Mono and double Mizoroki-Heck reaction of aryl halides with dialkyl vinylphosphonates using a reusable palladium catalyst under aqueous medium

Article abstract of DOI:10.1039/c7ra06464k

Operationally-simple and reusable Pd-catalyzed mono and double Mizoroki-Heck reactions of aryl halides and dialkyl vinylphosphonates using ⁱPr₂NH as a base in aqueous medium under air were developed. For aryl iodides, the reaction could be conducted at 80 °C under a low catalyst loading (0.1-1 mol%). When aryl bromides were applied, however, a greater amount of catalyst (5 mol%) and a longer reaction time at 120 °C were required. Simply changing dialkyl vinylphosphonates as the limiting reagent led to the formation of 2,2-diaryl vinylphosphonates in good to high yields. After reaction, the residual aqueous solution could be reused for both mono and double Mizoroki-Heck reactions, making the reactions greener and reducing wastage of precious metals and use of harmful organic solvents as the reaction medium.

Full text of DOI:10.1039/c7ra06464k

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Mono and double Mizoroki–Heck reaction of aryl
halides with dialkyl vinylphosphonates using
a reusable palladium catalyst under aqueous
medium†
Cite this: RSC Adv., 2017, 7, 34293
*
Han-Sheng Lee, Shao-Hsuan Pai, Wei-Ting Liao, Xin-Jing Yang and Fu-Yu Tsai
Operationally-simple and reusable Pd-catalyzed mono and double Mizoroki–Heck reactions of aryl halides
and dialkyl vinylphosphonates using iPr2NH as a base in aqueous medium under air were developed. For aryl
iodides, the reaction could be conducted at 80 ꢀC under a low catalyst loading (0.1–1 mol%). When aryl
bromides were applied, however, a greater amount of catalyst (5 mol%) and a longer reaction time at
120 ꢀC were required. Simply changing dialkyl vinylphosphonates as the limiting reagent led to the
formation of 2,2-diaryl vinylphosphonates in good to high yields. After reaction, the residual aqueous
solution could be reused for both mono and double Mizoroki–Heck reactions, making the reactions
greener and reducing wastage of precious metals and use of harmful organic solvents as the reaction
medium.
Received 9th June 2017
Accepted 30th June 2017
DOI: 10.1039/c7ra06464k
rsc.li/rsc-advances
Although heterogeneous supported palladium catalysts have
been applied to study recyclability, harmful DMF was employed
as the reaction medium.64
Introduction
Alkenylphosphonates are important molecules that have been
widely applied in organic synthesis,1–14 materials science,15–17
medical chemistry,18–21 and as polymer additives22 and ame
retardants.23,24 Transition-metal-catalyzed reactions for the
formation of alkenylphosphonates mainly include cross-
coupling of P(O)H with vinyl halides or pseudo halides,25–40
olen cross-metathesis,41 reaction of HP(O) compounds with
alkynes42–50 or alkenes,51,52 Suzuki–Miyaura coupling of boronic
acids with vinylphosphonates,53–59 and Mizoroki–Heck reaction
of vinylphosphonates with various aryl partners.60–66 Although
diverse methods have been used and impressive results ob-
tained for the aforementioned reactions, most methods of such
catalytic reactions use harmful organic solvents, such as
CH2Cl2, toluene, and DMF, as the reaction medium. It would
therefore be highly valuable to develop a transition-metal-
catalyzed reaction for the synthesis of alkenylphosphonates
that does not employ an organic solvent as the reaction
medium. The introduction of neat water as the reaction
medium possesses several advantages, including a low cost,
nontoxicity, non-ammable nature, and easy separation from
the organic products and reuse of water-soluble catalysts.67–84
On the other hand, transition-metal-catalyzed cross-coupling
for the formation of 2,2-diaryl vinylphosphonates is rare. Known
procedures include phosphorylation of 1,1-diarylethene by Ag51,85
or Cu,26,27,86 arylzincation of alkynylphosphonates by Co,87 Negishi
coupling using vinylic tellurides,88 arylation of alkynylphospho-
nates with aryl halides or arylboronic acids,53,89,90 and HUSY
zeolite-promoted hydrophenylation of diethyl (2-phenylethynyl)
phosphonate with benzene.91 However, the coupling of aryl
halides and vinylphosphonates via a double Mizoroki–Heck
reaction has not yet been explored.
