Diphosphino-functionalized MCM-41-immobilized rhodium complex: A highly efficient and recyclable catalyst for the hydrophosphinylation of terminal alkynes

Article abstract of DOI:10.1007/s10562-012-0781-9

Diphosphino-functionalized MCM-41-immobilized rhodium complex (MCM-41-2P-RhCl₃) was conveniently synthesized from commercially available and cheap γ-aminopropyltriethoxysilane via immobilization on mesoporous MCM-41, followed by reacting with diphenylphosphinomethanol and rhodium chloride. It was found that this heterogeneous rhodium complex is a highly efficient catalyst for the hydrophosphinylation of terminal alkynes with diphenylphosphine oxide and can be recovered and recycled by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity.

Full text of DOI:10.1007/s10562-012-0781-9

Catal Lett (2012) 142:803–808
DOI 10.1007/s10562-012-0781-9
Diphosphino-Functionalized MCM-41-Immobilized Rhodium
Complex: A Highly Efficient and Recyclable Catalyst
for the Hydrophosphinylation of Terminal Alkynes
•
•
•
Fang Yao Jian Peng Wenyan Hao
Mingzhong Cai
Received: 12 December 2011 / Accepted: 30 January 2012 / Published online: 4 April 2012
Ó Springer Science+Business Media, LLC 2012
Abstract Diphosphino-functionalized MCM-41-immo-
bilized rhodium complex (MCM-41-2P-RhCl3) was con-
veniently synthesized from commercially available and
cheap c-aminopropyltriethoxysilane via immobilization on
mesoporous MCM-41, followed by reacting with diphe-
nylphosphinomethanol and rhodium chloride. It was found
that this heterogeneous rhodium complex is a highly effi-
cient catalyst for the hydrophosphinylation of terminal
alkynes with diphenylphosphine oxide and can be recov-
ered and recycled by a simple filtration of the reaction
solution and used for at least 10 consecutive trials without
any decreases in activity.
alkenylphosphine oxides to afford versatile bifunctional
compounds, which allow further synthetic transformations.
Alkenylphosphine oxides have also been used for the for-
mation of carbon–carbon bond via reactions with carbanion
species [13] or carbon-centered radicals [14, 15]. Transition-
metal-catalyzed addition of an P–H bond to alkynes is a
straightforward method for the generation of alkenylphos-
phorus compounds [16–20], but this transformation always
results in a mixture of E/Z configurations, and it is difficult to
obtain one single product. Han et al. [21] described a rho-
dium-catalyzed regio- and stereoselective hydrophosphiny-
lation of alkynes with Ph2P(O)H, which provides a new
convenient and clean method for the preparation of (E)-al-
kenylphosphine oxides. However, industrial applications of
homogeneous rhodium complexes remain a challenge
because they are expensive, cannot be recycled, and difficult
to separate from the product mixture, which is a particularly
significant drawback for their application in the pharma-
ceutical industry. The immobilization of catalytically active
species, i.e., organometallic complexes, onto a solid support
to produce a molecular heterogeneous catalyst is one
potential solution to the latter two problems [22].
Keywords Supported rhodium catalyst Á Functionalized
MCM-41 Á Phosphine rhodium complex Á
Hydrophosphinylation Á Heterogeneous catalysis
1 Introduction
Alkenylphosphine oxides are key synthetic intermediates for
the preparation of various phosphine ligands and present in
numerous biologically active products [1–6]. In addition, a
variety of heteroatom nucleophiles such as alcohols [7],
thiols [8], primary and secondary amines [9–11], and phos-
phines [12] readily add to the double bond in
The high costs of the transition metal catalysts coupled
with toxic effects associated with many transition metals
has led to an increased interest in immobilizing catalysts
onto a support. Heterogeneous catalysis also helps to
minimize wastes derived from reaction workup, contrib-
uting to the development of green chemical processes [23,
24]. Supported rhodium catalysts have successfully been
used for hydrogenation [25, 26], hydroformylation [27–29],
hydrosilylation [30, 31], polymerization of aromatic acet-
ylenes [32] and hydrothiolation of acetylenes [33].
Developments on the mesoporous material MCM-41 pro-
vided a new possible candidate for a solid support
for immobilization of homogeneous catalysts [34–36].
