Microporousand MesoporousMaterials21( 1998)173-182

Zeolite-based catalysts for chemicals synthesis

M.E. Davis
Chemical Engineering. Calijbrnia Institute of Technology, Pasadena, Calfirniu

9112.5, USA

Received 25 August 1997;accepted28 October 1997

Abstract

A survey of the types of active sites and reaction chemistries possible with zeolite-based catalyst systemsis presented.
Several trends in zeolite catalysis for chemicals synthesis are enumerated and suggestions for work provided. Two
emerging areas of zeolite catalysis for fine chemicals preparation, namely, extra-large pore zeolite catalysts and chiral
zeolite catalysis, are described. 0 1998 Elsevier Science B.V. All rights reserved.
Keywords:

Zeolites; Catalysis; Fine chemicals; Chirality; Organic-inorganic hybrid

1. Introduction
The use of zeolites as catalysts for organic
reactions began in the early 1960s.Initially, zeolitebased catalysts were investigated for applications
in the petrochemical industries. In 1968, Venuto
and Landis provided the first comprehensive overview of zeolite catalysis for organic reactions
within and outside the area of fuels synthesis [ 11.
Over the past few decades, zeolites have bad a
significant impact on the petrochemicals industries
and Venuto has provided an extensive review of
the literature through about 1994 [2]. In addition
to increased use in petrochemicals manufacture,
zeolite catalysis is expanding into the areas of
speciality and fine chemicals synthesis.These efforts
are expected to increase and in the not too distant
future it is likely that a drug molecule or one of
its intermediates will be synthesized over a zeolitebased catalyst. Here, I briefly survey the types of
zeolite-based catalysts that have been reported for
chemicals synthesis and outline several issues of

concern when applying these catalytic systems for

the preparation of fine chemicals. Additionally, I
discuss two emerging areas of importance for
future applications of zeolite-based catalysts for
the synthesis of specially and fine chemicals.
2. Survey of catalyst types for chemicals synthesis
Table 1 provides examples of reactions performed via zeolite-based catalysts that involve the
synthesis of chemicals. Each entry illustrates a
different type of active site.
Several varieties of active sites are directly
related to the types of framework atoms. For
example framework A13+ atoms in zeolites create
anionic lattice sites that can be charge balanced
by protons (BrGnsted acid site) or other cations,
e.g. transition-metal ions. Entries 1 and 2 in Table 1
show reactions catalysed by balancing protons and
cations, respectively. Acylation of methoxynaphthalene is a highly desired reaction if the ketone
functionality can be placed at the 6 position Gnce

1387-181
l/98/$19.000 1998ElsevierScienceB.V. All rights reserved.
PII: s1387-1811(98)00007-9

174

M. E. Davis / Microporous and Mexoporous Materials 21 (1998) 173-182

Table 1
Examples of zeolitic-based catalysis for the synthesis of chemicals
Nature of the active site Example reaction

Comments

Refs.

1. Framework Al3 ,
Bronsted acid

Possible intermediate for

naproxen [ 31, a nonsteroidal
anti-inflammatory agent

141

Intermediate

[X61

(CH,CO),O

CH,CN

H&O

2. Framework A13+,
exchanged ions,
e.g. CO+

CH,CH,

+ NH, + O2

intermediate for acetamino- 171

phen. a pain-killer

3. Framework Ti4 * .
oxidation
+ NH,

+ H,O>

OH

4. Extraframework
metal cluster. e.g. Pd

5. Extraframework
metal oxide cluster,
e.g. Cs,O,
6. Extraframework
(entrapped) organometallic complexes,
e.g. Mn saien

OH
0

OH

OH

SO2 + (CH,),C=NCH,

Intermediate in the synthesis

of vitamin E, (1000 tons/year)

Intermediate for thiabenda- [91

zole, a systemic fungicide

Chiral epoxides used as

intermediates
+

181

[lOI

NaCCl

Only the desired product is illustrated. See the appropriate reference in each case for product distribution and selectivities.