In this study, we developed a green and operationally-simple
palladium-catalyzed procedure to synthesize 2-aryl and 2,2-
diaryl vinylphosphonates using water as the reaction medium
under aerobic conditions. The use of aryl halides as the limiting
reagent produces mono Mizoroki–Heck products; on the
contrary, double Mizoroki–Heck products are selectively formed
when vinylphosphonate plays the role of limiting reagent
(Scheme 1). Moreover, the reusability of the residual aqueous
solution for these two kinds of reaction was also examined.
Institute of Organic and Polymeric Materials, National Taipei University of
Technology, 1, Sec. 3, Chung-Hsiao E. Rd., Taipei 10608, Taiwan. E-mail: fuyutsai@
ntut.edu.tw
† Electronic supplementary information (ESI) available: Spectroscopic
characterization data of all mono and double Mizoroki–Heck products; HRMS
data; copies of 1H, 13C, and 31P NMR spectra for unknown compounds. See
DOI: 10.1039/c7ra06464k
Scheme 1 Pd-catalyzed mono and double Mizoroki–Heck reactions
in water.
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replaced by diisopropyl vinylphosphonate, 2b, a near quantita-
tive yield of 4a was also delivered under the conditions of Entry
4 (Entry 9). Other commonly-used palladium salts were also
examined; however, the product yields were much lower than
those obtained with PdCl2(NH3)2 (Entries 10–12). Therefore,
reaction with 1 mol% PdCl2(NH3)2 in the absence of an auxiliary
ligand (Entry 4) was chosen as the optimal condition.
Following optimization of the reaction conditions (Table 1,
Entry 4), a variety of aryl iodides 1 were reacted with 2 in order to
explore the scope of this catalytic system. As shown in Table 2,
electron-rich aryl iodides 1b and 1c were arylated to 2 smoothly,
delivering the corresponding products in high yields (Entries 1
and 2). With electron-decient aryl iodides, for instance 1d–j,
the reactions took place very efficiently, and the desired prod-
ucts 3d–j and 4d–j were obtained in excellent yields (Entries 3–
9). Sterically-congested 1k–m did not affect the reaction, and
excellent product yields were achieved (Entries 10–12). 3-
Substituted aryl iodides 1n–p, without an electronic effect on
the aromatic ring, were able to be applied as reactants to couple
with 2, providing the desired products 3n–p and 4n–p in
excellent yields (Entries 13–15).
The oxidative addition of aryl bromides to palladium is more
difficult than that of iodides. So, increases of the reaction
temperature and catalyst loading were required to achieve the
coupling reaction when aryl bromides were employed. As
illustrated in Table 3, Mizoroki–Heck reaction of 5a and 2 with 5
mol% PdCl2(NH3)2 at 120 ꢀC in a sealable tube for 36 h led to the
formation of 3a and 4a in 68% and 69% yields, respectively
(Entry 1). Coupling of electron-rich aryl bromides 5b–c with 2
(Entries 2 and 3) was much slower than with electron-poor 5d–j
(Entries 4–9). A steric effect on 2-substituted aryl bromides was
apparent; therefore, coupling of 5k–m with 2 gave the target
products in yields of between 35% and 61%, respectively
(Entries 10–12). For 3-substituted aryl bromides, such as 5n–p,
the products were given in yields comparable with those
produced using 5a (Entries 13–15).
Results and discussion
i
In previous studies, we found that Pr2NH is the best base to
employ for the coupling of aryl halides and dialkyl allyl-
phosphonates;92 therefore, it was also used as the base in the
Mizoroki–Heck reaction of aryl halides and dialkyl vinyl-
phosphonate. As shown in Table 1, iodobenzene 1a (1 mmol),
diethyl vinylphosphonate 2a (2 mmol), iPr2NH (1.1 mmol), and
PdCl2(NH3)2 (5 mol%) were reacted in an open-air reactor at
80 ꢀC using water (3 mL) as the solvent. Under such conditions,
3a was obtained in a near-quantitative yield within 24 h (Entry
1). In order to optimize the conditions, reducing the catalyst
loading to 1 mol% afforded 3a in a 98% isolated yield (Entry 2).
