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Metathesis Reaction: Sriatun, S.Si, M.Si Department of Chemistry Faculty of Science and Mathematics Diponegoro University

Metathesis reactions involve the breaking and forming of C=C bonds to generate new unsaturated compounds. They are catalyzed by metal carbene intermediates and are gaining popularity in synthesizing olefins and polymers. While many metal-carbene catalysts exist, ruthenium-based catalysts are particularly tolerant of functional groups. Variants of metathesis include ring-closing, ring-opening, acyclic diene, and ring-opening polymerization reactions. Mechanistically, they likely proceed through a metalacyclobutane intermediate. Important applications include the commercial synthesis of housefly pheromone and strong polycyclopentadiene polymers.

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Wulan Sari
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35 views

Metathesis Reaction: Sriatun, S.Si, M.Si Department of Chemistry Faculty of Science and Mathematics Diponegoro University

Metathesis reactions involve the breaking and forming of C=C bonds to generate new unsaturated compounds. They are catalyzed by metal carbene intermediates and are gaining popularity in synthesizing olefins and polymers. While many metal-carbene catalysts exist, ruthenium-based catalysts are particularly tolerant of functional groups. Variants of metathesis include ring-closing, ring-opening, acyclic diene, and ring-opening polymerization reactions. Mechanistically, they likely proceed through a metalacyclobutane intermediate. Important applications include the commercial synthesis of housefly pheromone and strong polycyclopentadiene polymers.

Uploaded by

Wulan Sari
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Metathesis

Reaction
Sriatun, S.Si, M.Si
Department of Chemistry
Faculty of Science and Mathematics
Diponegoro University
Alkene metathesis
Alkene metathesis reactions are gaining wide popularity
in synthesizing unsaturated olefinic compounds as well
as the unsaturated polymeric counterparts.

Central to this catalysis is a metal carbene intermediate


that reacts with olefins to give different olefinic
compounds or even the unsaturated olefinic polymers
depending upon the reaction conditions of the
metathesis reaction. Metathesis is an unusual
transformation in which a C=C is broken and also formed
during catalysis to generate new unsaturated olefins.
Though a large variety of metal−carbene catalysts
have been developed for the metathesis reaction,
only a few have been found to be functional group
tolerant. Thus a critical step in broadening the utility
of metathesis reaction has been in developing
catalysts that are functional group tolerant. In this
regard, the early-transition metal based carbene
catalysts like that of the Ti based ones are highly
oxophilic and hence are intolerant to the functional
groups. On the other hand, the more electron-rich Mo
and W based catalysts are of intermediate character.
Finally, the late-transition metal based Ru catalysts
are found to be exceptionally tolerant toward
functional groups but all the while exhibiting high
reactivity toward olefinic bonds. In this context
notable are the Grubb’s Ru catalyst, which is easy to
handle, and the Schrock’s Mo catalyst, which display
high activity.
The metathesis reaction as such stands for
a family of related reactions all of which
involve a “cutting and stitching” of olefinic
bonds leading to different unsaturated
products. When two different olefin
substrates are used, the reaction is called
the “cross metathesis” owing to the fact
that the olefinic ends are exchanged.

The metathesis reactions can even extend


further to the conjugated dienes that can
undergo Ring Closing Metathesis (RCM) in
systems where the ring strain is not too
high in the final product.
The reverse of Ring Closing Metathesis
(RCM) is called the Ring Opening
Metathesis (ROM), and which is usually
favored in the presence of large excess of
C2H4.
The variants of metathesis often used in
producing polymers are,
(i) the Acyclic Diene Metathesis (ADMET)
(ii) (ii) the Ring Opening Metathesis
Polymerization (ROMP), in which the
relief of ring-strain of cycloalkenes
drives the polymerization reaction
forward. Both of these reactions,
produce long chain polymers in a living
fashion and as a result of which these
reactions are useful for producing block
copolymers −(AAABBBB) n−.

Though several possibilities have been


debated for the mechanism of the
metathesis reaction, the one proceeding
via a metalacyclobutane intermediate has
gained credence.
Several important industrial applications have emerged out of the
metathesis reaction like that of the commercial synthesis of the housefly
pheromone.

Similarly, the polycyclopentadiene polymer, which is formed from the Ring Opening
Metathesis Polymerization (ROMP) of dicyclopentadiene substrate, is used for bullet
proof related applications because of its exceptional strength owing to its cross-
linked nature.

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