MeC6H4B(OH)2 (0.45 mmol), Cs2CO3 (0.75 mmol), 5
mol% Pd(OAc)2, 10 mol% phosphine ligand, toluene (2 mL), r.t.,
5 h, isolated yield. b Numbers in parentheses indicate yield of a
c
mixture of β-o-tolylvinylphosphonates. E/Z isomer ratio of
β-o-tolylvinylphosphonates was determined by GC-MS analysis.
d
e
The ratio of E/Z was 33∶1. A 9∶1 mixture of (E)- and
(Z)-β-o-tolylvinylphosphonates was isolated.
of phenylboronic acid (3b), the Suzuki reaction pro-
ceeded well in the absence of external ligand and the
isolated yield could be 92%. It is noteworthy that halo-
gen substituents at the arene moiety of arylboronic acids
such as fluoride, chloride, and bromide are tolerable in
the present cross-coupling reaction (3e－3j), which
makes this method useful. It should be noted that the
choice of XPhos as the ligand is crucial for the coupling
reaction of 2-chlorophenylboronic acid (3g). A variety
of functional groups including methoxyl (3k－3n), ester
(3o), and alkene (3p) were tolerated under these condi-
tions. Furthermore, the coupling of 4-biphenylboronic
acid and naphthylboronic acids led to the corresponding
target products (3q－3t) in excellent yields. Of particu-
lar note is that the challenging coupling partners,[19]
such as 2,6-dimethoxylphenylboronic acid (3u) and
2,4,6-trimethylphenylboronic acid (3v), underwent the
reaction in excellent yields by raising the reaction tem-
perature to 50 ℃.
After demonstrating the scope of arylboronic acids,
we turned our attention to the heterocyclic boronic ac-
ids.[18b] A variety of sulfur-containing heterocyclic bo-
ronic acids such as thiophene, benzothiophene, and
dibenzothiophene could be employed, albeit at higher
temperature (50 ℃) (Scheme 2). Of note, thio-
With our optimized reaction conditions we set out to
investigate the cross-coupling of 1a with different aryl-
boronic acids (Scheme 1). In general, electron-neutral,
electron-rich, and electron-deficient arylboronic acids
are good coupling partners. Interestingly, as in the case
1120
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© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2015, 33, 1119—1123

Synthesis of α-Aryl Vinylphosphonates via Suzuki Arylation of α-Phosphonovinyl Nonaflates
Scheme 1 Cross-coupling of 1a with diverse arylboronic acids
Scheme 2 Cross-coupling of 1a with thiophene-derived boronic
acids
Pd(OAc)2 (5 mol%)
B(OH)2
PO(OEt)2
R
SPhos (10 mol%)
Pd(OAc)2 (5 mol%)
SPhos (10 mol%)
PO(OEt)2
+
S
ONf
Cs2CO3 (2.5 equiv.)
toluene (0.15 mol/L)
r.t., 5 - 8 h
R
R
B(OH)2
+
ONf
Cs2CO3 (2.5 equiv)
toluene (0.15 mol/L)
50 oC, 12 -15 h
R
PO(OEt)2
1a
S
PO(OEt)2
1a
2
3
4
5
PO(OEt)2
PO(OEt)2
PO(OEt)2
PO(OEt)2
PO(OEt)2
PO(OEt)2
PO(OEt)2
S
S
S
Me
3c, 99%
5a
, 38%
5b, 90%
Me
3d, 95%
5c, 82%
F
3b, 96% (92%a)
3e, 94%
PO(OEt)2
PO(OEt)2
PO(OEt)2
PO(OEt)2
PO(OEt)2
S
5d, 97%
Cl
Br
F
Cl
3g, 94%b
3i
, 92%
3f, 88%
3h
, 90%
Scheme 3 Pd-Catalyzed cross-coupling of (E)-vinylphos-
phonate (1b) with arylboronic acids
PO(OEt)2
PO(OEt)2
PO(OEt)2
PO(OEt)2
B(OH)2
Pd(OAc)2 (5 mol%)
SPhos (10 mol%)
Me
MeO
OMe
OMe
Br
OMe
3k
OMe
3m, 95%
+
(EtO)2OP
1b
ONf
Cs2CO3 (2.5 equiv)
toluene (0.15 mol/L)
50 oC , 5 h
3l, 99%
3j, 91%
, 91%
R
2
PO(OEt)2
PO(OEt)2
PO(OEt)2
PO(OEt)2
Me
O
O
(EtO)2OP
CO2Me
R
3p, 88%c
3q
, 92%
c
3o
, 86%
3n, 92%
6a: R = H, 97%
6b: R = Me, 98%
6c: R = OMe, 95%
PO(OEt)2
PO(OEt)2
PO(OEt)2
MeO
tantly, no trace of the alkene geometry erosion was ob-
served.[7d] Such exclusive stereoselectivity is of great
value due to the easy access of alkenyl nonaflate 1b
with well-defined stereochemistry.