Upon investigation of the reaction time, it was found that 6 h
was sufficient for the reaction to reach completion, indicating
the high efficiency of this catalytic system (Entries 3–5). With an
auxiliary water-soluble cationic 2,20-bipyridyl ligand,93 a 99%
product yield was achieved under conditions identical to those
for Entry 4 (Entry 6). The results showed that the water-soluble
cationic 2,20-bipyridyl ligand may be not crucial in the coupling
reaction. Use of this catalyst without an auxiliary ligand to fulll
the Mizoroki–Heck reaction has been described previously, in
which Pd nanoparticles were formed during the coupling
reaction.92 The reaction rates of vinylphosphonates were faster
than those of allylphosphonates, which may be due to the
electron-withdrawing phosphonate group of 2a becoming
attached directly to the vinyl carbon, which lowers the p* energy
level of the olen, facilitating coordination of the p bond to
palladium. Then, the catalyst loading was further reduced to 0.1
mol%, resulting in 68% and 70% product yields, respectively,
with a prolonged reaction time (Entries 7 and 8). When 2a was
Table 1 Optimization of palladium-catalyzed Mizoroki–Heck reaction
of 1a and 2a in watera
When the limiting reagent was changed from aryl halides to
vinylphosphonates, we were pleased to nd that double Miz-
oroki–Heck products could be selectively obtained (Table 4).
Under a lower catalyst loading, the reaction gave only a 47%
ꢀ
yield of 6a when conducted at 80 C for 48 h (Entry 1). Further
increasing the catalyst loading to 5 mol% was required to obtain
a satisfactory outcome (Entry 2). Both electron-rich and -de-
cient aryl iodides were able to couple with 2, giving the desired
products in good to high yields (Entries 3–6). However, low
yields were furnished when the triuoromethyl group was
located at the para position (Entry 7). It was known that 4-
substituted aryl iodides with strong electron-withdrawing
functional groups such as NO2- and CF3-render the double
Mizoroki–Heck reaction inert.94 Sterically-congested aryl
iodides, such as 1k and 1l, were transformed efficiently to the
corresponding 2,2-diaryl vinylphosphonates in higher yields,
indicating that the steric effect did not hinder this double
Mizoroki–Heck reaction (Entries 8 and 9). 3-Substituted aryl
iodides 1n–1p were also well-tolerated under such conditions,
which provided the corresponding double Mizoroki–Heck
products in good to high yields (Entries 10–12).
Entry
Pd (mol%)
Time (h)
Yield (%)b
1
2
3
4
PdCl2(NH3)2 (5)
(1)
(1)
(1)
(1)
(1)
(0.1)
(0.1)
24
24
12
6
3
6
36
48
6
6
6
99
98
97
99
81
99
68
70
99
72
42
28
5
6c
7
8
9d
10
11
12
(1)
Pd(OAc)2 (1)
PdCl2 (1)
PdCl2(MeCN)2 (1)
6
a
Reaction conditions: 1a (1.0 mmol), 2a (2.0 mmol) iPr2NH (1.1 mmol),
b
PdCl2(NH3)2, and H2O (3 mL) at 80 ꢀC under air. Isolated yields.
c
d
Cationic 2,20-bipyridyl was used as the ligand.
Diisopropyl
vinylphosphonate (2b) was used as the reactant.
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Table
2 Pd-catalyzed monoarylation of aryl iodides 1 to dialkyl
Table 3 Pd-catalyzed monoarylation of aryl bromides 5 to dialkyl
vinylphosphonate 2 in watera
vinylphosphonate 2 in watera
Entry
1
Aryl iodide
Phosphonate
Product
Yield (%)b
Entry
1
Aryl bromide
Phosphonate
Product
Yield (%)b
R ¼ Et, 2a
R ¼ iPr, 2b
3b
4b
92
88
R ¼ Et, 2a
R ¼ iPr, 2b
3a
4a
68
69
2a
2b
3c
4c
90
84
2a
2b
3b
4b
54
50
2
3
4
5
2
3
4
2a
2b
3d
4d
97
98
2a
2b
3c
4c
51
58
2a
2b
3e
4e
95
96
2a
2b
3d
4d
71
68
2a
2b
3f
4f
88
90
2a
2b
3e
4e
73
81
5
6
2a
2b
3g
4g
92
96
2a
2b
3g
4g
80
82
6
7
8
2a
2b
3h
4h
97
96
2a
2b
3h
4h
78
82
7
8
2a
2b
3i
4i
98
98
2a
2b
3i
4i
83
80
2a
2b
3j
4j
91
93
2a
2b
3j
4j
76
77
9
9
2a
2b
3k
4k
93
86
2a
2b
3k
4k
43
43
10
11
10
11
2a
2b
3l
4l
92
85
2a
2b
3l
4l
35
40
2a
2b
3m
4m
90
88
2a
2b
3m
4m
56
61
12
12
2a
2b
3n
4n
64
70
2a
2b
3n
4n
94
91
13
14
13
14
2a
2b
3o
4o
69
66
2a
2b
3o
4o
93
88
2a
2b
3p
4p
67
69
2a
2b
3p
4p
94
91
15
15
a
a
Reaction conditions: 5 (1.0 mmol), 2 (2.0 mmol), PdCl2(NH3)2 (5
Reaction conditions: 1 (1.0 mmol), 2 (2.0 mmol), PdCl2(NH3)2 (1
mol%) iPr2NH (1.1 mmol), and H2O (3 mL) at 120 ꢀC for 36 h.
