Microporousand Mesoporous Materials21( 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/$19.00 1998 0 ElsevierScience All rights reserved. B.V. PII: s1387-1811(98)00007-9

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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 1. Framework Al3 , Bronsted acid
H&O

Comments Possible intermediate for naproxen [ 31, a nonsteroidal anti-inflammatory agent Intermediate

Refs. 141

(CH,CO),O

2. Framework A13+, exchanged ions, e.g. CO+ 3. Framework Ti4 * . oxidation

CH,CH,

+ NH, + O2

CH,CN

[X61

intermediate for acetamino- 171 phen. a pain-killer

+ NH, OH + H,O> -

OH 0 OH

4. Extraframework metal cluster. e.g. Pd

Intermediate in the synthesis of vitamin E, (1000 tons/year)

181

OH

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

SO2 + (CH,),C=NCH,

Intermediate for thiabenda- [91 zole, a systemic fungicide

Chiral epoxides used as intermediates

+ NaCCl

[lOI

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

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Table 2 Possible intermediates for the preparation of naproxen (from Ref. [3]) Compound 2-bromo-6-methoxynaphthalene ,.mBr 2-acetyl-6-methoxynaphthalene $15.-2O/kg Structure Current cost estimate $lO,kg

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-

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M. E. Davis j Microporous and Mesoporous Materials 21 f 1998) 173-182 Table 3 Trends in zeolite catalysis for chemicals synthesis

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,

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 -

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

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

177

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

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

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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 possesses octairon hedra 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
Table 4 Summary of extra-large pore materials Material VPI-5 AlPO,-8 Cloverite JDF-20 ULM-5 AIMePO-/I TPA-SnS-3 Not named ULM-16 UTD-1 ULM-I5 CIT-5 Year reported 1988 I990 1991 1992 I994 I995 1995 1996 1996 1996 1997 1997 Main framework composition AIPO, AIPO, GaPO, AIPO, &P(), A 1&H$QA SbS, V5O,~PO,L GaPO, SO, FePO, SK),

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

Ring size (0 atoms) 1s 14 20 20 16 18 32 16 I6 I4 lb 14

Pore size proven by adsorption 13A <lOA <lOA h NRC 6A NR NR NR 10 b, NR ali

Refs.

[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.

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21 (1998) 173-182

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

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 I 2 3 4 5 6 7 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 Reaction Hydrogenation, Hydrogenation Epoxidation of allylic alcohols hydroformylation Above 90 e.e., % Refs. [481 Comment

Up to

65

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

up to 85

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 [55] Zeolite necessary to achieve e.c Gas phase, chiral effect not longlived

up LO 30

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)

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

Enrichment [ 56.571 of one of the enantiomers of 2-butanol up to 88 [IO] Above 90 [58] [591 15 Up to 65 Around 5 [601 [61] [62]

Andlogue of the Jacobsen catalyst Immobilized Noyori catalyst Chirality from reactant Chirality from reactant alcohol: slow rates Epoxidation of I -hexene Zeoiite framework chirahty is the origin of

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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-

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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