this intermediate could be used to prepare

naproxen [3]. Harvey and Mgider have studied this
reaction over zeolite beta and showed that 1-acetyl2-methoxynaphthalene is the main produce [4].
However, it was speculated that the 2-6 substitution can occur at intrazeolite active sites while the
favored l-2 substitution is from surface active
sites. The 226 difunctionalization of naphthalene
is well documented in the literature on shapeselective, acid-mediated catalysis. The synthesis of
an intermediate for naproxen (world market in
1991was $971 million [3]) presents a new challenge
for 2,6-difunctionalization of naphthalene via zeolite catalysis, and Table 2 lists several of the intermediates that are of interest [3].
In addition to acid sites, cations like transitionmetal ions can function as active sites. A vast
amount literature now exists on transition-metal,
zeolite catalysts for NO, conversion. A recent

example in the area of chemicals synthesis is

from Li and Armor [ 561 (entry 2 in Table 1).
Acetonitrile can be produced by ammoxidation of
ethane using transition-metal zeolites as catalysts
and cobalt appears to be the favored metal ion for
the exchange [5,6].
In principle, any framework substitution of
Si4+ by non-tetravalent ions, e.g. Ga3+, Fe3+,
CO+ Zn+, etc., creates lattice charge. However,
the stability of the framework substitution must
be carefully investigated. Additionally, it is wellknown that the acid strength of a balancing proton
can be affected by the type of substituting element,
e.g., A13+ vs Ga3+ vs Fe3+. An area that has not
been sufficiently explored is that of the acid
strength of protons created by lattice substitutions
of divalent ions, e.g., Zn2+. since they could provide two protons adjacent to one another.
When Si4+ is substituted by Ti4+, then lattice

175

M.E. Davis / Microporous and Mesoporous Materials 21 (1998) 173-182

Table 2
Possible intermediates for the preparation of naproxen (from Ref. [3])
Current cost estimate

Structure

Compound

$lO,kg

2-bromo-6-methoxynaphthalene
,.mBr

$15.-2O/kg

2-acetyl-6-methoxynaphthalene

H,co&cH3
2-methoxy-6-propionylnaphthalene

$15-2O/kg

2-methoxy-6-vinylnaphthalene

$20.-25/kg

$?/kg
COOH

charge is not created. However, the Ti4+, can be

exploited as an active center for oxidation catalysis
when using H,O, and/or hydroperoxides as oxidants. The initial materials discovery in this area is
TS-I and it has been commercialized for several
reactions [ 11,121. In addition to TS-I , other titanium zeohtes have been prepared and Ti-zeolite
beta appears to be the most promising material
[ 13,141. An interesting example of the types of
reactions that can be catalysed by titanium zeolites
is epoxidation of olefins and the reaction listed
in entry 3 of Table 1. The ammoxidation of 4hydroxyacetophenone to the oxime occurs almost
quantitatively over TS-1 (yields near 100%) [7].
The oxime can then form acetaminophen (Tylenol,
paracetamol, etc.) by a Beckman rearrangement as
shown below:

OH

OH

Elements other than Ti4+, e.g. V4+, Cr6+ etc.,

have been incorporated into zeolite samples and
their oxidation behavior investigated. It is not.
clear for elements other than Ti4+ that they remain
in the zeolite during the catalysis. Thus, I believe
that Ti4+ is the only substitution where sufficient
proof is available to conclude that the catalytic
active site is from the framework element when
performing oxidation reactions in the liquid-phase
[I l--14].
In addition to Ti4+ substitution, recent claims
of Sn4 [ 151 and even Zr4 [ 161 have appeared.
These developments could be of interest for performing oxidation and Lewis acid-mediated catalytic reactions, respectively. Verification of the
preparation methods is therefore merited.
In addition to active sites that are created as a
consequenceof lattice substitutions, the zeolite can
be used as a host to encapsulate guest speciesthat
can serve as the active center. lntrazeolitic metal
particles have long been known to be active sites
that can be used alone or in a bifunctional manner
with zeolitic acid sites. A good example of a metal-

M. E. Davis j Microporous and Mesoporous Materials 21 f 1998) 173-182

176

mediated reaction by intrazeolitic metal clusters in

addition to entry 4 in Table 1 is the aromatization
of n-hexane to benzene (shown below) that is now
commercialized by Chevron:

C6HM

-03 t4H,

This reaction can proceed with selectivities

above 90% when using Pt inside of zeolite L (notice
that two useful products are produced from
n-hexane). In addition to metal particles, ionic
clusters (for base catalysis) [ 171. metal oxide clusters (for base [ 18,191and oxidation [20] catalysis)
and organometallic complexes (the number of
examples is very large but an early preparation is
given in Ref. [ 2 11,examples of catalysis in Ref. [ 221
(and referencestherein) and of asymmetric catalysis in Ref. [lo]) have been encapsulated within the
void spaces of zeolites. Entries 4.-6 in Table 1
illustrate examples of reactions catalysed by
entrapped species. The reaction given by entry 4
in Table 1 is a liquid-phase hydrogenation to form
an intermediate for the preparation of vitamin E
and appears to be the first example of a zeolitebased catalyst used for the synthesis of a molecule
for human consumption (commercialized in 1988
[8]). Entry 5 shows a reaction for the preparation
of 4-methylthiazole (4-MT) that is an intermediate
in the synthesis of thiabendazole (a systemic fungicide) [9]. The reaction proceeds over cesiumloaded ZSM-5 and beta and has been operated
at pilot--plant scale [9]. Numerous reports
of entrapped organometallic complexes have
appeared and entry 6 of Table 1 is only a representative case that does however show that chiral
reactions can also proceed with zeolite-based catalysts (vide infra).
3. Trends in zeolite catalysis for chemicals synthesis

Table 3 contains a subjective list of trends in

zeolite catalysis for chemicals synthesis. Most fine
chemicals are prepared via low temperature liquidphase reactions and the use of zeolite-based catalysts is not to likely change this trend. This is due

Table 3
Trends in zeolite catalysis for chemicals synthesis

.-

0 Increased emphasis on low temperature,

liquid-phase
reactions
l Reactants/products containing heteroatoms, e.g. N, !i. 0. P
0 Smaller scale processes
0 Increase in the variety of reaction chemistries
-

in part to the thermal stability of many fine

chemicals and/or their intermediates as well as to
the size scale of the product. Thus, the necessity
of working in the liquid-phase normally implies
the use of a solvent. Zeolites provide the means to
control solvent access to the active sites in that
solvent molecules can be size excluded (shapeselective rejection of large solvent molecules) and
solvent partitioning between the bulk phase and
the intracrystalline void spaceby tuning the hydrophobicity of the solvent and zeolite. Published
work on titanium zeolites suggest the later effect
can be accomplished [23,24].
In addition to the effect attributable to solvent
molecules, low temperature, liquid-phase conversions present challenges for achieving commercially acceptable rates. Clearly this can be done as
exemplified by the commercialization of TS-.1 for
low temperature, liquid-phase oxidations with
aqueous H20, [ 11,121. A possible solution to the
achievement of acceptable rates is the use of
nanocrystalline zeolites, i.e., colloidal sized crystals. Lovallo and Tsapatsis have reviewed this
topic [25]. Zeolite nanocrystals in the size :range
of below 50 nm would be of particular interest to
limit diffusion pathlengths and t.his size range is
feasible with several zeolite structure types, e.g.,
LTL. MFI. MWW and BEA. Of critical importance to catalysis with nanocrystalline zeolites is
the external surface active sites that can now be in
appreciable quantity and readily accessible from
the bulk liquid-phase with the absence of ~diffusional limitations (unlike intracrystalline sites).
Thus, successfulapplication of nanocrystalline zeolite catalysis is likely to involve surface passivation.
New methodologies for surface passivation are
needed since this must be accomplished without
sintering of the nanocrystalline material.
Another feature in performing fine chemicals