i
b
mol%) Pr2NH (1.1 mmol), and H2O (3 mL) at 80 ꢀC for 6 h. Isolated
yields.
b
Isolated yields.
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Table 4 Pd-catalyzed double arylation of aryl iodides 1 to dialkyl
vinylphosphonate 2 in watera
Entry
Aryl iodide
Phosphonate
Product
Yield (%)b
47
1c
2
2a
6a
1a
2a
2b
2a
2b
6a
7a
6b
7b
80
82
66
74
3
4
5
6
2a
2b
6c
7c
64
59
Scheme 2 Proposed mechanism for the mono and double Mizoroki–
Heck reaction.
2a
2b
6d
7d
64
74
b-hydride elimination, the double Mizoroki–Heck product was
afforded.
2a
2b
6e
7e
56
59
On the basis of the broad scope of this catalytic reaction,
the reusability of the aqueous catalytic solution was then
examined, and the results are summarized in Table 5. Under
conditions identical to those described in Table 2, Entry 4,
aer the initial reaction of 1e and 2a, the reaction mixture was
extracted with ethyl acetate (3 ꢁ 3 mL) and 3e was puried by
column chromatography. The remaining aqueous solution
was then charged with 1e, 2a, and base for the reuse run. Only
slightly decreased product yields were obtained in the reuse
runs (Entry 1). When 5i was employed, we found that the
catalytic activity decayed quickly, and the formation of palla-
dium black on the glass reactor was observed due to the higher
reaction temperature (Entry 2).92 In reuse studies for the
double Mizoroki–Heck reaction, 1p and 2a were chosen as the
representative reactants. Aer extracting with ethyl acetate (3
ꢁ 3 mL), a 54% isolated yield of 6p could be still achieved in
the second reuse run (Entry 3). This operationally-simple
procedure therefore provides opportunities to reduce
wastage of precious metals and decrease use of harmful
organic solvents as the reaction medium, and meets the
criteria of green chemistry.
2a
2b
6g
7g
36
26
7
8
2a
2b
6k
7k
82
89
2a
2b
6l
7l
86
90
9
2a
2b
6n
7n
68
73
10
11
2a
2b
6o
7o
73
83
2a
2b
6p
7p
74
69
12
a
Reaction conditions: 1 (2.5 mmol), 2 (1.0 mmol), PdCl2(NH3)2 (5
mol%) iPr2NH (2.5 mmol), and H2O (3 mL) at 80 ꢀC for 48 h.
Isolated yields. c 1 mol% of PdCl2(NH3)2 was used.
b
Table 5 Reuse studies of aryl halides and 2a for mono and double
Mizoroki–Heck reactionsa
The proposed mechanism for both mono and double Miz-
oroki–Heck reactions was shown in Scheme 2. Aer the oxida-
tive addition of an aryl halide to Pd(0) nanoparticles,
coordination of a dialkyl vinylphosphonate to Pd(II) and
subsequent migratory insertion of the aryl group occurred. The
following b-hydride elimination delivered a mono Mizoroki–
Heck product along with palladium hydride, which was
neutralized by a base to regenerate Pd(0) nanoparticles. With
regard to the double Mizoroki–Heck reaction, the produced
mono Mizoroki–Heck product in the rst cycle acted as the
alkene for the Pd(II) coordination. Aer migratory insertion and
Yield (%)b
Entry
ArX
Product
Initial run
1st reuse
2nd reuse
1
2
3
1e
5i
1p
3e
3i
6p
95
83
74
88
68
63
76
23
54
a
Reaction conditions: ArX (1 mmol for Entries 1 and 2, 2.5 mmol for
Entry 3), 2a (2 mmol for Entries 1 and 2, 1 mmol for Entry 3),
i
PdCl2(NH3)2 (1 mol% for Entry 1, 5 mol% for Entries 2 and 3) Pr2NH
(1.1 mmol for Entries 1 and 2, 2.5 mmol for Entry 3), and H2O (3 mL)
b
at 80 ꢀC (Entries 1 and 3) or 120 ꢀC (Entry 2). Isolated yields.