F. Yao Á J. Peng Á W. Hao Á M. Cai (&)
Department of Chemistry, Jiangxi Normal University,
Nanchang 330022, People’s Republic of China
e-mail: caimzhong@163.com
F. Yao
Department of Chemistry and Pharmaceutical Engineering,
West Branch of Zhejiang University of Technology,
Quzhou 324000, People’s Republic of China
123

804
F. Yao et al.
MCM-41 has a regular pore diameter of ca. 5 nm and a
specific surface area [700 m2 g-1 [37]. Its large pore size
allows passage of large molecules such as organic reactants
and metal complexes through the pores to reach to the surface
of the channel [38–40]. It is generally believed that high
surface area of heterogeneous catalyst results in high cata-
lytic activity. Considering the fact that the MCM-41 support
has an extremely high surface area and the catalytic rhodium
species is anchored on the inner surface of the mesopore of
MCM-41 support, we expect that MCM-41-immobilized
rhodium catalyst will exhibit high activity and good reus-
ability. Shyu et al. [41] reported phosphinated MCM-41-
supported rhodium complex for catalytic hydrogenation of
olefins and found that it is an excellent hydrogenation cata-
lyst with turnover frequency (TOF) three times higher than
that of RhCl(PPh3)3 in the hydrogenation of cyclohexene.
However, to the best of our knowledge, no hydrophosph-
inylation of alkynes with diphenylphosphine oxide catalyzed
by MCM-41-immobilized phosphine rhodium complex has
been reported until now. In this paper, we wish to report the
synthesis of diphosphino-functionalized MCM-41-immobi-
lized rhodium complex (MCM-41-2P-RhCl3) and its cata-
lytic properties in the hydrophosphinylation reaction of
alkynes with diphenylphosphine oxide.
dry toluene (180 mL). The mixture was stirred for 48 h at
100 °C. Then the solid was filtered and washed by CHCl3
(2 9 20 mL), and dried in vacuum at 160 °C for 5 h. The
dried white solid was then soaked in a solution of Me3SiCl
(4.36 g, 40 mmol) in dry toluene (150 mL) at room tem-
perature under stirring for 24 h. Then the solid was filtered,
washed with acetone (3 9 20 mL) and diethyl ether
(3 9 20 mL), and dried in vacuum at 120 °C for 5 h to
obtain 3.54 g of hybrid material MCM-41-NH2. The
nitrogen content was found to be 1.27 mmol/g by ele-
mental analysis.
2.2 Preparation of MCM-41-2P
A Schlenk flask was charged with paraformaldehyde
(0.701 g, 23.3 mmol), dry MeOH (20 mL) and diphenyl-
phosphine (4.340 g, 23.3 mmol). The reaction mixture was
heated to 60 °C under Ar until the white suspension formed
a colorless solution. After removal of MeOH in vacuo the
remaining viscous oil was diluted in dry toluene (20 mL).
This solution was added to a suspension of MCM-41-NH2
(3.020 g) in dry toluene (60 mL) and the reaction mixture
was heated to 105 °C under Ar for 24 h. In the cooler
regions of the flask the water-toluene azeotrope separated
indicating the reaction progress. After cooling to room
temperature the solid product was collected by filtration
under Ar, washed with dry toluene (4 9 30 mL), CH2Cl2/
THF (1/1) (2 9 30 mL), CH2Cl2 (2 9 30 mL) and dried in
vacuo (100 °C) for 5 h to give 4.08 g of the light yellow
MCM-41-2P. The nitrogen and phosphine content was
found to be 0.76 and 1.44 mmol/g, respectively.
2 Experimental
All chemicals were reagent grade and used as purchased. The
mesoporous material MCM-41 was prepared according to a
literature procedure [42]. All reactions were performed
under an inert atmosphere of dry argon using distilled dried
solvents. All hydrophosphinylation products were charac-
terized by comparison of their spectra and physical data with
authentic samples. IR spectra were determined on a Perkin-
2.3 Preparation of MCM-41-2P-RhCl3
To a solution of RhCl3 (0.171 g) in acetone (40 mL) was
added MCM-41-2P (1.85 g). The mixture was heated at
reflux under Ar for 72 h. The solid product was filtered by
suction, washed with acetone, distilled water and acetone
successively and dried at 70 °C/26.7 Pa under Ar for 3 h to
give 1.91 g of the brown yellow polymeric rhodium com-
plex (MCM-41-2P-RhCl3). The phosphine and rhodium
content was 1.23 and 0.29 mmol/g, respectively.