M. IT. Davis !/ Microporous and Mesoporous Materials 21 (1998) I73-I82

synthesis that demands thought in catalyst preparation is the fact that most fine chemicals contain
heteroatoms, e.g. N, S, 0 and P. Entry 5 of Table 1
is a good illustration of this point. These heteroatoms create sites for interaction with the zeolite
that can lead to adsorption energies above those
of weak interactions such as van der Waals interactions. Thus, the issue of hydrophobicity of the
zeolite is again important. Also of concern is the
possibility that one functionality of the reactant
molecule poisons the active site necessary to react
a different functional group on the molecule.
Becausefine chemicals are synthesized in smaller
quantities than bulk chemicals or fuels, they
require lower capital investment. This feature is
particularly helpful in tunes of low availability of
capital and in minimizing the barriers for commercialization of new processes. On the other hand,
fine chemicals syntheses require faster times from
initial discovery to commercialization because the
lifetime of the product is not as long as with bulk
chemicals or fuels. Finally, the value added is high
so the catalyst costs can be higher than with
catalysts for bulk chemicals synthesis. This feature
favors the development of new catalysts/processes.
One negative feature of the small scale is the low
amount of catalyst use makes manufacturing the
zeolite at a profit difficult. Thus, I suggest that
zeolite producers form partnerships with the end
users in order to provide an avenue for profit
sharing by both enterprises.
It is obvious from the entries in Table 1 that
the variety of chemistries now being developed
with zeolite-based catalysts is greatly expanding.
However, there is still plenty of room for new
reactions. Of particular importance would be acylation using acetic acid as the acylating agent,
nitration with nitric acid and any antiMarkovnikov additions to name a few. RhonePoulene has commercialized at multi-ton scale the
first Friedel-crafts acylation over a zeolite catalyst
[26]. Activated aromatics, e.g., anisole, can be
acylated with acetic anhydride over zeolite catalysts like HY and Hp. However, acylation using
acetic acid and/or unactivated reactants remains a
challenge. Recently, Pandey and Singh reported
the acylation of aromatics, e.g. benzene, toluene,
with acetic acid and claimed high activity and

177

paraselectivity with MFI [27]. Much further work

is necessary in this direction. The vapor-phase
nitration of benzene with nitric acid has been
accomplished over several zeolites [28]. A surprising result from this work is that clinoptilolite is a
better catalyst than zeolite Y, MOR or MFI
despite the fact that benzene is not expected to
enter the intracrystalline void space [28]. Again,
further work in this area is merited.
At present, bromination and hydroformylation
reactions proceed at commercial scale t0
provide anti-Markovnikov additions. New antiMarkovnikov additions, e.g., hydration of terminal
olefins to synthesize terminal alcohols, amination
of terminal olefins to produce terminal amines,
would be revolutionary. Any reaction pathways
that could be made to proceed in an anti-,
Markovnikov fashion by the use of a zeolite cata,,.
lyst are of interest.
Although the view presented here is of course:
subjective and by no means all inclusive, it does
provide a basis for suggestions of future areas of
concentration. In addition to those topics mentioned previously, below several other areas of
importance that are currently emerging are
discussed.
4. Emerang areas of zeolite-based catalysis for tie
chemicals synthesis

Although great progress has been made in applying zeolite-based catalysts for the synthesis of fine
chemicals, numerous other obstacles exist. For
example, many fine chemicals and their intermediates are too large to enter the pores of zeolites and
many contain chiral centers. Below, the progress
on extra-large pore zeolites and asymmetric reactions using zeolite-based catalysts are discussed.
Like so many other pioneering ideas and concepts in molecular sieve science and technology,
Barrer and his collaborators were the first to report
on the idea of preparing extra-large pore materials
[29]. Barrer and Villiger presented a series of
hypothetical structures related to zeolite L (large
pore) that had 24 membered ring (24MR) pores
with a free diameter of approximately 15 A. Some
of thesenetworks were comprised of known atomic

178

M. E. Davis / Microporous and Mesoporous Materials 21 (1998) 173-182

arrangements that do not violate crystal chemistry

constraints, e.g., bond distances and angles (the
model having a hexagonal unit cell of a =22 A,
c = 7.5 A gives a satisfactory distance least-squares
refinement (DLS-76 [ 301) of the atomic positions).
Subsequently, other hypothetical extra-large pore
networks were reported. For example, Smith and
Dytrych illustrated several nets with channels of
unlimited diameter one of which turned out to be
VPI-5 [31].
In addition to hypothetical, extra-large pore
networks, the structure of an extra-large pore
material, the mineral cacoxenite, was reported by
Moore and Shen in 1983 and contained a channel
of 15 A diameter [32]. Cacoxenite is a hydrated,
basic, ferric oxyphosphate mineral that has yet to
be synthesized. Additionally, it possessesiron octahedra and structural (OH) and H,O groups:

[Al (ALW3Fe21WOHh2WXdI.U-W),41 WI.