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Experimental
Conclusions
General information
In conclusion, we have successfully developed an operationally-
Chemicals were purchased from commercial suppliers and simple and environmentally-benign Pd-catalyzed reaction for
were used without further purication. 2b was synthesized mono and double Mizoroki–Heck arylation of aryl halides and
according to the published procedure using P(OiPr)3 as the dialkyl vinylphosphonates using the greenest solvent, water, as
starting material.95 All 1H and 13C NMR spectra were recorded in the reaction medium under air. 2-Arylvinylphosphonates or 2,2-
CDCl3 at 25 ꢀC on a Bruker 300 NMR spectrometer, where diarylvinylphosphonates can be selectively obtained by simply
chemical shis (d in ppm) were determined with respect to the employing aryl halides or dialkyl vinylphosphonates as the
nondeuterated solvent as a reference (1H NMR: CHCl3 at limiting reagent. In addition, although the employment of aryl
7.24 ppm; 13C NMR: CDCl3 at 77.0 ppm). 31P NMR spectra for bromide showed poor reusability, the residual aqueous solution
unknown compounds were recorded in CDCl3 at 25 ꢀC on can be reused several times, making the reaction greener and
a Varian 400 NMR spectrometer using 85% H3PO4 as an external greatly reduces the wastage of precious metals and use of
standard. Melting points were recorded using melting point harmful organic solvents.
apparatus and were uncorrected. HRMS for unknown
compounds were recorded at the Instrument Center Service of
National Central University, Ministry of Science and Technology
Acknowledgements
of Taiwan. All known products obtained were pure, and their
This research was nancially supported by the Ministry of
spectra (1H and 13C NMR) were in agreement with those of
Science and Technology of Taiwan (MOST 105-2113-M-027-004).
authentic samples (see the ESI† for the spectral data of all mono
We thank Prof. Yi-Tsu Chan (National Taiwan University) for
and double Mizoroki–Heck products).
obtaining the 31P NMR spectra.
Typical procedure for the mono Mizoroki–Heck reaction
References
In a 25 mL reaction tube, PdCl2(NH3)2 (1 mol% for 1 or 5 mol%
1 I. P. Beletskaya and M. A. Kazankova, Russ. J. Org. Chem.,
2002, 38, 1391.
2 F. Alonso, I. P. Beletskaya and M. Yus, Chem. Rev., 2004, 104,
3079.
for 5) was added to H2O (3 mL) and the solution was stirred at
room temperature for 10 min. The tube was then charged with 1
or 5 (1.0 mmol), 2 (2.0 mmol), and Pr2NH (1.1 mmol) and
stirred at 80 ꢀC for 6 h or 120 ꢀC (for which a sealable tube was
used) for 36 h. Aer cooling the reaction to room temperature,
the resulting mixture was extracted with EtOAc (3 ꢁ 3 mL). The
combined organic phase was dried over MgSO4, and the solvent
was then removed under vacuum. Column chromatography on
silica gel (hexane/EtOAc ¼ 1/9) afforded the desired product.
i
3 A. L. Schwan, Chem. Soc. Rev., 2004, 33, 218.
ˆ
4 D. Leca, L. Fensterbank, E. Lacote and M. Malacria, Chem.
Soc. Rev., 2005, 34, 858.
5 S. Marque and P. Tordo, Top. Curr. Chem., 2005, 250, 43.
6 O. Delacroix and A. C. Gaumont, Curr. Org. Chem., 2005, 9,
1851.
7 S. N. Arbuzova, N. K. Gusarova and B. A. Tromov, ARKIVOC,
2006, 12.
Typical procedure for the double Mizoroki–Heck reaction
8 L. Coudray and J. L. Montchamp, Eur. J. Org. Chem., 2008,
3601.
