Solid supported palladium(0) nanoparticles: An efficient heterogeneous catalyst for regioselective hydrosilylation of alkynes and suzuki coupling of β-arylvinyl iodides

Article abstract of DOI:10.1007/s10562-014-1311-8

The solid supported palladium(0) nanoparticles (NPs) were found as an active heterogeneous catalyst for regioselective hydrosilylation of alkynes with organosilanes in the presence of NaI as additive. Aliphatic as well as aromatic terminal/substituted alkynes with both electron releasing and withdrawing functionalities similarly participated in the hydrosilylation to produce regioselective β-isomers of vinylsilanes under mild reaction conditions. Reducible functional groups such as nitrile, ester, halide, alkene and alkyne were also found to be tolerated under this condition. Furthermore, the triethylsilylstyrene was applied for consecutive iododesilylation followed by Suzuki coupling reaction to produce stilbenes. The air/moisture stable SS-Pd catalyst was recycled for hydrosilylation reaction up to ten runs without significant loss of its catalytic activity. Graphical Abstract: Solid Supported Palladium(0) Nanoparticles: An Efficient Heterogeneous Catalyst for Regioselective Hydrosilylation of Alkynes and Suzuki Coupling of β-Arylvinyl Iodides[Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-014-1311-8

Catal Lett (2014) 144:1530–1536
DOI 10.1007/s10562-014-1311-8
Solid Supported Palladium(0) Nanoparticles: An Efficient
Heterogeneous Catalyst for Regioselective Hydrosilylation
of Alkynes and Suzuki Coupling of b-Arylvinyl Iodides
•
C. Bal Reddy Arun K. Shil Nitul Ranjan Guha
•
•
•
Dharminder Sharma Pralay Das
Received: 15 April 2014 / Accepted: 28 June 2014 / Published online: 16 July 2014
Ó Springer Science+Business Media New York 2014
Abstract The solid supported palladium(0) nanoparticles
(NPs) were found as an active heterogeneous catalyst for
regioselective hydrosilylation of alkynes with organosi-
lanes in the presence of NaI as additive. Aliphatic as well
as aromatic terminal/substituted alkynes with both electron
releasing and withdrawing functionalities similarly partic-
ipated in the hydrosilylation to produce regioselective
b-isomers of vinylsilanes under mild reaction conditions.
Reducible functional groups such as nitrile, ester, halide,
alkene and alkyne were also found to be tolerated under
this condition. Furthermore, the triethylsilylstyrene was
applied for consecutive iododesilylation followed by Su-
zuki coupling reaction to produce stilbenes. The air/mois-
ture stable SS–Pd catalyst was recycled for hydrosilylation
reaction up to ten runs without significant loss of its cata-
lytic activity.
1 Introduction
Vinylsilanes, generally synthesized by catalytic hydrosi-
lylation of alkynes, have proven to be versatile building
blocks in organic syntheses [1, 2] and allowed for a
plethora of organic transformations such as Hiyama cou-
pling for carbon–carbon bond formation [3–7],Tamao-
Fleming oxidation providing the carbonyl compounds [8–
10], protodesilylation affording the corresponding alkenes
and as terminators for cationcyclizations [11]. Silylalk-
enes have also received greater growing importance over
other metal alkenes in terms of stability, cost, low tox-
icity, ease of handling and simplicity of byproduct
removal. Among the possible routes to these compounds
[12, 13], the transition-metal-catalyzed hydrosilylation of
alkynes has been established to be the most powerful,
atom economic, convenient and most frequently adopted
route [14–16]. Recently, significant progress has been
made in this area and a myriad of catalytic systems have
been developed, including the metal catalyst of ruthenium
[17–20], rhodium [21, 22], and platinum [23–32] as cat-
alyst for its formation, but encountered difficulty in con-
trolling regioselectivity of product depending on the
catalyst and the alkyne. Despite considerable progress in
this field, examples of palladium catalyzed hydrosilylation
with triorganosilanes are much less abundant and are
more limited. The homogeneous palladium particularly
with phosphine ligands are found to be effective catalyst
for hydrosilylation of alkynes with triorganosilanes to
generate a- and b-regio isomers as well [33, 34], however
in some cases well designed substrates are required to
attain the regioselectivity [35]. Moreover, hydrosilylation
of alkynes using Pd(NO3)2 as catalyst suffered with lim-
ited substrate scope and unusual byproduct formation
along with silylation products [36].