1
Elmer 683 instrument. H NMR (400 MHz) spectra were
recorded on a Bruker Avance 400 MHz spectrometer with
TMS as an internal standard in CDCl3 as solvent. 13C NMR
(100 MHz) spectra were recorded on a Bruker Avance
400 MHz spectrometer in CDCl3 as solvent. Rhodium con-
tent was determined with inductively coupled plasma atom
emission Atomscan16 (ICP-AES, TJA Corporation). X-ray
powder diffraction patterns were obtained on Damx-rA
(Rigaka). The BET surface area and pore analysis were
performed on ASAP2010 (micromeritics) by N2 physical
adsorption–desorption at 77.4 K. X-ray photoelectron
spectra were recorded on XSAM 800 (Kratos).
2.4 Hydrophosphinylation Reaction of Alkynes
with Diphenylphosphine Oxide
A mixture of terminal alkyne (1.0 mmol), diphenylphos-
phine oxide (1.0 mmol), toluene (3 mL), and the MCM-41-
2P-RhCl3 complex (105 mg, 0.03 mmol of Rh) was stirred
under Ar in an oil bath at 80 °C for 4–12 h. The mixture
was cooled, diluted with Et2O (30 mL) and filtered. The
MCM-41-2P-RhCl3 complex was washed with EtOH
(2 9 10 mL) and Et2O (2 9 10 mL) and reused in the next
2.1 Preparation of MCM-41-NH2
A solution of c-aminopropyltriethoxysilane (2.20 g,
10 mmol) in dry chloroform (18 mL) was added to a sus-
pension of the mesoporous support MCM-41 (2.80 g) in
123

Diphosphino-Functionalized MCM-41-Immobilized Rhodium Complex
805
run. The ether solution was concentrated under a reduced
pressure, and the residue was purified by column chroma-
tography on silica gel (EtOAc/hexane = 1/1).
with decreased intensity remained after functionalization,
while the (110) and (200) reflections became weak and
diffuse, which could be due to contrast matching between
the silicate framework and organic moieties which are
located inside the channels of MCM-41. These results
indicated that the basic structure of the parent MCM-41
was not damaged in the whole process of catalyst prepa-
ration. The nitrogen adsorption studies demonstrated that a
significant decrease in pore size by virtue of silylation of
the MCM-41 channels was observed. Additionally, upon
modification the surface area and pore volume decreased
obviously. These results are in good agreement with the
fact that the surface modification indeed occurred inside
2.5 The Recyclability of the MCM-41-2P-RhCl3
and Rhodium Leaching Tests
After carrying out the reaction, the mixture was vacuum
filtered using a sintered glass funnel and the residue
washed with EtOH (2 9 10 mL) and Et2O (2 9 10 mL).
After being dried in an oven, the catalyst can be reused
directly without further purification. The rhodium content
of the catalyst was determined by ICP analysis to be
0.29 mmol/g after ten consecutive runs, no rhodium
leaching from the MCM-41 support was observed.
3 Results and Discussion
(100)
1
The novel diphosphino-functionalized MCM-41-immobi-
lized rhodium complex (MCM-41-2P-RhCl3) was conve-
niently synthesized from commercially available and cheap
c-aminopropyltriethoxysilane via immobilization on
MCM-41, followed by reacting with diphenylpho-
sphinomethanol which resulted from adduct formation
between diphenylphosphine and paraformaldehyde, and
rhodium chloride (Scheme 1). X-ray powder diffraction
(XRD) patterns of the parent MCM-41 and the modified
materials MCM-41-2P, MCM-41-2P-RhCl3 are displayed
in Fig. 1. Small angle X-ray powder diffraction of the
parent MCM-41 gave peaks corresponding to hexagonally
ordered mesoporous phases. For MCM-41-2P and MCM-
41-2P-RhCl3, the (100) reflection of the parent MCM-41
2
3
(110)
(200)
1
2
3
4
5
6
2θ (degrees)
Fig. 1 XRD patterns of the parent MCM-41 (1), MCM-41-2P (2),
and MCM-41-2P-RhCl3 (3)
OSiMe3
O
OH
OH
1.Toluene, 100 o
C, 48 h
Si(CH2)3NH2
+ (EtO)3Si(CH2)3NH2
O
2. Me3SiCl, rt, 24 h
OH
OEt
MCM-41-NH2
OSiMe3
PPh2
PPh2
Ph PCH OH
Toluene, 105 oC, 24 h
2
2
O
RhCl , CH COCH
3
3
3
Si(CH2)3N
OEt
reflux, 72 h
O
MCM-41-2P
OSiMe3
PPh2
RhCl3
PPh2
O
Si(CH2)3N
OEt
O
MCM-41-2P-RhCl3
Scheme 1 Preparation of the MCM-41-2P-RhCl3
123