3t
, 93%
3s, 93%
3r, 92%
PO(OEt)2
Me
PO(OEt)2
OMe
Me
After realizing the arylation of α-phosphonovinyl
nonaflates 1a and 1b, we were intrigued to discover
whether the present method could be suitable for the
coupling of 1c. Satisfyingly, the reactions of phenylbo-
ronic acid and 4-methylphenylboronic acid with 1c af-
forded the desired β-dimethyl vinylphosphonates 7a and
7b in excellent yields (Scheme 4). For the more hin-
dered 2-methylphenylboronic acid, the Suzuki arylation
was performed with a higher catalyst loading (10 mol%
Pd(OAc)2 and 20 mol% SPhos) and 2 equiv.
2-tolylboronic acid at 75 ℃ for 15 h and resulted in
87% yield of the product 7c. However, the conditions
employed for the 2-tolylboronic acid was fruitless when
applied to the more challenging 2,6-dimethylphenyl-
boronic acid. To the best of our knowledge, there is no
general protocol for the synthesis of β-disubstituted
α-aryl vinylphosphonates,[6d,20] thus our method may be
a good choice.
MeO
Me
3v, 90%c
3u, 88%c
Reaction conditions: 1a (0.3 mmol), 2 (0.45 mmol), Cs2CO3 (0.75 mmol),
5 mol% Pd(OAc)2, 10 mol% SPhos, N2, toluene (2 mL), r.t., 5－8 h,
isolated yield. a The reaction was conducted in the absence of the ligand.
b XPhos was used as the ligand. c The reaction temperature for 3o, 3p,
3u, and 3v is 50 ℃ and the reaction time is 12－15 h.
phene-2-boronic acid 4a provided a much lower yield
compared to the other three thiophene-derived boronic
acids (4b－4d). Unfortunately, all attempts to introduce
pyridine groups using 3- and 4-pyridineboronic acids
were unsuccessful.
To evaluate the stereochemical course of this reac-
tion, we examined the cross-coupling of (E)-vinylphos-
phonate 1b with some arylboronic acids. Pleasingly, the
use of slightly higher temperature (50 ℃) allowed full
conversion and excellent yields (Scheme 3). Impor-
Conclusions
We have developed a new protocol for the efficient
Chin. J. Chem. 2015, 33, 1119—1123
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Yuan et al.
COMMUNICATION
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Scheme 4 Synthesis of tetrasubstituted α-aryl alkenylphospho-
nates
Pd(OAc)2 (5 mol%)
SPhos (10 mol%)
B(OH)2
ONf
PO(OEt)2
Me
+
Cs2CO3 (2.5 equiv.)
toluene (0.15 mol/L)
50 oC , 15 h
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PO(OEt)2
Me
7
Me
Me
Me
Me
(EtO)2OP
(EtO)2OP
(EtO)2OP
Me
Me
Me
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7b, 94%
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a Reaction conditions: 1c (0.3 mmol), 2 (0.6 mmol), Cs2CO3 (0.75 mmol),
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synthesis of α-aryl vinylphosphonates via the Pd-cata-
lyzed Suzuki coupling reactions of α-phosphonovinyl
nonaflates with arylboronic acids. We also demonstrated
that the reaction of (E)-alkenylphosphonate with aryl-
boronic acids proceeded well with retention of the
original olefin stereochemistry. Particularly noteworthy
is that our new method is suitable for the efficient syn-
thesis of tetrasubstituted alkenylphosphonates. Addi-
tional investigations towards the application of α-phos-
phonovinyl nonaflates in cross-coupling reactions are
underway in our lab and will be reported in due course.
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The National Natural Science Foundation of China
(No. 21202090), the Zhejiang Provincial Natural Sci-
ence Foundation of China (No. LQ13B010004), the
Qianjiang Talents Project (B) (No. 2013R10076), the
Ningbo Science and Technology Innovation Team (No.
2011B82002), the National Training Programs of Inno-
vation and Entrepreneurship for Undergraduates (No.
201411058005), and NBUT are greatly acknowledged
for funding this work.
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