Keywords Solid supported palladium Á Heterogeneous
nanocatalyst Á Alkynes Á Hydrosilylation Á Suzuki reaction
CSIR-IHBT communication no. 3546
Electronic supplementary material The online version of this
article (doi:10.1007/s10562-014-1311-8) contains supplementary
material, which is available to authorized users.
C. Bal Reddy Á A. K. Shil Á N. R. Guha Á D. Sharma Á
P. Das (&)
Natural Plant Products Division, CSIR-Institute of Himalayan
Bioresource Technology, Palampur 176061, Himachal Pradesh,
India
e-mail: pdas@ihbt.res.in
C. Bal Reddy Á A. K. Shil Á N. R. Guha Á P. Das
Academy of Scientific & Innovative Research, New Delhi, India
123

Heterogeneous Palladium Catalyzed Hydrosilylation of Alkynes
1531
2 Experimental Section
Table 1 Optimization of reaction conditions for hydrosilylation of
alkynes
2.1 General Remarks
Reagents of high quality were purchased from Sigma
Aldrich. AmberliteÒ IRA 900 (Chloride form) was pur-
chased from Across Organics. Silica gel (60–120 mesh
size) for column chromatography was procured from Sd
Fine-chem Ltd. Commercial reagents and solvents were
of analytical grade and were purified by standard pro-
cedures prior to use. Thin layer chromatography was
performed using precoated silica gel plates 60 F254
(Merck) in UV light detector. GC–MS analysis was
carried out on a Shimadzu (QP 2010) series GC–MS
(Tokyo, Japan), equipped with a FID, AOC 5000 auto-
sampler, DB-5MS capillary column (30 m 9 0.25 mm
i.d. with film thickness 0.25 lm). ICP–AES analysis
carried out on ARCOS from M/S. Spectro, Germany.
A TEM image was taken using a carbon coated copper
grid (Microscopy sciences) in a transmission electron
microscope JEOL 2100F and FEI Tecnoi G20, 200 kV,
Netherlands. 1H and 13C NMR spectra were recorded
using a Bruker Avance 300 spectrometer operating at
300 MHz (1H) and 75 MHz (13C). Spectra were recorded
at 25 °C in CDCl3 [residual CHCl3 (dH 7.26 ppm) or
CDCl3 (dC 77.00 ppm) as international standard] with
TMS as internal standard. Chemical shifts were recorded
in d (ppm) relative to the TMS and CDCl3 signal,
coupling constants (J) are given in Hz and multiplicities
of signals are reported as follows: s, singlet; d, doublet;
t, triplet; m, multiplet; br, broad singlet. HRMS–ESI
spectra were analysed using micromass Q-TOF ultima
spectrometer. The melting points were determined on a
digital Barnsted Electrothermal 9100 apparatus.