Thus, it is not a network containing only oxide
tetahedra in zeolites. Cacoxenite is not able to
function as an adsorbent or catalyst because the
structure collapses upon heating to remove the
water occluded within the pore network.
By the mid-1980s hypothetical, extra-large pore
nets were known, phosphate-based molecular
sieves were known and the structure of the 15 A
pore, phosphate-containing mineral cacoxenite

was known. Thus, it is not surprising that the first

extra-large pore material, VPI-5, is a phosphatebased material-namely
an aluminophosphate.
After the discovery of VPI-5, numerous phosphatebased, extra-large pore materials were prepared.
Table 4 summarizes these materials. All of these
solids except UTD-1, CIT-5 and TPA-SnS-3 are
phosphate-based molecular sieves. Although the
materials listed in Table 4 all have extra-large rings
in their as-synthesizedform, some of these materials decompose upon attempts to remove occluded
material (mostly organic molecules) from their
void spaces,e.g. JDF-20, or have limited thermal
stability that make their use as a molecular sieve
difficult. This is not surprising in view of the fact
that all the materials listed in Table 4 except
UTD-1 and CIT-5 have at least one of the
following features: mixed metal ion coordinations,
e.g., octahedral/tetrahedral aluminum, terminal
(OH ) groups and other nontetrahedral framework
groups, e.g. OH, H,O and F that like cacoxenite
lead to low stability relative to zeolites. For example, the as-synthesized form of VW-5 possesses
octahedral and tetrahedral aluminum. The octahedral aluminum is in the center of the so-called
triple crankshaft chains that make-up the fused
four-rings. The dehydrated triple crankshaft chain
is very strained and the hydration and coordination

Table 4
Summary of extra-large pore materials
Material

Year
reported

Main framework
composition

Ring size
(0 atoms)

Pore size proven

by adsorption

Refs.

VPI-5
AlPO,-8
Cloverite
JDF-20
ULM-5
AIMePO-/I
TPA-SnS-3
Not named
ULM-16
UTD-1
ULM-I5
CIT-5

1988
I990
1991
1992
I994
I995
1995
1996
1996
1996
1997
1997

AIPO,
AIPO,
GaPO,
AIPO,
&P(),
A 1&H$QA
SbS,
V5O,~PO,L
GaPO,
SO,
FePO,
SK),

1s
14
20
20
16
18
32
16
I6
I4
lb
14

13A
<lOA
<lOA
h
NRC
6A
NR
NR
NR
10 b,
NR
ali

[331
[ 14,351
[361
[371
[381
[391
[401
[411
~421
[431
[Ml
[451

Contains a total of 32 atoms.

Vollapse upon activation.
NR: not reported.

M. E. Davis / Microporous and Mesoporous Materiuls 21 (1998) 173-182

179

Silicn-Bad

Fig. 1. Pore sizes of zeolites and molecular sieves.

change (tetrahedral to octahedral) releases this

strain. If the water from as-synthesized VPI-5 is
not carefully removed, it can assist in the transformation of VPI-5 to AlPOd- by participating in
the hydrolysis of Al-O-P linkages. Because the
re-organization of the VPI-5 structure occurs randomly, the AlPOd- thus formed has a high degree
of stacking disorder rendering it with very low
adsorption capacity.
The practical value of phosphate-based extralarge pore materials is limited by their poor thermal
and hydrothermal stabilities compared with zeolites. Thus, the desire for extra-large pore zeolites
is high and the preparation of UTD-1 and CIT-5
proves that the formation of extra-large pore materials is not limited to non-tetrahedral frameworks
and phosphate-based materials. UTD- 1 and CIT-5
are two 14MR high-silica zeolites possessingonly
tetrahedral atoms of silicon and aluminum and
they are thermally stable like other known zeolites.
Fig. 1 schematically illustrates the timeframe for
the movement to extra-large pore materials and
the very recent discoveries of silica-base, extralarge pore solids (UTD-1 and CIT-5). Although
it is not straightforward to prepare aluminumcontaining UTD-1 [43], both UTD-1 and CIT-5