9 S. Van der Jeught and C. V. Stevens, Chem. Rev., 2009, 109,
2672.
In a 25 mL reaction tube, PdCl2(NH3)2 (5 mol%) was added to
H2O (3 mL) and the solution was stirred at room temperature
for 10 min. The tube was then charged with 1 (2.5 mmol), 2
(1.0 mmol), and iPr2NH (2.5 mmol) and stirred at 80 ꢀC for 48 h.
Aer cooling the reaction to room temperature, the resulting
mixture was extracted with EtOAc (3 ꢁ 3 mL). The combined
10 T. Janecki, J. K˛edzia and T. W˛asek, Synthesis, 2009, 1227.
11 D. S. Glueck, Top. Organomet. Chem., 2010, 31, 65.
organic phase was dried over MgSO4, and the solvent was then 12 F. M. J. Tappe, V. T. Trepohl and M. Oestreich, Synthesis,
2010, 3037.
removed under vacuum. Column chromatography on silica gel
13 D. Zhao and R. Wang, Chem. Soc. Rev., 2012, 41, 2095.
14 H. Yorimitsu, Beilstein J. Org. Chem., 2013, 9, 1269.
15 H. Steininger, M. Schuster, K. D. Kreuer, A. Kaltbeitzel,
B. Bingol, W. H. Meyer, S. Schauff, G. Brunklaus, J. Maier
and H. W. Spiess, Phys. Chem. Chem. Phys., 2007, 9, 1764.
(hexane/EtOAc ¼ 1/9) gave the desired product.
Typical procedure for reuse of the residual aqueous solution
for mono and double Mizoroki–Heck reactions
The reaction was conducted following the previously-described 16 S. Kirumakki, J. Huang, A. Subbiah, J. Yao, A. Rowland,
procedure. Aer reaction, the aqueous reaction mixture was
extracted three times with EtOAc (3 mL) under vigorous stirring,
B. Smith, A. Mukherjee, S. Samarajeewa and A. Cleareld,
J. Mater. Chem., 2009, 19, 2593.
and the organic product was isolated from the combined 17 V. Spampinato, N. Tuccitto, S. Quici, V. Calabrese,
organic phase according to the previously-described procedure.
The residual aqueous solution was then charged with 1 or 5, 2,
and iPr2NH for the next run.
G. Marletta, A. Torrisi and A. Licciardello, Langmuir, 2010,
26, 8400.
18 T. Minami and J. Motoyoshiya, Synthesis, 1992, 333.
This journal is © The Royal Society of Chemistry 2017
RSC Adv., 2017, 7, 34293–34299 | 34297

View Article Online
RSC Advances
Paper
19 H. B. Lazrek, A. Rochdi, H. Khaider, J.-L. Barascut,
J.-L. Imbach, J. Balzrini, M. Witvrouw, C. Pannecouque and
E. De Clercq, Tetrahedron, 1998, 54, 3807.
20 P. Page, C. Blonski and J. Perie, Eur. J. Org. Chem., 1999,
2853.
C. Theunissen, J. Gatignol and A. C. Silvanus, Tetrahedron,
2014, 70, 1529.
48 I. G. Trostyanskaya and I. P. Beletskaya, Tetrahedron, 2014,
70, 2556.
49 L.-B. Han and M. Tanaka, J. Am. Chem. Soc., 1996, 118, 1571.
21 D. L. Jakeman, A. J. Ivory, M. P. Williamson and 50 L. Liu, Y. Wu, Z. Wang, J. Zhu and Y. Zhao, J. Org. Chem.,
G. M. Blackburn, J. Med. Chem., 1998, 41, 4439.
22 S. Jin and K. E. Gonsalves, Macromolecules, 1998, 31, 1010.
23 G. A. Russell, C.-F. Yao, H. I. Tashtoush, J. E. Russell and
D. F. Dedolph, J. Org. Chem., 1991, 56, 663.
24 M. Ruiz, M. C. Fernandez, S. Conde, A. Diaz and
J. M. Quintela, Synlett, 1999, 1903.
2014, 79, 6816.
51 Q. Gui, L. Hu, X. Chen, J. Liu and Z. Tan, Chem. Commun.,
2015, 51, 13922.
52 J.-W. Yuan, L.-R. Yang, P. Mao and L.-B. Qu, RSC Adv., 2016,
6, 87058.