Entry
Catalyst [mol% Pd]
Solvent
Additive
Yield [%]b
1
SS–Pd [2]
SS–Pd [2]
SS–Pd [2]
SS–Pd [2]
SS–Pd [2]
SS–Pd [2]
SS–Pd [1]
SS–Pd [3]
–
THF
KI
76
nr
2
THF
–
3
THF
KF
10
77
15
97
81
97
nr
4
THF
LiCl
TBAB
NaI
NaI
NaI
NaI
NaI
NaI
NaI
NaI
NaI
NaI
NaI
5
THF
6
THF
7
THF
8
THF
9
THF
10
11
12
13
14
15
16
a
SS–Pd [2]
Pd(OAc)2 [2]
Pd/C [2]
Pd(PPh3)4 [2]
SS–Pd [2]
SS–Pd [2]
SS–Pd [2]
1
DMF
THF
95
64
78
70
nr
THF
THF
H2O
Toluene
Dioxane
nr
35
E:Z ratio determined by H NMR
b
Isolated yield
To circumvent the aforementioned drawbacks, estab-
lishing a phosphine free protocol for the hydrosilylation of
alkynes affording a specific regioisomer with broader
substrate scope remains a challenge. So there is an urgent
need to develop a new generation palladium catalysts for
the selective hydrosilylation of alkynes in presence of
vulnerable functional groups. To the best of our knowledge
there is no precedent found yet for the hydrosilylation of
alkynes under heterogeneous palladium catalyzed condi-
tions. However recently Buchmeiser et al. [37–40] have
developed polymer supported transition metals NPs for
hydrosilylation and cross coupling reactions. As part of our
continuous research on the development of solid supported
transition metal NPs as a heterogeneous catalyst and its
applications in various organic transformations [41–49],
herein we wish to present the hydrosilylation of alkynes
catalyzed by highly reusable palladium NPs supported on
polystyrene polymeric resin. In sharp contrast to previously
reported homogeneous palladium catalyzed conditions,
reactions proceeded in air, low temperature, under ligand
free conditions and exclusively gives b-regioisomer as sole
product.
2.2 Preparation of Solid Supported Palladium(0)
Catalyst
In our previous reports, according to the well established
simple procedure for the preparation of solid supported
Pd(0) NPs it has been inferred that partially borohydride
ions (BH4-) exchanged Amberlite chloride form resin
(polystyrene-NR3?Cl--BH4-) in situ reduces Pd(II) to
Pd(0) (characterized by UV-Visspectra and XRD) with the
simultaneous impregnation of Pd(0) NPs inside the
hydrophobic pocket of polymeric resin matrix produced
SS–Pd(0) catalyst [41, 46]. The large surface area of resin
beads and suitable porous dimension helps to bind the
Pd(0) NPs in the inner surface region.
123

1532
C. Bal Reddy et al.
Fig. 2 HRTEM image showing Pd (0) nanocrystals formation in SS–Pd
(3 9 3 mL). The crude mixture was purified by column
chromatography (EtOAc:Hexane, 1:99), afforded 4-(2-tri-
ethylsilyl-vinyl)-benzonitrile 2 as colourless liquid (185 mg,
1
97 % yield); H NMR (300 MHz, CDCl3) d 0.64–0.72 (q,
6H), 0.97–1.02 (t, J = 7.8 Hz, 9H), 6.57–6.64 (d,
J = 19.5 Hz, 1H), 6.87–6.93 (d, J = 19.2 Hz, 1H),
7.49–7.52(d, J = 8.3 Hz, 2H) 7.58–7.61(d, J = 8.4 Hz, 2H);
13C NMR (75 MHz, CDCl3) d 3.76, 7.72, 111.64, 118.02,
126.75, 131.48, 132.29, 142.94, 145.41. HREIMS data: m/
z calcd. for [M?H]? C15H22NSi 244.4274 obsd. 244.4234.
