Along a plethora of organometallic reactions, which are viable in aqueous media and do not need inert conditions or even a glove box 2,3, several research groups have intensively studied aqueous metathesis reaction. Journal of the american chemical society 2012, 4 45, 1858118584. Safe and generalizable catalyst for carbonylolefin metathesis reaction. Olefin metathesis represents a versatile synthetic tool for the construction of carboncarbon bonds 19. In addition, the aqueous workup required in the tebbe reaction it is typical to quench with a 15% aqueous. It starts by discussing some general reaction parameters and practical considerations for running routine olefin metathesis reactions.
Rutheniumbased heterocyclic carbenecoordinated olefin metathesis catalysts. In addition to the simple metathesis reaction of a single alkene scheme 1. The olefin metathesis reaction displays one of these atom efficient catalysis reactions under m ild conditions 1. Scheme1 displays the most common metathesis reactions. The olefin metathesis reaction grubbs 1978 progress. Burnett and hughes showed that passage of butane over a mix of platinum on alumina a dehydrogenation catalyst and tungsten oxide on silica an olefin metathesis catalyst at high temperatures 399c results in formation of lower and higher mw alkanes, predominantly propane and pentane. The remarkable metalcatalysed olefin metathesis reaction. The astonishing efficiency and selectivity of the reaction to form 6 is due to the mechanism of cm.
This metallacycle then breaks up in the opposite fashion to afford a new alkylidene and new olefin. The widely accepted view that olefin metathesis revolutionized the different fields of synthetic chemistry led to the. It allows a formation of a variety of structurally diverse molecules that cannot be easily prepared by alternative. Department of chemistry, university of regensburg 7,335 views 1. Grubbs discovered that the reaction of the tebbe reagent 61 with alkenes to form metallacycles that can then be used for methylene transfer, has distinct advantages over the tebbe reagent itself. This is a complete examination of the theory and methods of modern olefin metathesis, one of the most widely used chemical reactions in research and industry. The metathesis experts at materia have assembled this guide to help chemists who are interested in applying olefin metathesis in their own synthetic routes. Dft investigations on model complexes of group 4, 5, and 6 transition metals. The reaction involves the rearrangement of carboncarbon double bonds, through the use of metal catalysts, such as the grubbs ru catalyst, schrock w, mo, and re catalysts, and titanocenebased catalysts. Traditional catalysts are derived from a reaction of the metal halides with alkylation agents for example wcl 6etohetalcl 2. The most commonly synthesized ring sizes are between 57 atoms. Olefin metathesis consists of a unique metalcatalyzed. Olefin metathesis 1 involves two olefin substrates which form a fourmembered ring intermediate first proposed by chauvin and then rearrange the substituents to. Schrock for the development of the metathesis method in organic synthesis.
Us8440874b2 olefin isomerization and metathesis catalyst. Olefin metathesis is a chemical reaction in which a molecule with a pair of carboncarbon double bonds, known also as olefins or hydrocarbons, come together and exchange carbon atoms with one another, forming new valueadded molecules in the process. Provides basic information for nonspecialists, while also explaining the latest trends and advancements in the field to experts. Low catalyst activity to effect a reaction without an enthalipic driving force ring strain newer catalysts have been developed low product selectivity for cross methathesis lack of a model current publication deals with this issue predict when it can not be predicted. This book is a followup to ivins olefin metathesis, academic press, 1983. Grubbs metathesis an overview sciencedirect topics. Reaction pathway of diene depends on catalyst, dilution, ring size, and substrate functional groups and sterics. Metathesis reactions have had a tremendous impact in organic synthesis, enabling a variety of applications in polymer chemistry, drug discovery and chemical biology.
Although different isomeric metathesis products could be formed initially, equilibration of the products is promoted by a secondary. The olefin metathesis reaction grubbs 1978 progress in. The nobel prize in chemistry 2005 was awarded jointly to yves chauvin, robert h. It allows a it allows a formation of a variety of structurally diverse molecules that cannot be easily prepared by alternative routes. The type ii olefin will undergo a cross metathesis reaction with the type i olefin. The metathesis reaction mechanism, proposed by chauvin in 1971, suggests that the reaction proceeds via the reversible formation of a metallacyclobutane intermediate scheme 2, intermediates ii and iv. New catalysts with high metathesis activity grubbs, r. Olefin metathesis introduction 3 olefin metathesis constitutes a catalytic method for both cleaving and forming cc double bonds. Olefin metathesis allows the exchange of substituents between different olefins a transalkylidenation. Abstract olefin metathesis is a powerful transformation based on catalytic reaction between alkenes. Olefin metathesis opens up new industrial routes to important petrochemicals, oleochemicals, polymers, and specialty chemicals. Pdf tropyliumpromoted carbonylolefin metathesis reactions.
Grubbs gave synthetic chemists an air stable and watersoluble metal carbene. Olefin metathesis 3 2005 the nobel prize in chemistry yves chauvin prize share. The reaction involves the rearrangement of carboncarbon double bonds, through the use of metal catalysts, such as the grubbs ru catalyst, schrock. Since its first report in 1956, a tiiicatalyzed polymerization of norbornene, metathesis rapidly attracted interest among organic chemists and has been used in different research fields spanning polymer chemistry 1112 to drug discovery 15. The metathesis reaction of 1hexene with the wcl 4 oar 2 catalyst yields 5decene 8 plus many byproducts from secondary metathesis reactions historical overview. Mechanism of the olefin metathesis reaction journal of. Mechanism of the olefin metathesis reaction journal of the. Bringing the standard text in the field up to date, this second edition is a result of rapid growth in the field, sparked by the discovery of numerous welldefined metal carbene complexes that can act as very efficient initiators of all types of olefin metathesis reaction, including ringclosing metathesis of acyclic. Catalyst and process for olefin metathesis reaction download pdf info publication number us20180093933a1. Grubbs gave synthetic chemists an air stable and watersoluble metalcarbene catalyst.