806
F. Yao et al.
the primary mesopores of the parent MCM-41. The results
in detail are summarized in Table 1.
of Rh3d in MCM-41-2P-RhCl3 is 1.9 eV less than that in
RhCl3, but 1.4 eV larger than that in Rh foil. These results
show that a coordination bond between P and Rh is formed.
The hydrophosphinylation reaction of 1-octyne with
diphenylphosphine oxide was chosen as a model reaction,
and the influences of various reaction parameters such as
solvent, reaction temperature, and rhodium catalyst quantity
on the reaction were tested. The results are summarized in
Table 3. For the temperatures evaluated (25, 40, 60, 80, and
100 °C), 80 °C gave the best result and no reaction occurred
at 25 or 40 °C. Other reaction temperatures such as 60 and
100 °C were substantially less effective. We then turned our
attention to investigate the effect of solvents on the hydro-
phosphinylation reaction. Among the solvents used (THF,
dioxane, toluene, and benzene), toluene was the best choice.
Increasing the amount of rhodium catalyst could shorten the
reaction time, but did not increase the yield of (E)-1-
(diphenylphosphinyl)-1-octene (entry 9). The low rhodium
concentration usually led to a long period of reaction, which
was consistent with our experimental results (entries 10 and
11). Taken together, good result was obtained when the hy-
drophosphinylation reaction was carried out with 3 mol% of
the catalyst in toluene at 80 °C (entry 4).
Elemental analyses and X-ray photoelectron spectros-
copy (XPS) were used to characterize this heterogeneous
rhodium complex. The P: Rh mole ratio of the MCM-41-
2P-RhCl3 was determined to be 4.24. The XPS data for
MCM-41-2P-RhCl3, MCM-41-2P, RhCl3 and Rh foil are
listed in Table 2. It can be seen that the binding energies of
N1s, Si2p and O1s of MCM-41-2P-RhCl3 are similar to
those of MCM-41-2P and the binding energy of Cl2p of
MCM-41-2P-RhCl3 is similar to that of RhCl3. However,
the difference of P2p binding energies between MCM-41-
2P-RhCl3 and MCM-41-2P is 0.5 eV. The binding energy
Table 1 Textural parameters of the catalytic materials
Materials
Surface areaa
(m2/g)
Pore volumeb
(cm3/g)
Diameterc
(nm)
MCM-41
904.6
617.5
564.7
0.84
0.47
0.41
2.7
1.9
1.8
MCM-41-2P
MCM-41-2P-RhCl3
a
BET surface area; b Single point total pore volume; c Pore diameter
according to the maximum of the BJH pore size distribution
To examine the scope for this heterogeneous hydro-
phosphinylation reaction, we have investigated the reaction
using a variety of terminal alkynes as the substrates under
the optimized reaction conditions (Scheme 2) and the
results are outlined in Table 4. As shown in Table 4, this
heterogeneous rhodium complex-catalyzed hydrophosph-
inylation reaction can be readily applied to a variety of
Table 2 XPS data for MCM-41-2P-RhCl3, MCM-41-2P, RhCl3 and
Rh foil (in eV)
Sample
Rh3d P2p
N1s
Si2p
O1s
Cl2p
MCM-41-2P-RhCl3 308.5 133.5 399.2 103.4 532.7 199.6
R
H
H
MCM-41-2P
RhCl3
133.0 399.1 103.4 532.7
3 mol% MCM-41-2P-RhCl3
toluene, 80 oC
R
+
Ph2P(O)H
310.4
307.1
199.7
P(O)Ph2
3
1
2
Rh foil
The binding energies are referenced to C1s(284.6 eV), and the energy
differences were determined with an accuracy of 0.2 eV
