Journal of Scientific & Industrial Research

Vol 65, December 2006, pp 957-965

Metathesis catalysts: Historical perspective, recent developments

and practical applications
Okram Mukherjee Singh*
Department of Chemistry, Manipur University, Canchipur 795 003
Received 29 May 2006; accepted 02 August 2006

Metathesis, a recently developed synthetic chemical methodology, has widespread applications in industries in large-
scale production of organic compounds, pharmaceutical products and polymeric materials.

Keywords: Catalysis, Drugs, Mechanism, Olefin-metathesis, Polymer

Introduction [Mo(CO)6] on alumina}, led to ethylene and 2-

Nobel Prize in Chemistry for 2005 has been butenes. In 1967, 2-butene and 3-hexene were
awarded1 to Frenchman Yves Chauvin and Americans synthesized from 2-pentene by employing a catalytic
Richard Schrock and Robert Grubbs for their system formed from tungsten hexachloride, ethanol
contributions to metathesis. Chauvin2 proposed a new and ethyl-aluminium dichloride and used the term
mechanism of metathesis, whereas Schrock3 and olefin metathesis for the first time8. Calderon9 applied
Grubbs4 developed new catalysts for metathesis. the metathesis to ring-opening polymerization of
Metathesis is a kind of organic synthesis where cyclo-olefins to polyalkenamers. Bradshaw et al10
carbon compounds from very simple and small suggested a reaction mechanism through a four-
molecular weight to very large, complex polymers; centered cyclobutanic intermediate. First order kinetic
macromolecules and even natural products are studies on propene metathesis in the heterogeneous
synthesized. In metathesis, double bonds are broken phase were reported by Begley & Wilson11 and on 2-
and made between carbon atoms in ways that cause pentene metathesis in the homogeneous phase by
atom groups to change places. This happens with the Hughes12. Although the results obtained by Begley &
assistance of special catalyst molecules. Wilson11 indicate a first order kinetics for the reaction
Metathesis of olefins is the reaction in which the of propene, contradicting the mechanism through a
molecules of these hydrocarbons are formally cyclobutanic intermediate, further investigations
fragmented at their double bonds and new olefin carried out in homogeneous catalysis13-14 seemed to
molecules result by recombination of fragments indicate a second order kinetics. The real kinetics of
originating from different molecules (Scheme 1). the process was remaining uncertain until the
Metathesis reactions (Schemes 2-6) are generally discovery of Chauvin mechanism2, which was
reversible and, with the right catalyst system, awarded Nobel Prize in Chemistry for 2005.
equilibrium can be attained in seconds, even with
In 1970, Chauvin & Herisson15 suggested a chain
substrate/catalyst ratios of 104.
mechanism for metathesis and ring opening
polymerization in the homogeneous phase, through
History of Catalytic Metathesis Non-catalytic
carbonic intermediates. In 1973, Chauvin published16
metathesis of olefins has been known since 1931,
that WCl6 + MeLi mixture catalyzes the formation of
when Schneider & Frolich5 obtained ethene and 2-
propene by reaction of 2-butene, which was proposed
butene by pyrolyzing propene at 852°C. Under first
to proceed via methylation of tungsten, followed by
catalyzed metathesis reactions6,7, propene heated with
-elimination in the tungsten-carbon bond of W–CH3
molybdenum {in the form of the metal, oxide or
to form W CH2 (H), then metathesis. Carbonic chain
_____________ mechanism suggested by Chauvin was supported later
*E-mail: ok_mukherjee@yahoo.co.in by the new experimental results17-30.
958 J SCI IND RES VOL 65 DECEMBER 2006

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6
 SINGH: METATHESIS CATALYSTS: DEVELOPMENTS & APPLICATIONS 959

Developing Catalyst Molecules With catalytic metathesis, shorter synthetic routes to