53 I. Pergament and M. Srebnik, Org. Lett., 2001, 3, 217.
25 S. Thielges, P. Bisseret and J. Eustache, Org. Lett., 2005, 7, 54 Y. Kobayashi and A. D. William, Org. Lett., 2002, 4, 4241.
681. 55 G. W. Kabalka and S. K. Guchhait, Org. Lett., 2003, 5, 729.
26 G. Evano, K. Tadiparthi and F. Couty, Chem. Commun., 2011, 56 G. W. Kabalka, S. K. Guchhait and A. Naravane, Tetrahedron
47, 179. Lett., 2004, 45, 4685.
27 K. Jouvin, A. Coste, A. Bayle, F. Legrand, G. Karthikeyan, 57 Y. Kobayashi and A. D. William, Adv. Synth. Catal., 2004, 346,
K. Tadiparthi and G. Evano, Organometallics, 2012, 31,
7933.
28 L. Liu, Y. Wang, Z. Zeng, P. Xu, Y. Gao, Y. Yin and Y. Zhao,
Adv. Synth. Catal., 2013, 355, 659.
29 Y. Wu, L. Liu, K. Yan, P. Xu, Y. Gao and Y. Zhao, J. Org.
Chem., 2014, 79, 8118.
30 L. Liu, Y. Lv, Y. Wu, X. Gao, Z. Zeng, Y. Gao, G. Tang and
Y. Zhao, RSC Adv., 2014, 4, 2322.
1749.
58 R. Zhuang, J. Xu, Z. Cai, G. Tang, M. Fang and Y. Zhao, Org.
Lett., 2011, 13, 2110.
59 X. Mi, M. Huang, H. Guo and Y. Wu, Tetrahedron, 2013, 69,
5123.
60 A. Burini, S. Cacchi, P. Pace and B. R. Pietroni, Synlett, 1995,
677.
61 Y. Na, S. Park, S. B. Han, H. Han, S. Ko and S. Chang, J. Am.
Chem. Soc., 2004, 126, 250.
31 J.-F. Xue, S.-F. Zhou, Y.-Y. Liu, X. Pan, J.-P. Zou and
O. T. Asekun, Org. Biomol. Chem., 2015, 13, 4896.
32 D. A. Holt and J. M. Erb, Tetrahedron Lett., 1989, 30, 5393.
62 L. K. Hwang, Y. Na, J. Lee, Y. Do and S. Chang, Angew. Chem.,
Int. Ed., 2005, 44, 6166.
33 M. A. Kazankova, I. G. Trostyanskaya, S. V. Lutsenko and 63 W. Al-Maksoud, J. Mesnager, F. Jaber, C. Pinel and
I. P. Beletskaya, Tetrahedron Lett., 1999, 40, 569. L. Djakovitch, J. Organomet. Chem., 2009, 694, 3222.
34 T. Okuchi, T. Yano, T. Fukamachi, J. Ichikawa and 64 J. Tarabay, W. Al-Maksoud, F. Jaber, C. Pinel, S. Prakash and
T. Minami, Tetrahedron Lett., 1999, 40, 5337. L. Djakovitch, Appl. Catal., A, 2010, 388, 124.
35 P. Zhong, Z. X. Xiong and X. Huang, Synth. Commun., 2000, 65 H. Brunner, N. Le Cousturier de Courcy and J.-P. Genet,
30, 273. Synlett, 2000, 201.
36 T. Hirao, T. Masunaga, Y. Ohshiro and T. Agawa, Tetrahedron 66 N. N. Demik, M. M. Kabachnij, Z. S. Novikova and
Lett., 1980, 21, 3595. I. P. Beletskaya, Zh. Org. Khim., 1995, 31, 64.
37 N. B. Karlstedt, M. V. Anokhin and I. P. Beletskaya, Russ. 67 E. Levin, E. Ivry, C. E. Diesendruck and N. G. Lemcoff, Chem.
Chem. Bull., Int. Ed., 2013, 62, 2498. Rev., 2015, 115, 4607.
38 T. Ogawa, N. Usuki and N. Ono, J. Chem. Soc., Perkin Trans. 1, 68 B. Li and P. H. Dixneuf, Chem. Soc. Rev., 2013, 42, 5744.
1998, 2953. 69 M.-O. Simon and C.-J. Li, Chem. Soc. Rev., 2012, 41, 1415.
39 T. Hirao, T. Masunaga, N. Yamada, Y. Ohshiro and T. Agawa, 70 R. N. Butler and A. G. Coyne, Chem. Rev., 2010, 110, 6302.