can show acid-mediated, catalytic activity and

selectivities not observed from other zeolites. For
example when m-xylene is reacted at atmospheric
pressure and around 31YC-320C the para/ortho
ratio of the isomerized product is below one for
both UTD-1 and CIT-5 while such is not the case
for other known large-pore zeolites. Additionally,
Ti4+ has been included in UTD-1 and shown to
function as a partial oxidation catalyst for liquidphase reactions [46].
The search for new and larger-pore zeolites will
be very helpful in creating catalysts for fine chemical synthesis. Of particular interest is a multidimensional, extra-large pore material. Davis
has discussed some of the issues of concern in
the quest for extra-large pore materials [47].
Additionally, the mesoporous materials like
MCM41 may find application in this area of
chemicals synthesis. The question of concern is
whether the phosphate-based, crystalline materials
and the mesoporous materials will have stabi1it.y
sufficient for commercial application. The chances
of successwith lower stability materials are higher
with fine chemicals synthesis because of the less
severelifetime demands compared with petrochemical applications.

M. E. Davis / Microporous and Mesoporous Matrrials

180

When performing an asymmetric reaction with

a zeolite catalyst, there are numerous ways in
which the chirality can be brought into the system
(seeTable 5). Examples of introducing asymmetry
via an auxiliary (entries 1,4,6,7), a ligand around
a metal center (entries 2,3,5,8,9), a reactant (entries
10,11,12) and the zeolite framework itself (entry
13) are provided in Table 5. It is interesting to
note that only the concept of performing chiral
reactions with a zeolite catalyst (entry 1) was
recorded prior to the 1990s. Thus, it is clear that
asymmetric catalysis with zeolite containing catalysts is a relatively new field of endeavor. A survey
of the literature provided by the entries in Table 5
shows that several key issues are illustrated by
the results. First, confinement of chiral materials
within the micropores of the zeolite can induce or
enhance enantioselectivities above these observed
in homogeneous solutions. For example with the

21 (1998) 173-182

hydrogenation reactions investigated by Corma

and co-workers [49,50] and the photochemical
conversions of Ramamurthy and co-workers;,[ 551,
the enantioselection is improved by conducting the
reactions within the void spacesof the solid materials. For the hydrogenation reaction, one possible
explanation for the increase in enantioselection
could be due to the locking-in of a particular
conformation of the organometallic complex by
entrapment in the restricted, spatial environment
within the void space of the solid. Second, it
appears that zeolite-based catalysts are not really
providing new reaction chemistries but ,rather
endowing the catalyst with additional features
not observed from the homogeneous analogues,
e.g. immobilization, reactant shape-selectivity. The
exceptions are: (i) the photochemical reaction
where no enantiomeric excess(e.e.) is obtained in
solution (however, if the reaction occurs in the

Table 5
Chiral reactions using zeolite-based catalysts
Catalyst

Reaction
Hydrogenation,

4
5

Metal particle in zeolite with

addition of chiral amine
Rh and Ni chiral complexes in
mesoporous USY
Mo chiral complexes in
mesoporous USY
Pt zeolites with (- )cinchonidine
Ru zeolite with chiiai &and

NaY with a chiral inductor

Zeohte Y with chiral dithiane oxide

I
2
3

8 Chiral Mn salen complexes in EMT

9 Ru-BINAP on zeolite beta
IO Ti zeolite beta
11 Zeolite beta
12 Ti-Zeolite

beta

13 Zeolite beta (some chirality)

e.e., %
hydroformylation

Hydrogenation
Epoxidation

Refs.