Scheme 2 Hydrophosphinylation of terminal alkynes with diphen-
ylphosphine oxide catalyzed by MCM-41-2P-RhCl3
Table 3 Reaction condition
screening for the
hydrophosphinylation reaction
of 1-octyne with
diphenylphosphine oxide
Entry
Solvent
MCM-41-2P-RhCl3
(mol%)
Temp. (°C)
Time (h)
Yielda (%)
1
Toluene
Toluene
Toluene
Toluene
Toluene
THF
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
5.0
1.5
1.0
25
40
60
80
100
60
80
80
80
80
80
24
24
24
4
0
2
Trace
74
90
85
78
73
64
89
87
82
3
4
5
3
6
8
7
Benzene
Dioxane
Toluene
Toluene
Toluene
8
All reactions were performed
using 1.0 mmol of 1-octyne,
1.0 mmol of diphenylphosphine
oxide in 3.0 mL of solvent
under Ar
8
8
9
3
10
11
12
24
a
Isolated yield
123

Diphosphino-Functionalized MCM-41-Immobilized Rhodium Complex
807
the present reaction conditions. The reactions of heteroa-
rylacetylenes such as 2-ethynylthiophene and 2-ethynyl-
pyridine also proceeded efficiently under same reaction
conditions to give the desired addition products 3o and 3p
in high yields (entries 15 and 16). 1-Ethynylcyclohexene
underwent hydrophosphinylation exclusively at the triple
bond to afford the corresponding (1E)-1,3-dienylphosphine
oxide 3r in high yield (entry 18). The formation of the anti-
Markovnikov b-adduct from 1-ethynylcyclohexene is
noteworthy since the related palladium-catalyzed reaction
afforded the Markovnikov a-adduct instead [43].
In order to determine whether the catalysis was due to
the MCM-41-2P-RhCl3 complex or to a homogeneous
rhodium complex that comes off the support during the
reaction and then returns to the support at the end, we
performed the hot filtration test [44]. We focused on the
hydrophosphinylation reaction of 1-octyne with diphenyl-
phosphine oxide. We filtered off the MCM-41-2P-RhCl3
complex after 2 h of reaction time and allowed the filtrate
to react further. The catalyst filtration was performed at the
reaction temperature (80 °C) in order to avoid possible
recoordination or precipitation of soluble rhodium upon
cooling. We found that, after this hot filtration, no further
reaction was observed and no rhodium could be detected in
the hot filtered solution by ICP-AES. This result suggests
that the rhodium catalyst remains on the support at elevated
temperatures during the reaction and points to a process of
heterogeneous nature.
Table 4 Hydrophosphinylation of terminal alkynes catalyzed by
MCM-41-2P-RhCl3
Entry
R
Time (h) Product Yielda (%)
1
2b
n-C6H13
4
6
3a
3b
3c
3d
3e
3f
90
87
89
86
88
81
84
87
85
87
84
86
78
82
89
85
83
88
n-C4H9
3
Ph
6
4
4-MeC6H4
6
5
4-FC6H4
5
6
2-ClC6H4
10
8
7
4-CH3OC6H4
HOCH2CH2
MeOCH2CH2
1-Hydroxycyclohexyl
ClCH2CH2CH2
NCCH2CH2CH2
Me3SiCH2
3g
3h
3i
8
6
9
6
10
11
12
13b
14
15
16
17
18
5
3j
10
10
12
12
8
3k
3l
3m
3n
3o
3p
3q
3r
n-Bu2NCH2
Thiophen-2-yl
Pyridin-2-yl
t-BuCO2CH2CH2
1-Cyclohexenyl
6
6
5
All reactions were performed using 1.0 mmol of terminal alkyne,
1.0 mmol of diphenylphosphine oxide, and 3 mol% MCM-41-2P-
RhCl3 in 3.0 mL of toluene at 80 °C under Ar
a
b
Isolated yield; At 70 °C
terminal alkynes, proving to be a practically useful method
for the stereoselective synthesis of (E)-alkenylphosphine