Fig. 1 a Solid supported palladium (SS–Pd); b transmission electron
micrograph (TEM) of SS–Pd catalyst; c EDX spectrum and d histo-
gram describing the particle size distribution
2.4 Typical Experimental Procedure for Suzuki
Coupling Reaction
2.2.1 Typical Procedure
The solution of 100 mg of NaBH4 in 30 mL of water was
added to 4 g of Amberlite IRA 900 resin (chloride form)
(Across, BE) in a 100 mL flask. The mixture was stirred
for 4 h at room temperature. Then the resin was washed
with water till pH became neutral and then with acetone to
remove water from the solid surface. The resin beads
(borohydride exchanged) were dried under reduced pres-
sure. The dried borohydride exchanged resin beads (solid
surface) (1 g) was added into the warm (100 °C) solution
of palladium acetate (10 mg) in DMF (3 mL) then the
mixture was stirred for 1 h or till the dark brown colour of
the solution changed into colourless and simultaneously
white solid beads were turned into blackish. After cooling,
the beads were filtered through a cotton bed, washed with
water and acetone, and dried under reduced pressure.
To
a mixture of 2-phenylvinyliodide 27 (100 mg,
0.43 mmol), SS–Pd (291 mg, 3 mol % Pd), phenylboronic
acid (63.5 mg, 0.52 mmol) and K2CO3 (119.78 mg,
0.86 mmol) in a 25 mL round bottom flask was added 1 mL
DMF. The reaction mixture was then magnetically stirred at
90 °C for 6 h. The progress of the reaction was monitored
by TLC. On completion, the reaction mixture was extracted
with ethyl acetate (3 9 3 mL) by addition of 2 mL of water
and dried over anhydrous Na2SO4. Evaporation of the
combined organic layer followed by column chromatogra-
phy (EtOAc:Hexane, 2:98) over silica gel (mesh 60–120)
afforded stilbene 29 as white crystalline solid (60.30 mg,
77 % yield), m.p. 124–125 °C; 1H NMR (300 MHz,
CDCl3) 7.10–7.17 (m, 2H), 7.27–7.31 (m, 2H), 7.37–7.42
(m, 4H), 7.54–7.56 (m, 4H); 13C NMR (75 MHz, CDCl3) d
126.92, 128.40, 128.04, 129.09, 137.73.
2.3 Typical Experimental Procedure
for Hydrosilylation of Alkyne
3 Results and Discussion
To
a mixture of 4-ethynyl benzonitrile 1(100 mg,
0.78 mmol), SS–Pd (352 mg, 2 mol % Pd), NaI (117 mg,
0.78 mmol) inTHF(2 mL)wasaddedtriethylsilane(110 mg,
0.94 mmol). The reaction mixture was magnetically stirred at
60 °C for 20 min. The progress of the reaction was monitored
by TLC. The reaction mixture was extracted with ethylacetate
3.1 Characterization of Solid Supported Palladium(0)
Catalyst by TEM-EDX
The transmission electron micrograph (TEM) was per-
formed to analyze the morphological feature of SS–Pd and
123

Heterogeneous Palladium Catalyzed Hydrosilylation of Alkynes
1533
Scheme 1 Comparative study
for selective hydrosilylation
reaction
SiEt3
Homogeneous
Pd(NO3)2
C
C
C
C
SiEt3
+
H H
5: 30%
Kim et al. 2006
H
rt, Toluene
4: 70%
Et3SiH
+
b (E:Z = 96:4)
3
SS-Pd
NaI, THF, 60 0C
Our work
4: 86%
b (E:Z = 86:14)
Heterogeneous
Table 2 Solid supported
palladium(0) catalyzed
hydrosilylation of alkynes
a
a
a
1
E:Z ratio determined by H
NMR
Isolated yields
a
Performed at room
temperature
histogram indicated the average particle size distribution of
Pd(0) over the matrix was in the range of 1–2 nm (Fig. 1).
High resolution transmission electron micrograph
(HRTEM) image demonstrated the formation of Pd(0)
single crystal planes over the polymeric matrix (Fig. 2).
different solvents, THF was found to be the most suitable
for this transformation (Table 1, entries 6, 10, 14–16).
Various palladium catalysts were also examined, but SS–
Pd (2 mol % Pd) gave the best results for hydrosilylation
reaction (Table 1, entries 11–13).