Catalyst systems for the olefin metathesis generally the products give higher yields. Metathesis is
contain a transition metal compound, but often require significant to green chemistry because: 1) Reactions
the presence of a second compound (co catalyst), and are more efficient (fewer steps, fewer resources, less
sometimes a third (promoter). System most waste); 2) Reactions are easier to use (stable under
commonly used is based on the chlorides, oxides, or ambient conditions); and 3) Environmentally benign
other easily accessible compounds of Mo, Ru, W, Re, (non-hazardous solvents, less hazardous waste). For
Os, Ir, Ti, V, Cr, Co, Nb, Rh, or Ta compounds. example, Grubbs used a green approach, from RuCl3
Typical co catalysts are EtAlCl2, R3AlCl2, R3Al and in water to the sophisticated chiral version of the
R4Sn(R=Ph, Me, Et, Bu), while promoters often second-generation ruthenium benzylidene catalyst, to
contain oxygen as O2, EtOH or PhOH. It has now provide the organic and polymer communities with
been realized that metathesis could assume great most environment friendly metathesis catalysts,
importance for organic synthesis if reliable and because of their stability to air and even to some
effective catalysts could be found. Molybdenum and extent to aqueous media and their high compatibility
tungsten soon appeared to be the most suitable metals. with most organic functionalities. A few examples of
Some catalysts were produced with those metals, but the synthetic applications of metathesis in
there was still uncertainty as to what groups would pharmaceuticals are as follows:
bind to the metal to give stable yet active alkylidene Metathesis was used in the synthesis of a
complexes. 7-membered azepin compound called balanol, which
A breakthrough came in 1990 when Schrock is used as anticancer agents and in controlling
et al31-33 reported construction of a group very active, inflammation, cardiovascular disorders, central
well-defined Mo catalyst (Scheme 7). With this nervous system dysfunction, and even HIV infection.
discovery, chemists began to realize that olefin Fuerstner38 & Thiel39 claimed that by using ring-
metathesis could be used for general purposes in closing metathesis, total synthesis of this compound
organic synthesis. Metathesis gained increasing was shortened by 4-5 steps from the earlier methods
attention among researchers active in synthetic (Scheme 9).
chemistry. Yet another breakthrough in the Another anticancer drug epothilone40 and its
development of metathesis catalysts came in 1992 derivatives were also prepared by using the ring
when Grubbs et al34-36 discovered a catalyst with the closing metathesis (Scheme 10). Nicolaou et al41
metal ruthenium. It was stable in air and demonstrated reviewed the efficiency of ring closing metathesis in
higher selectivity but lower reactivity than Mo the total synthesis of macrocyclic lactones and several
catalysts. New catalyst also had the ability to initiate natural products.
metathesis in the presence of alcohols, water and
Similar type of ring closing metathesis was applied
carboxyl acids (Scheme 8).
to produce Civetone42 (cyclo-9-heptadecenone) used
Grubbs’ catalysts have become the first well-
in the perfume industry from ethyl oleate. Another
defined catalysts for general metathesis applications
class of natural compounds, easily obtainable through
in ordinary laboratories. Catalyst 2 in Scheme 8 is
metathesis are insect pheromones, which are useful as
generally named Grubbs’ catalyst and has become a
environment friendly pest-control agents. Pederson
standard with which all new catalysts are compared.
et al43 reported a typical metathesis reaction to yield
The general applicability of Grubbs’ catalyst has
the pheromone, 11-tetradecenyl acetate from a long
given rise to future prospects of the possibilities of
chain olefinic ester and 3-hexene catalyzed by Grubbs
organic synthesis. Grubbs bases his catalyst design on
catalyst B (Scheme 11).
detailed mechanical studies.
Materia Medica, an international drug company has
Practical Applications of Metathesis produced three pheromones: i) (E)-5-decenyl acetate,
Pharmaceutical Industries a pheromone of peach twig borer (Anarsia lineatella);
Metathesis is an important tool for new ii) a mixture of (E)- and (Z)-11-tetradecenyl acetate,
pharmaceuticals used in treating major diseases such as of omnivorous leafroller (Platynota stultana); and (iii)
bacterial infections, hepatitis C, cancer, Alzheimer’s different mixture of (E)- and (Z)-11-tetradecenyl
disease, Down’s syndrome, osteoporosis, arthritis, acetate, of Sparganothis fruit worm, a pest of
inflammation, fibrosis, HIV/AIDS, migraine, etc37. cranberries and blueberries.
960 J SCI IND RES VOL 65 DECEMBER 2006