Bull. Chem. Soc. Jpn., 1982, 55, 909. 71 K. H. Shaughnessy, Chem. Rev., 2009, 109, 643.
40 X. Zhang, H. Liu, X. Hu, G. Tang, J. Zhu and Y. Zhao, Org. 72 I. T. Horvath, Green Chem., 2008, 10, 1024.
´
Lett., 2011, 13, 3478.
73 C.-J. Li and B. M. Trost, Proc. Natl. Acad. Sci. U. S. A., 2008,
41 A. K. Chatterjee, T.-L. Choi and R. H. Grubbs, Synlett, 2001,
105, 13197.
1034.
74 S. Liu and J. Xiao, J. Mol. Catal. A: Chem., 2007, 270, 1.
42 L.-B. Han, C.-Q. Zhao, S. Onozawa, M. Goto and M. Tanaka, J. 75 D. Dallinger and C. O. Kappe, Chem. Rev., 2007, 107, 2563.
´
76 I. T. Horvath and P. T. Anastas, Chem. Rev., 2007, 107, 2167.
Am. Chem. Soc., 2002, 124, 3842.
43 L.-B. Han, C. Zhang, H. Yazawa and S. Shimada, J. Am. Chem. 77 C.-J. Li and L. Chen, Chem. Soc. Rev., 2006, 35, 68.
Soc., 2004, 126, 5080. 78 C.-J. Li, Chem. Rev., 2005, 105, 3095.
44 M. Niu, H. Fu, Y. Jiang and Y. Zhao, Chem. Commun., 2007, 79 N. E. Leadbeater, Chem. Commun., 2005, 2881.
272.
80 R. N. Butler and A. G. Coyne, Org. Biomol. Chem., 2016, 14,
45 S. K. Nune and M. Tanaka, Chem. Commun., 2007, 2858.
9945.
46 V. P. Ananikov, L. L. Khemchyan, I. P. Beletskaya and 81 K. Piradashvili, E. M. Alexandrino, F. R. Wurm and
Z. A. Starikova, Adv. Synth. Catal., 2010, 352, 2979. K. Landfester, Chem. Rev., 2016, 116, 2141.
47 G. Evano, A.-C. Gaumont, C. Alayrac, I. E. Wrona, 82 M. B. Gawande, V. B. D. Bonifacio, R. Luque, P. S. Branco and
´
J. R. Giguere, O. Delacroix, A. Bayle, K. Jouvin,
R. S. Varma, Chem. Soc. Rev., 2013, 42, 5522.
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RSC Advances
83 N. Mase and C. F. Barbas III, Org. Biomol. Chem., 2010, 8, 90 K. V. Sajna, V. Srinivas and K. C. K. Swamy, Adv. Synth. Catal.,
4043.
2010, 352, 3069.
84 A. Chanda and V. V. Fokin, Chem. Rev., 2009, 109, 725.
85 J. Zhao, P. Li, X. Li, C. Xia and F. Li, Chem. Commun., 2016,
91 D. S. Ryabukhin and A. V. Vasilyev, Mendeleev Commun.,
2016, 26, 500.
52, 3661.
92 W.-T. Liao, X.-J. Yang, Y.-Y. Tseng, C.-C. Wu, L.-J. Liu and
F.-Y. Tsai, Asian J. Org. Chem., 2015, 4, 1112.
93 S.-N. Chen, W.-Y. Wu and F.-Y. Tsai, Tetrahedron, 2008, 64,
8164.
86 L.-L. Mao, A.-X. Zhou, N. Liu and S.-D. Yang, Synlett, 2014,
2727.
87 K. Murakami, H. Yorimitsu and K. Oshima, Org. Lett., 2009,
11, 2373.
94 D. Xu, C. Lu and W. Chen, Tetrahedron, 2012, 68, 1466.
˜
88 D. Alves, R. F. Schumacher, R. Brandao, C. W. Nogueira and 95 P. Fourgeaud, C. Midrier, J.-P. Vors, J.-N. Volle, J.-L. Pirat and
G. Zeni, Synlett, 2006, 1035.
D. Virieux, Tetrahedron, 2010, 66, 758.
89 I. Pergament and M. Srebnik, Tetrahedron Lett., 2001, 42,
8059.
This journal is © The Royal Society of Chemistry 2017
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