Motoda et al. reported hydrosilylation of alkynes with
triorganosilanes in presence of homogeneous palladium
catalyst leading to the formation of mixture of a- and
b-isomers. Similarly, Kim et al. have demonstrated the
hydrosilylation reaction of phenylacetylene 3 and Et3SiH
in presence of Pd(NO3)2 but dialkynylated silanes 5 (30 %)
has also been observed as byproduct which has restricted
the existing method. Hydrosilylation of electro neutral
phenylacetylene 3 under our standard reaction conditions
3.2 Hydrosilylation Reactions of Alkynes
We initiated our investigation by studying the hydrosily-
lation reaction of 4-ethynylbenzonitrile 1 with triethylsi-
lane in presence of SS–Pd as a catalyst under various
reaction conditions (Table 1). In our initial screening of
additive, it was gratifying to find that NaI could afford the
desired product in high yield (Table 1, entry 6). Among the
123

1534
C. Bal Reddy et al.
under standard catalytic conditions with Et3SiH and
PhMe2SiH to produce selective b-hydrosilylated products
6–9 in 85–96 % yields. Unsubstituted as well as electron
rich –CH3 and –OCH3 functionalized phenylacetylenes
also responded to produce corresponding vinylsilanes 11–
14 in substantial yields. No significant effects of ortho-
substituted –OCH3 and –CH3 groups were observed in the
reactivity of respective alkynes to produce 15–17 in
73–93 % yields. Polycyclic aromatic alkynes also reacted
smoothly to furnish the desired vinylsilanes 18–19 in rea-
sonable yields 73–82 %. Heterocyclic 3-thiophene acety-
lene also delivered the hydrosilylated product 20 in 82 %
yield (Table 2).
Table 3 Hydrosilylation reaction of aliphatic terminal alkynes
a
The aliphatic terminal alkynes oct-1-yne and pent-1-yne
were subjected to hydrosilylation with Et3SiH and
PhMe2SiH under the present catalytic conditions and
resulted in the targeted vinylsilanes 21–23 in 72–87 %
yields. Interestingly, for disubstituted alkyne (ethyl but-2-
ynoate), regioselective hydrosilylationreaction was also
observed at electron deficient a-carbon of alkyne to pro-
duce major E-configured isomer (E:Z = 90:10) 24 in 77 %
yield (Table 3).
1
E:Z ratio determined by H NMR
Isolated yields
a
performed at room temperature
afforded the b-triethylsilylstyrene 4 exclusively in 86 %
yield (Scheme 1).
With the set reaction conditions, we further extended the
protocol for wide substrate scope with aromatic, heteroar-
omatic and aliphatic alkynes. In all the cases regioselective
b-isomers were identified as only product and no a-isomer
was detected. Electron deficient p-CF3, -F and -CN
substituted phenylacetylenes participated in the reaction
As per our knowledge, hydrosilylation of symmetric
1,3-diynes for selective mono-silylation is rarely reported
in the literature and in most of the cases poly-silylated
product appeared as major one [50, 51].Interestingly, when
symmetric 1,4-diphenylbuta-1,3-diyne and 2-(4-(thiophen-
2-yl)buta-1,3-diynyl)thiophene were treated with Et3SiH
Table 4 Mono-hydrosilylation
of symmetric 1,3-diynes
Isolated yields
Scheme 2 SS–Pd catalyzed
R'-B(OH)2 (1.2 eq.)
SS-Pd (3 mol% Pd)
I
SiEt3
NIS (1.5 eq.)
R'
synthesis of stilbenes starting
from triethylsilyl styrene;
isolated yields; E/Z ratio was
determined by GC–MS
CH3CN, 12 h, rt
OCH3
K2CO3 (2 eq.)