Scheme 7

Scheme 8

Scheme 9
SINGH: METATHESIS CATALYSTS: DEVELOPMENTS & APPLICATIONS 961

Scheme 10

Scheme 11
962 J SCI IND RES VOL 65 DECEMBER 2006

Hydrocarbon Industries disproportionated by metathesis to detergent range

First metathesis process applied on an industrial internal olefins (C11-C14) in the disproportionation
scale, developed by Phillips Petroleum Co., USA, and reactor, and the product is fractionated in distillation
known as The Triolefin Process44, produces high- columns, into fractions of higher olefins.
purity ethene and but-2-ene from propene. This Shell Chemicals began large-scale production of
process operated for 6 years from 1996 by detergent alcohols and esters, which are made of long
Shawanigan Chemicals near Montreal in Canada chain alkenes that are prepared from ethane using
(capacity, 50,000 tons/year). It is based on the metathesis procedure45. Shell Chemicals produced
following metathesis reaction: 200000 tons of detergent-range alkenes in 1979 in
Geismar, Luisiana (USA), the capacity increased in
2 CH3CH=CH2 ↔ CH2=CH2 + CH3CH=CHCH3 1989 to 590000 tons per year. A second plant came in
1982 in Stanlow (UK) to produce 270000 tons per
The reaction is carried out in a tubular reactor with year of higher alkenes. Similarly, various other
a fixed bed of catalyst. The catalyst used was industrial companies have developed metathesis
WO3/SiO2, doped with sodium to prevent double- process46 for the production of 2-methylbut-2-ene
bond shift reactions at 350-425°C. The 2-butene (isoamylene, a precursor for isoprene, and α, ω-
(yield, 90%), obtained by this process, can be used as disubstituted olefins, starting materials of aroma
a starting material for gasoline or it can be isomerized chemicals, pharmaceuticals, and agricultural
to but-1-ene, which is in demand as a co-monomer in chemicals. A representative example of α, ω-
polyethylene production. The Triolefin Process was disubstituted olefins, hexa-1,5-diene was produced in
modified afterwards to produce higher olefins such as 1987 by FEAST(Further Exploitation of Advanced
hexenes, heptenes and octenes. An important Shell Technology) in a plant (capacity of 3000
industrial method, which produces ethene and tons/year) at Berre 1, Etang (France).
butadiene through propene metathesis, starts directly
from a naphtha cracker. Polymer Industries
Catalyzed metathesis was discovered in the
In 1969, the Phillips Petroleum Co. started industry following observations in the 1950s of the
producing 3,3-dimethylbut-1-ene (neohexene) as an polymerization of ethylene by Ziegler (Nobel Prize in
important intermediate in the synthesis of musk Chemistry 1963)47,48. Polymerization of cyclopentene
perfume. In 1985, the Lyondell Petrochemical Co., to polypentenamer found application immediately
started producing 136000 tons of propene per year at after the discovery of olefin metathesis49. Trans- and
a plant in Channelview, texas, USA. In this process, cis- polypentenamer produced by the metathesis has
part of the ethane from ethane-cracking unit was aroused the rubber industry as the former has
dimerized to but-2-ene using a homogeneous Ni- properties close to those of natural rubber while the
catalyst developed by Phillips, which reacts via the latter is similar to some special rubbers50. Chemische
reverse Phillips triolefin process with the rest of the Werke Huls, Marl, Germany, first marketed the
ethene to produce propene. The Institue Francais du ring-opened polymer of cyclooctene, under the trade
Petrole(IFP) and the Chinese petroleum name Vestenamer 8012 (Scheme 12)51, 52.
corporation(Taiwan) have jointly developed a Vestenamer 8012 possesses extremely unusual
commercial process, called Meta-4, in which ethene properties for an elastomer. At 20°C, it is hard and
and but-2-ene react with each other in the liquid phase has an exceptionally high viscosity; above 60°C it
in the presence of an Re2O7/Al2O3 catalyst. becomes a fluid with a honey-like consistency. It is
A large-scale industrial process incorporating especially suitable for use in blends with other
olefin metathesis is the Shell Higher Olefins Process rubbers and blending was improved in terms of
(SHOP)45 for converting ethene to detergent-range excellent co-vulcanization with other elastomers,
alkenes for the production of lubricants, plasticizer higher hardness and elasticity of vulcanizate and very
alcohols, detergent alcohols, synthetic fatty acids etc. high stability against thermal, oxidative and
In the second stage, these alkenes undergo double- photochemical degradation. In 1976, CdF Chimie and
bond isomerization over a solid alkali-metal based Elf Atochem in Carling, France started producing
isomerization reactor to an equilibrium mixture of polymers of norbornene53. Monomer was made by the
internal alkenes. In third stage, mixture is Diels-Alder reaction of cyclopentadiene and ethane.
 SINGH: METATHESIS CATALYSTS: DEVELOPMENTS & APPLICATIONS 963

Scheme 12

Ring-opening metathesis used a RuCl3/HCl catalyst in streamline the development and industrial production
butanol. The polymer is marketed as a moulding of pharmaceuticals, plastics and other materials.
powder under the trade name Norsorex and contains a
small amount of non-staining antioxidant. It can be Acknowledgements
moulded and cured in the usual way up to 185°C. Author thanks DST, New Delhi, Govt of India for a
Vulcanized product has important special BOYSCAST fellowship and grateful to Prof P J
applications, particularly for engine mountings, anti- Stang, Department of Chemistry, University of Utah,
vibration mounts, shock-proof bumpers, and flexible USA for the encouragement.
couplings. Another extension plant using ring-
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