Ti-exchanged ZSM-5 as heterogeneous catalyst for allylation of aldehydes with allyltributylstannane

Article abstract of DOI:10.1016/j.tetlet.2011.03.056

Titanium exchanged ZSM-5 catalyst has been prepared by treating an aqueous solution of titanium (IV) chloride with ZSM-5. The supported catalyst has been explored as effective and reusable catalyst for allylation reaction of aldehydes with allyltributylst

Full text of DOI:10.1016/j.tetlet.2011.03.056

Tetrahedron Letters 52 (2011) 2649–2651
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Tetrahedron Letters
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Ti-exchanged ZSM-5 as heterogeneous catalyst for allylation of aldehydes
with allyltributylstannane
⇑
Balin Kumar Bhuyan, Arun Jyoti Borah, Kula Kamal Senapati, Prodeep Phukan
Department of Chemistry, Gauhati University, Guwahati 781014, Assam, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Titanium exchanged ZSM-5 catalyst has been prepared by treating an aqueous solution of titanium (IV)
chloride with ZSM-5. The supported catalyst has been explored as effective and reusable catalyst for ally-
lation reaction of aldehydes with allyltributylstannane. The new catalytic system promotes efficiently the
allylation reaction in toluene condition to produce homoallylic alcohols in high yield.
Ó 2011 Elsevier Ltd. All rights reserved.
Received 6 January 2011
Revised 9 March 2011
Accepted 11 March 2011
Available online 21 March 2011
Keywords:
ZSM-5
Heterogeneous catalyst
Allylation
Allyltributylstannane
Homoallylic alcohol
ZSM-5 is one of the widely applied solid acid catalysts in indus-
try for various synthetic transformations.1 In the past decades, sig-
nificant efforts have been undertaken to design zeolite catalysts by
incorporating certain transition metals in zeolite framework for
task specific applications.1 In this regard, TS-1 and VS-1 were found
to be very successful zeolite catalysts for various oxidative trans-
formations.2 However, study on the titanium containing ZSM-5
made by post synthetic modification using ion-exchange method
has received scant attention in the literature.
The addition of allyl metal reagents to aldehydes is an important
method for formation of carbon–carbon bond.3 The utility of this
method has been demonstrated by numerous applications in or-
ganic synthesis.3 Allyltributylstannane is one of the most common
reagents used for the synthesis of homoallylic alcohols. In recent
years, several Lewis acids, especially metal Lewis acids, or transi-
tion metal complexes have been utilized extensively to catalyze
this transformation including those based on B,4 Sn,5 Ti,6 Zr,7 Rh,8
Re,9 Sc,10 Gd,11 Ce,12 Pd,13 Ag14 and Cu.15 However many methods
using Lewis acids require strictly anhydrous conditions. Although
rhenium complex9 or scandium triflate10 are very effective as air-
stable and water-tolerant catalysts for allylation reaction, these cat-
alysts are expensive. Moreover, the rhenium complex was found to
be effective for allylation reactions only at higher temperature. Cer-
ium (III) chloride (CeCl3Á7H2O) in combination with NaI, has been
used as a stoichiometric promoter for the allylation of various alde-
hydes with allyltributyltin.12 The major drawback of this method is
the use of a stoichiometric amount of the promoter to effect the
reaction. Several Pd-complexes13 and silver triflate14 has been re-
ported by many researchers. However, palladium and silver com-
pounds are expensive and in many cases the method requires
stringent dry reaction conditions at low temperature. We have also
reported a method for the synthesis of homoallyl alcohols using CuI
as catalyst.15 However, this catalyst is effective only in homoge-
neous condition. Although several homogeneous metal complexes
have been examined, a very limited effort has been made to use
heterogeneous catalyst for the allylation reaction. Wang16 may be
the first to report a heterogeneous resin supported catalyst for ally-
lation of aldehyde with tetraallyltin. But they have applied the
method only in the case of hexanal and no detail investigation
was made to generalize the procedure with other aldehydes. Later,
Portnoy17 reported the preparation of pincer bis(oxazolinyl)phenyl
ligands on polymer support for rhodium catalyzed allylation reac-
tion of various aldehydes with allyltributylstannane. Very recently,
Zhao and Li reported a new method for homoallylic alcohol synthe-
sis using a polymer-supported sulfonamide of N-glycine as cata-
lyst.18 As
a part of our investigations on various allylation
reactions,15,19 we report herein, for the first time, the use of a
heterogeneous titanium catalyst viz. Ti-exchanged ZSM-5 for the
synthesis of homoallylic alcohols (Scheme 1).
Since an extensive study has already been carried out for allyla-
tion of aldehydes using various titanium complexes,6 we sought to
develop a heterogeneous titanium catalyst by post synthetic
modification of ZSM-5. Initially ZSM-5 samples were prepared by
following a procedure reported in the literature.20 Formation of
⇑
Corresponding author. Tel.: +91 361 2674360.
E-mail address: pphukan@yahoo.com (P. Phukan).
0040-4039/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2011.03.056