28-30
4
DMF, 90 oC, 6 h
27: 80% (E:Z = 86:14)
CH3
28: 75% (E:Z = 84: 16)
30: 73% (E:Z = 75: 25)
29: 77% (E:Z = 96: 4)
123

Heterogeneous Palladium Catalyzed Hydrosilylation of Alkynes
1535
were performed in hydrosilylation reaction of 2-ethynyl-6-
methoxy naphthalene and triethylsilane (1: 1.2 eq.), NaI
(1 eq.) additive, SS–Pd (2 mol % Pd) in THF with excess
of Hg(0). After heating the reaction mixture at 60 °C for
20 min, almost no activity of catalyst was observed for
hydrosilylation reaction indicating poisoning of Pd(0)
impregnated over support and the reaction occurred at the
surface of catalyst.
3.5 Active Palladium Species in Solution
To check the presence of active palladium in the solution,
hydrosilylation reaction of 2-ethynyl-6-methoxy naphtha-
lene, triethylsilane, SS–Pd and NaI in THF was carried out
under standard condition and the catalyst separated from
reaction mixture through filtration. Fresh substrates were
added to the filtrate and stirred for another 20 min at 60 °C,
but no further improvement of hydrosilylation product was
observed which indicate the absence of active palladium
species in the reaction mixture.
Fig. 3 Recyclability experiment of SS–Pd catalyst for hydrosilyla-
tion reaction
under our standard conditions, only mono-hydrosilylated
compounds 25 and 26 were isolated as major products in
70–75 % yields with minor unreacted starting materials
(Table 4).
The prepared vinylsilane4 was further utilized for the
synthesis of b-styryliodide [42–55] 27 which has huge
application as a starting material for several bio-active
molecules synthesis [56]. The Suzuki coupling is a par-
ticularly important reaction in organic chemistry, since it is
a powerful tool for constructing C–C bond [57]. To our
delight, under the SS–Pd catalyzed conditions 27 was
subjected to the Suzuki coupling reaction with phenyl
boronic acids to produce stilbenes 28–30 in considerably
good yields (Scheme 2).
4 Conclusion
In conclusion, we explored the efficiency of solid sup-
ported palladium(0) NPs as heterogeneous catalyst for the
hydrosilylation reaction of alkynes under milder reaction
condition. Good to excellent yields to vinylsilanes were
observed for the aliphatic, aromatic, heterocyclic alkynes,
disubstituted alkyne and most challenging symmetric 1,3-
diynes irrespective of functional groups attached to aro-
matic ring. Furthermore, the b-arylvinyl iodide prepared
from vinylsilane was applied for Suzuki coupling reaction
under same catalytic condition to produce stilbenes. Due to
versatile application, negligible leaching and high reus-
ability, SS–Pd catalyst could find interest as atom-eco-
nomic and inexpensive reagent for general lab practices.
3.3 Recyclability Experiment
The recyclability experiment of SS–Pd catalyst was con-
ducted on 4-ethynylbenzonitrile 1 as test substrate. After
the reaction, the SS–Pd catalyst was recovered by simple
filtration, washed with water and acetone, dried under
reduce pressure and reused under the standard conditions.
The SS–Pd catalyst could be recycled up to ten times with
the lower yield obtained 92 % (Fig. 3) which revealed by
leaching experiment studied by ICP–AES analysis of the
resulting reaction solution mixture, and only \1 ppm of
palladium was detected. TEM experiment of SS–Pd cata-
lyst was done after ten catalytic cycles and it was observed
that the change in average palladium NPs diameter from
2.5 to 15 nm (see supporting information).
Acknowledgments Authors are grateful to Director CSIR-IHBT for
providing necessary facilities during the course of the work. We
gratefully acknowledge AIRF-JNU for HRTEM analysis. The authors
thank CSIR, New Delhi for financial support as part of XII Five Year
Plan programme under title ORIGIN (CSC-0108). CBR (UGC-JRF),
AKS (CSIR-SRF), NRG (UGC-SRF) and DS (CSIR-SRF) thanks
CSIR and UGC New Delhi for awarding fellowships.
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