oxides which are not readily available by conventional
methods. The hydrophosphinylation reaction of aliphatic
terminal alkynes with HP(O)Ph2 proceeded smoothly at
80 °C to afford the corresponding (E)-adducts by the reg-
ioselective addition of the phosphorus atom at the terminal
carbon of the triple bond in good to high yields (entries 1,
2, 8, 9, 11, 12, 17). The catalytic activity of this hetero-
geneous rhodium complex catalyst is comparable to that of
homogeneous RhCl3. For example, the hydrophosphinyla-
tion of 1-octyne in the presence of 3 mol% of MCM-41-
2P-RhCl3 in toluene at 80 °C under Ar for 4 h gave a 90%
yield of the addition product 3a (entry 1), the same reaction
in the presence of 3 mol% RhCl3 in toluene at 80 °C under
Ar for 3 h gave 3a in 91% yield [21]. Under the above
reaction conditions, aromatic terminal alkynes reacted
efficiently with HP(O)Ph2 affording the corresponding (E)-
alkenylphosphine oxides 3c–3g in good to high yields
(entries 3–7). The reactions of propargylic alcohol, silane
and amine with HP(O)Ph2 proceeded readily to give the
corresponding (E)-adducts 3j, 3m and 3n in good yields
(entries 10, 13 and 14). A variety of functionalities such as
chloro, cyano, amino, alkoxycarbonyl, hydroxyl, silyl,
fluoro, methyl, and methoxy groups were all tolerant under
For a heterogeneous transition-metal catalyst, it is very
important to examine its ease of separation, good of
recoverability and reusability. We also investigated the
recyclability of the MCM-41-2P-RhCl3 by using the reac-
tion of 1-octyne with diphenylphosphine oxide. This het-
erogeneous rhodium catalyst can be easily recovered by
simple filtration and washed with ethanol and diethyl ether.
After being air-dried, it can be reused directly without
further purification. The recovered rhodium catalyst was
used in the next run, and almost consistent activity was
observed for ten consecutive cycles (Table 5). In addition,
Table 5 Hydrophosphinylation reaction of 1-octyne with diphenyl-
phosphine oxide catalyzed by recycled catalyst
Cycle
Yielda (%)
Cycle
Yielda (%)
1
3
5
7
9
90
89
89
87
88
2
4
89
90
88
89
87
6
8
10
Reaction conditions: 1.0 mmol of 1-octyne, 1.0 mmol of diphenyl-
phosphine oxide, and 3.0 mol% MCM-41-2P-RhCl3 in 3.0 mL of
toluene at 80 °C for 4 h under Ar
a
Isolated yield
123

808
F. Yao et al.
7. Johnson CR, Imamoto T (1987) J Org Chem 52:2170
8. Pietrusiewicz KM, Wisniewski W, Zablocka M (1989) Tetrahe-
dron 45:337
rhodium leaching in the supported catalyst was also
determined. The rhodium content of the catalyst was found
by ICP analysis to be 0.29 mmol/g after ten consecutive
runs, no rhodium had been lost from the MCM-41 support.
The high stability and excellent reusability of the catalyst
should result from the chelating action of bidentate phos-
phine ligand on rhodium and the mesoporous structure of
the MCM-41 support. The result is important from a
practical point of view. The high catalytic activity, excel-
lent reusability and the easy accessibility of the MCM-41-
2P-RhCl3 make them a highly attractive heterogeneous
rhodium catalyst for the parallel solution phase synthesis of
diverse libraries of compounds.