The widely accepted view that olefin metathesis revolutionized the different fields. Why does olefin metathesis lead to the formation of internal alkenes. He realized that olefin metathesis is initiated by the formation of a metal carbene. Us8440874b2 us12554,805 us55480509a us8440874b2 us 8440874 b2 us8440874 b2 us 8440874b2 us 55480509 a us55480509 a us 55480509a us 8440874 b2 us8440874 b2 us 8440874b2 authority us united states prior art keywords butene metathesis catalyst isomerization process prior art date 20080904 legal status the legal status is an assumption and is not a legal. Ring opening metathesis polymerization romp acyclic diene metathesis polymerization admet admet n admet. Catalytic olefin metathesis is a powerful chemical transformation that can convert simple doublebond containing compounds into more complex chemical entities. The reaction can be driven to the right by the loss of ethylene. Rutheniumbased olefin metathesis catalysts derived from alkynes. To date, two heterogeneous catalyst systems have been reported to effect the interconversion of alkanes. The carbonyl olefin metathesis com reaction is a highly valuable chemical transformation in a broad range of applications. Olefin metathesis was first commercialized in petroleum reformation for the synthesis of higher olefins from the products.
Known chemistry prior to the advent of olefin metathesis was introduced by karl ziegler in the 1950s who as part of ongoing work in what would later become known as zieglernatta catalysis studied ethylene polymerization which. In fact, olefin metathesis is a family of reactions connected by the same mechanism and principally the same catalysts vide infra. Schrock accidently created first stable metal carbene catalyst at mit. Intramolecular metathesis of a diene to form a cyclic olefin ring closing metathesis rcm m m m mch2h 2cch rcm n. Reaction pathway and stereoselectivity of olefin metathesis at high temperature. Ringclosing metathesis, or rcm, is a widely used variation of olefin metathesis in organic chemistry for the synthesis of various unsaturated rings via the intramolecular metathesis of two terminal alkenes, which forms the cycloalkene as the e or z isomers and volatile ethylene. In the presence of certain transitionmetal compounds, including various metal carbenes, olefins exchange the groups around the double bonds, resulting in several outcomes. Olefin metathesis catalysts for the preparation of molecules and materials nobel lecture, december 8, 2005 by robert h. This reaction was first used in petroleum reformation for the synthesis of higher olefins shell higher olefin process shop, with nickel catalysts under high pressure and high temperatures. Catalytic alkane metathesis by tandem alkane dehydrogenation. Olefin metathesis reaction in water and in air improved by.
These types of metathesis are called ring closing metathesis, cross metathesis or ring opening polymerization, respectively. Despite, this simplified illustration, the reacting alkenes need not be identical. Olefin metathesis is a thermodynamically controlled process. Olefin metathesis is a powerful reaction catalyzed by transition metals, in which two olefins can form a ring or rearrange their connectivity, or a double bond in a ring can be opened. Alkene metathesis, also known as olefin metathesis, was the subject of the 2005 nobel prize in chemistry. The carbonylolefin metathesis com reaction is a highly valuable chemical transformation in a broad range of applications. Olefin metathesis is a fundamental chemical reaction involving the rearrangement of carboncarbon double bonds, and can be used to couple, cleave, ringclose, ringopen, or polymerize olefinic molecules. The discovery of olefin metathesis dates back to the 1950s, when formation of olefins was observed when gaseous alkenes were passed over the mo catalyst. However, its scope is much less explored compared to analogous olefin.
Low catalyst activity to effect a reaction without an enthalipic driving force ring strain newer catalysts have been developed low product selectivity for cross methathesis lack of a model current publication deals with this issue predict when it can not be predicted low selectivity in the olefin e and z. In this video ill teach you about alkene olefin metathesis, with a few accompanying examples. Industrial applications of olefin metathesis springerlink. In total synthesis in 2011, olefin metathesis was used for times.
Chauvin, grubbs and schrock were awarded in 2005 for their work in olefin metathesis. Schrock created first stable metalcarbene complex at mit. The metathesis reaction mechanism, proposed by chauvin in 1971, suggests that the reaction proceeds via the reversible. Industrial applications of the olefin metathesis reaction known until 1997 have been described elsewhere, including processes that have not been commercialized and processes that are no longer commercial. Ill also discuss the contributions of grubbs, shrock, and chauvin to the field. Olefin metathesis and metathesis polymerization 2nd edition. Chauvin was the first to produce a viable mechanism for olefin metathesis. Olefin metathesis an overview sciencedirect topics. Olefin metathesis is one of the most powerful cc doublebondforming reactions. The reaction is generally reversible and limited to an equilibrium. Olefin metathesis is an organic chemical reaction that uses a metal catalyst for the transfer of substituents between olefins, or alkenes by a 4membered ring intermediate, also known as a chauvin mechanism. Olefin metathesis enables our next generation thermoset. Schrock for their contributions to the field of olefin metathesis. Each time the metallacyclobutane forms, it can form two different.
May 02, 2014 this is a complete examination of the theory and methods of modern olefin metathesis, one of the most widely used chemical reactions in research and industry. Olefin metathesis is a popular and useful reaction. The type i olefin will form a homodimer which will then undergo a cm reaction with the type ii olefin. Department of chemistry, michigan state university, east lansing, michigan. Grubbs california institute of technology caltech, the division of chemistry and chemical engineering, pasadena, ca, 91125, usa. Dielsalder and wittig reactions awarded in 1912, 1950 and 1979.
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