2650
B. K. Bhuyan et al. / Tetrahedron Letters 52 (2011) 2649–2651
OH
O
allyltributylstannane (1.05 mmol) was added to a mixture of 4-
Ti-ZSM-5 (Cat)
Toluene, rt
SnBu3
chlorobenzaldehyde (1 mmol) and Ti-ZSM-5 containing 0.4 wt %
of titanium as catalyst (10 wt % based on aldehyde) in acetonitrile
at room temperature (Table 1). Reaction at room temperature in
acetonitrile failed to yield the desired product after 24 h of reac-
tion. When, the reaction was carried out in benzene, corresponding
homoallyl alcohol was obtained in 78% isolated yield after 36 h of
reaction at room temperature. We have also tested the catalytic
efficiency of the parent ZSM-5 sample under the same reaction
condition. We found that the rate of the reaction is very slow in
the presence of ZSM-5 and the reaction furnished 28% yield of
the product after 48 h of reaction. Thereafter, a comparative study
was carried out for evaluation of the catalyst using different sol-
vents such as dichloromethane, toluene and diethylether (Table
1). The reaction took relatively longer time to occur in ether,
whereas, the reaction did not proceed in dichloromethane. Use of
toluene gave slightly lower yield than in benzene. Thereafter, we
carried out the experiment in toluene, increasing the amount of
catalyst. Although the reaction gives marginally better yield in
benzene, we have chosen toluene as solvent due to its nonhazard-
ous nature. It was found that the use of 35 wt % of the catalyst is
sufficient to drive the reaction to completion in 10 h in high yield.
After evaluating the most suitable condition for allylation reac-
tion, we carried out a comparative investigation of the catalytic
efficiency of the Ti-ZSM-5 samples (0.4, 1.34, and 15.6 wt % of tita-
nium). While the Ti-ZSM-5 with 1.34 wt % of Ti produced lower
yield of corresponding homoallyl alcohols, the deformed Ti-ZSM-
5 sample with 15.6 wt % of titanium was not at all catalytically ac-
tive for this reaction. Deformation of ZSM-5 structure due to higher
amount of titanium exchange may be the reason for decrease in
reactivity of the catalyst.
We have further extended the procedure in case of different
aldehydes, the results are summarized in Table 2. The reaction
was carried out using 1 mmol of aldehyde, 1.05 mmol of allyltrib-
utylstannane, 35 wt % of Ti-ZSM-5 in toluene (1 mL) at room tem-
perature.22 Both aromatic and aliphatic aldehydes underwent
homoallylation with high yields. Substituted benzaldehydes such
as 4-chloro-, 4-fluoro- 4-nitro-, 4-methoxy-, 4-methyl-, and 4-bro-
mo- were examined under the optimized reaction conditions (en-
tries 2–7). Aldehyde possessing electron withdrawing substituents
such as nitro group produced lower yield of corresponding homo-
allylic alcohol. We observed that aldehyde possessing methoxy
substituent gave slightly lower yield, which may be due to poor
defusibility of the substrate. Under similar conditions naphthalde-
hyde also underwent allylation reaction to the corresponding
homoallylic alcohol in 80% yield (Table 2, entry 8). We have suc-
cessfully extended the procedure to the aliphatic aldehyde octanal
+
R
H
R
Scheme 1. Allylation of aldehydes using Ti-ZSM-5 as catalyst.
ZSM-5 was confirmed by comparing the XRD and IR spectra with
standard data.21 The X-ray diffraction patterns show high crystal-
linity of the ZSM-5 samples. Morphology of the ZSM-5 samples
was further examined using scanning electron micrograph. The
Si/Al ratio of the ZSM-5 sample was determined from EDX analysis
and it was found to be 84.
The Ti-exchanged ZSM-5 was made by stirring ZSM-5 in an
aqueous solution of TiCl4 at room temperature. Different samples
of Ti-ZSM-5 were prepared by varying the amount of TiCl4.
XRD-patterns confirm the crystalline nature of the Ti-ZSM-5 sam-
ples (Fig. 1).
Morphology of the Ti-ZSM-5 samples was also analyzed by
using SEM. Titanium content of the Ti-exchanged ZSM-5 samples
was determined by EDX analysis. Analysis of the SEM pictures re-
vealed that there is a significant impact of titanium exchange on
the crystallinity of the parent ZSM-5 samples. We observed that
the catalyst retains typical ZSM-5 morphology when titanium
loading is about 0.4 wt % (Fig. 2). However, slight deformation of
the structure was observed in case of Ti-ZSM-5 samples having
1.34 wt % of titanium. Further increase of Ti-content led to defor-
mation of crystalline structure of the ZSM-5 sample.
After confirming the structure and morphology of the as pre-
pared Ti-ZSM-5 samples, we intended to test the efficacy of the
catalyst for allylstannation of aldehyde. Initially, a systematic
study on the synthesis of homoallylic alcohols was carried out
using 4-chlorobenzaldehyde as substrate. In a typical reaction,
1600
1400
1200
1000
800
600
400
200
0
5
10
15
20
25
30
35
40
45
50
Figure 1. XRD-pattern Ti-ZSM-5 (0.4 wt % Ti).
Table 1
Synthesis of homoallylic alcohols from benzaldehyde under various conditionsa
Sl. No. Catalystb
Catalyst amount (wt %) Solvent
T (h) Yieldc (%)
1
2
3
4
5
6
7
8
9
9
9
9
ZSM-5
Ti-ZSM-5 10
Ti-ZSM-5 10
10
MeCN
MeCN
Benzene 36
Benzene 48
Ether
DCM
Toluene
Benzene 24
Toluene
Toluene
Toluene
Toluene
24
24
NR
NR
78
28
56
NR
72
77
75
78
83
82
ZSM-5
10
Ti-ZSM-5 10
Ti-ZSM-5 10
Ti-ZSM-5 10
Ti-ZSM-5 20
Ti-ZSM-5 20
Ti-ZSM-5 30
Ti-ZSM-5 35
Ti-ZSM-5 40
36
36
36
24
12
10
10
a
Reaction conditions: chlorobenzaldehyde (1 mmol), allyltributylstannane
(1.05 mmol), solvent (1 mL), rt.
b
Ti-ZSM-5 samples with 0.4 wt % of Ti was used.
Isolated yield after chromatographic purification. NR: no reaction.
c
Figure 2. SEM picture of Ti-ZSM-5 (0.40 wt % of Ti).