9. Pietrusiewicz KM, Zablocka M (1988) Tetrahedron Lett 29:1991
10. Brunner H, Limmer S (1991) J Organomet Chem 417:173
11. Cavalla D, Warren S (1982) Tetrahedron Lett 23:4505
12. Brunner H, Limmer S (1991) J Organomet Chem 413:55
13. Pietrusiewicz KM, Zablocka M (1988) Tetrahedron Lett 29:937
14. Keck GE, Byers JH, Tafesh AM (1988) J Org Chem 53:1127
15. Brandi A, Cicchi S, Goti A (1991) Tetrahedron Lett 32:3265
16. Han L-B, Mirzael F, Zhao C-Q, Tanaka M (2000) J Am Chem
Soc 122:5407
17. Zhao C-Q, Han L-B, Tanaka M (2000) Organometallics 19:4196
18. Zhao C-Q, Han L-B, Coto M, Tanaka M (2001) Angew Chem Int
Ed 40:1929
19. Han L-B, Hua R, Tanaka M (1998) Angew Chem Int Ed 37:94
20. Han L-B, Zhang C, Yazawa H, Shimada S (2004) J Am Chem
Soc 126:5080
21. Han L-B, Zhao C-Q, Tanaka M (2001) J Org Chem 66:5929
22. Iwasawa Y (1986) Tailored metal catalysts. Reidel D Publishing
Company, Dordrecht
4 Conclusions
23. Poliakoff M, Fitzpatrick JM, Farren TR, Anastas PT (2002)
Science 297:807
24. Kirschnig A, Monenschein H, Wittenberg R (2001) Angew Chem
Int Ed 40:650
25. Sander AJ, Reek JNH, Kamer PCJ, van Leeuwen PWNM (2001)
J Am Chem Soc 123:8468
26. Merckle C, Blumel J (2003) Adv Synth Catal 345:584
27. Zhou W, He DH (2009) Green Chem 11:1146
28. Bourque SC, Mlatais F, Xiao WJ, Tardif O, Alper H, Arya P,
Manzer LE (1999) J Am Chem Soc 121:3035
29. Marras F, Wang J, Coppens MO, Reek JNH (2010) Chem
Commun 46:6587
30. Sayah R, Framery E, Dufaud V (2009) Green Chem 11:1694
31. Marciniec B, Szubert K, Fiedorow R, Kownacki I, Potrzebowski
MJ, Dutkiewicz M, Franczyk A (2009) J Mol Catal A Chem
310:9
32. Balcar H, Sedlacek J, Cejka J, Vohlidal J (2002) Macromol Rapid
Commun 23:32
33. Yang Y, Rioux RM (2011) Chem Commun 47:6557
34. Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS (1992)
Nature 359:710
35. Taguchi A, Schuth F (2005) Micropor Mesopor Mater 77:1
36. Martin-Aranda RM, Cejka J (2010) Top Catal 53:141
37. Beck JS, Vartuli JC, Roth WJ, Leonowicz ME, Kresge CT,
Schmitt KD, Chu CT-W, Olson DH, Sheppard EW, McCullen
SB, Higgins JB, Schlenker JL (1992) J Am Chem Soc 114:10834
38. Zhou W, Thomas JM, Shephard DS, Johnson BFG, Ozkaya D,
Maschmeyer T, Bell RG, Ge Q (1998) Science 280:705
39. Maschmeyer T, Rey F, Sankar G, Thomas JM (1995) Nature
378:159
40. Liu C-J, Li S-G, Pang W-Q, Che C-M (1997) Chem Commun 65
41. Shyu S-G, Cheng S-W, Tzou D-L (1999) Chem Commun 2337
42. Lim MH, Stein A (1999) Chem Mater 11:3285
43. Han L-B, Chol N, Tanaka M (1996) Organometallics 15:3259
44. Lempers HEB, Sheldon RA (1998) J Catal 175:62
In summary, we have developed a novel, practical and
environmentally friendly catalyst system for the hydro-
phosphinylation of terminal alkynes with diphenylphos-
phine oxide by using diphosphino-functionalized MCM-
41-immobilized rhodium complex as catalyst under mild
conditions. The reactions generated stereoselectively the
corresponding (E)-alkenylphosphine oxides in good to high
yields. This novel heterogeneous rhodium catalyst can be
easily prepared from commercially available and cheap
reagents and exhibits high catalytic activity and can be
reused at least 10 times without any decreases in activity.
The hydrophosphinylation of terminal alkynes with
diphenylphosphine oxide catalyzed by the MCM-41-2P-
RhCl3 complex provide a better and practical procedure for
the synthesis of a variety of (E)-alkenylphosphine oxides.
Acknowledgments We gratefully acknowledge the financial sup-
port of this work by the National Natural Science Foundation of
China (Project No. 20862008) and the Natural Science Foundation of
Jiangxi Province in China (Project No. 2010GZH0062).
References
1. Niu M, Fu H, Jiang Y, Zhao Y (2007) Chem Commun 272
2. Inoue H, Nagaoka Y, Tomioka K (2002) J Org Chem 67:5864
3. Rahman MS, Oliana M, Hii KK (2004) Tetrahedron Asymmetr
15:1835
4. Barbaro P, Bianchini C, Giambastiani G, Togni A (2002) Chem
Commun 2672
5. Han L-B, Zhao C-Q (2005) J Org Chem 70:10121
6. Nicolaou KC, Maligres P, Shin J, de Leon E, Rideout D (1990)
J Am Chem Soc 112:7825
123