Hydrogenation of ethyl pyruvate

Hydrogenation of d-fructose to
d-mannitol
Photochemical conversion of
ketones to alcohols
Dehydration of 2-butanol

Epoxidation of aromatic alkenes

Hydrogenation of p-ketoesters
Epoxidation of chiral. acyclic
allylic alcohols
MeerweinPonndart
-Verley reduction of ketones with chiral alcohol
Asymmetric epoxidation with
chiral hydroperoxides
Ring opening of trans.stilbene
oxide with water

Concept only no experiments

performed
[49,50 ] Chirahty from l&and, rate
enhancements over homogeneous
[51]
Chirality from l&and. rate
enhancements over homogeneous
[52.53] Chirality from (-)cinchonidine
Yields of d-mannitol below 30%
[541
[481

Above 90
of allylic alcohols

Comment

Up to

65

up to 85

up LO 30

[55]

Zeolite necessary to achieve e.c

Enrichment [ 56.571
of one
of the
enantiomers of
2-butanol
up to 88 [IO]
Above 90 [58]
[591

Gas phase, chiral effect not longlived

15

[601

Up to 65

[61]

Chirality from reactant alcohol:

slow rates
Epoxidation of I -hexene

Around 5

[62]

Andlogue of the Jacobsen catalyst

Immobilized Noyori catalyst
Chirality from reactant

Zeoiite framework
chirahty

is the origin of

M. E. Davi.s / Microporous and Mesoporous Materiuls 21 (1998) 173.-182

solid-state, then even higher e.e.s are observed

than those from the zeolite [ 551) and (ii) the very
interesting example of Shum et al. where I-hexene
is epoxidized with an e.e. of 65% in Ti-beta and
near zero with an amorphous titanosilicate using
chiral ethylbenzene hydroperoxide as oxidant [ 611.
When creating immobilized catalysts with zeolites, questions of leaching and catalyst stability
arise. The concern of leaching is a difficult issue
to resolve and initial results suggest that some of
the zeolite-based catalyst systems do not significantly leach. However, the question of catalyst
stability has not been adequately addressedwhich
is especially true for liquid-phase oxidation reactions. Although there are indications that the
immobilized materials reveal enhanced stability
over the homogeneous counterparts, it remains
unclear whether this stability is sufficient for
application.
All of the examples provided in Table 5 except
for entry 13 introduce chirdlity via an organic
component. When the chirality is introduced by
use of the reagents then long-term stability is more
likely. However, for these casesthere is no chiral
amplification (more than one turnover); that is,
the chirality is transferred in a stoichiometric sense.
When the chirality is brought about by a ligand
or auxiliary molecule, then the a.symmetry is
multiplied by true catalysis. In these cases, care
must be taken in order to follow the stability of
the agent inducing the chirality. If an enantiomerically pure zeolite could be synthesized (material
in entry 13 possesseda very small portion of a
chit-al zeolite) then the problem of stability would
be lessened.I-Iowever, the rigid framework would
not likely allow for a great variety of chiral reactions to occur with high e.e.
It is clear at this time that zeolites and chirality
is becoming an area of international interest. As
zeolite catalysis moves further into the developing
field of fine chemicals synthesis via catalytic reactions, the topic of asymmetric conversions with
zeolite-based materials will not disappear, For
zeolite catalysts to be employed in chiral reactions:
0 only small molecules will be converted;
l further
investigations on stability will be
necessary;
l ultimately it would be very nice to see accom-

181

plishment of reaction chemistries not currently

possible with nonzeolite-based catalyst system:s,
e.g., epoxidation of unhindered olefins with high
ee-the work of Shum et al. [6I] is likely t.o
be the first work to achieve this goal.

5. Summary

It is clear that zeolite catalysis is moving further

into the areas of chemicals and fine chemicals
synthesis. As this occurs, new challenges not
encountered with transformation in the petroleumbased industries will have to be overcome. It does
appear that zeolite-based catalyst systemsare wellpositioned to meet some of these challenges.

Acknowledgement

This paper was written while residing as

Professor Visitante Iberdrola de Ciencia y
Tecnologia at the Institute de Tecnologia
Quimica in Valencia, Spain and I thank Avelino
Corma and Miguel Camblor for such a stimulating visit.

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