B. K. Bhuyan et al. / Tetrahedron Letters 52 (2011) 2649–2651
2651
Table 2
Acknowledgments
Synthesis of homoallylic alcohols using Ti-ZSM-5 catalyst
Sl. No.
1
Aldehyde (a)
Product (b)
T (h)
Yielda
81
Financial Support from UGC (NERO) and DST is gratefully
acknowledged. A.J.B. thanks UGC for research fellowship. The
authors thank IIT Guwahati for analytical data.
CHO
OH
10
Supplementary data
CHO
OH
2
3
4
10
8
83
85
72
Cl
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.tetlet.2011.03.056.
Cl
CHO
OH
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OH
OH
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( )5
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and an aldehyde containing a double bond viz. cinnamaldehyde
(entries 9 and 10). All compounds were characterized by compar-
ing the NMR and IR values with those reported in the literature.
Reusability of the catalyst was examined in case of 4-chlorobenz-
aldehyde. The recovered catalyst was dried under vacuum oven
at 60 °C for 6 h before use. The catalyst could be reused success-
fully for two times without significant loss of activity (Table 2, en-
tries 11 and 12).
Ti-exchanged ZSM-5 was synthesized by treating ZSM-5 with
an aqueous solution of TiCl4 at room temperature. The newly
developed catalyst was found to be an active heterogeneous cata-
lyst for allylation of aldehyde with allyltributylstannane. Ti-ZSM-5
with 0.4 wt % of titanium was found to be more active catalyst than
that containing 1.34 wt % of titanium.
22. Typical procedure: To
a mixture of aldehyde (1 mmol) and Ti-ZSM-5
(0.35 mmol) in toluene (1 mL) allyltributylstannane (1.05 mmol) was added
and the reaction was stirred for appropriate time (TLC). After completion of the
reaction, catalyst was filtered off and the solvent was evaporated to get the
crude product. The crude product was purified by column chromatography
over silica gel (230–400 mesh) using petroleum ether–ethyl acetate mixture as
eluent.