The key to this reaction is a conceptual blueprint for. Thus a metal oxo species 26 engages an olefin substrate to form a metallooxetane 27. A proposed chauvintype catalytic cycle for a carbonyl olefin metathesis is shown in figure 6. Olefin metathesis is an organic reaction that entails the redistribution of fragments of alkenes olefins by the scission and regeneration of carboncarbon double bonds. The objective of this program is to develop a highly efficient and broadly applicable catalytic platform for carbonyl olefin metathesis. The generality of this protocol for carbonylolefin metathesis was later investigated for a series of acetophenones, bearing prenyl 26, geranyl 28, and homoprenyl 29 sidechains in the ortho position. Here we demonstrate a catalytic carbonyl olefin ringclosing metathesis reaction that uses iron, an earthabundant and environmentally benign transition metal, as a catalyst. To develop a catalytic carbonylolefin ringopening metathesis reaction, we focused on aryl aldehydes 5. Department of chemistry, jadavpur university, 188 raja s.
Key words iodonium, carbonyl olefin metathesis, metathesis, olefination, catalysis, functional group interconversion the carbonyl moiety is one of the most ubiquitous functional group in organic chemistry. Mar 15, 2019 specifically, in carbonylolefin metathesis reactions carbonyl and alkene substrates are interchanged directly to form new carbonyl and alkene products. Pdf tropyliumpromoted carbonylolefin metathesis reactions. Catalytic, transannular carbonylolefin metathesis reactions. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries. My research laboratory has developed a lewis acidcatalyzed carbonyl olefin metathesis that. Carbonyl coupling reactions mcmurry reaction smith ch. The metalmediated processes include a carbonylolefination and an olefinolefin metathesis event.
Carbonyl ketones or aldehydes metathesis byproduct r 1 r 5 r 4 r 3 r 2 alkyl, aryl alkyl, aryl alkyl h, alkyl, aryl h, alkyl, aryl origin routine methodologies for alkene formation rely on direct elimination, stoichiometric carbonyl ole. However, its scope is much less explored compared to analogous olefin. Grubbs gave synthetic chemists an air stable and watersoluble metal carbene. In organic chemistry, olefin olefin metathesis of two unsaturated substrates for the formation of a new carboncarbon bond has been widely explored and applied. Abstract the carbonylolefin metathesis reaction has experienced. Interrupted carbonylolefin metathesis via oxygen atom. Routine methodologies for alkene formation rely on direct elimination, stoichiometric carbonylolefination, and olefinolefin metathesis.
Ironiiicatalyzed ringclosing carbonylolefin metathesis. Supporting information catalytic, transannular carbonyl. The carbonyl olefin exchange reaction coer is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis om one carbon atom in the latter is replaced with an oxygen atom. The olefin metathesis reaction chemistry libretexts. Optimization of catalyst loading and reaction temperature showed that 15 mol% of tropylium tetrafluroborate at 90 c in neat conditions are optimal for this reaction on substrate 1a entry. Carbonylolefin metathesis reactions between olefin and carbonyl functionalities similarly enable the. Now, a simple lewis acid has been shown to catalyse metathesis. Feiiicatalyzed carbonylolefin metathesis of aryl ketone schindler, 2016 3. For their elucidation of the reaction mechanism and their.
The carbonyl olefin metathesis reaction similarly enables the construction of carboncarbon bonds and has the potentialto have an analogous impact on synthetic strategy. Iodoniumcatalyzed carbonylolefin metathesis reactions. This intermediate undergoes cycloreversion to generate an intermediate 28 bearing a carbonyl and a metal alkylidene. Because of the relative simplicity of olefin metathesis, it often creates fewer undesired byproducts and hazardous wastes than alternative organic reactions.
Tetrahydropyridines via fecl3catalyzed carbonylolefin. Exploration of the construction of a carboncarbon bond through the carbonylolefin metathesis reaction remains limited but has recently attracted significant interest and. Schindler university of michigan, department of chemistry and life sciences institute, 930 north university ave. Although carbonylolefin metathesis reactionsin which a c o bond and a c c bond switch bonding partners to make a new carbonyl and a new olefin have been known for decades, most require. Feiiicatalyzed carbonyl olefin metathesis of aryl ketone schindler, 2016 3. Iron iii catalysed carbonylolefin metathesis nature. The carbonyl olefin metathesis com reaction is a highly valuable chemical transformation in a broad range of applications. Although carbonylolefin metathesis reactionsin which a c o bond and a c c bond switch bonding partners to make a new carbonyl and a new olefinhave been known for decades, most require. Abstract the carbonylolefin metathesis reaction has become in creasingly important in organic synthesis due to its versatility in func. Tandem olefin metathesis big chemical encyclopedia. Intermolecular carbonylolefin metathesis with vinyl ethers. The carbonyl olefin metathesis reaction was discovered around the same time as the olefin metathesis reaction, but has had limited applicability due to.
Olefin metathesis by rhenium carbonyl halidealkylaluminum halide catalysts. However, currently available synthetic procedures are significantly less advanced. Herein, we describe the development of a synthetic strategy toward chiral 3pyrrolines based on the design principle of ironiiicatalyzed carbonyl olefin metathesis. Herein we describe the application of lewisacidcatalyzed carbonylolefin metathesis toward the synthesis of substituted tetrahydropyridines from commercially available amino acids as chiral pool reagents. The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carboncarbonbondforming reactions in organic chemistry. It is a powerful method in organic synthesis using simple carbonyls and olefins and converting them into less accessible products with higher structural. In organic chemistry, olefinolefin metathesis of two unsaturated substrates for the formation of a new carboncarbon bond has been widely explored and applied. The widely accepted view that olefin metathesis revolutionized the different fields. Olefin cross metathesis reported by pulin wang february 21, 2008 introduction olefins are important functional groups in organic synthesis. In total synthesis in 2011, olefin metathesis was used for times. Carbonylolefin metathesis represents a new, catalytic alternative for direct alkene formation from carbonyl and olefin substrates upon activation with a lewis acid. Nov 05, 2012 the development of a catalytic carbonyl olefin metathesis strategy is reported, in the context of the ringopening metathesis of cyclopropenes with aldehydes using a simple hydrazine catalyst. Dft study on the organocatalytic carbonyl olefin metathesis. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functionalgroup tolerance, and.
Compared with the ripeness of olefin metathesis, exploration of the construction of carboncarbon double bonds through the catalytic carbonyl olefin metathesis reaction remains stagnant and has received scant attention. Olefin metathesis is a thermodynamically controlled process. Synthesis of polyphenylacetylene by ironiii chloride. Carbonylolefin metathesis for the synthesis of cyclic. Towards the development of green organic synthesis volume. Schindler,1, 1 university ofmichigan, department chemistry, willard henry dow laboratory, 930 north ave. View enhanced pdf access article on wiley online library html view download pdf for offline viewing. Safe and generalizable catalyst for carbonylolefin metathesis reaction. The developed interrupted carbonylolefin metathesis reaction complements the repertoire of wellestablished reactions between carbonyls and olefins and provides entry into the formation of complex, polycyclic tetrahydrofluorenes in a single synthetic step relying on tfoh as an inexpensive catalyst. Chauvin was the first to produce a viable mechanism for olefin metathesis. Safe and generalizable catalyst for carbonylolefin metathesis reaction 1 june 2016, by heather zeiger scope of the ironiiicatalysed carbonyl olefin.
Safe and generalizable catalyst for carbonyl olefin metathesis reaction. Chiral tetrahydropyridines via fecl3catalyzed carbonylolefin. Jul 19, 2016 exploiting catalytic carbonylolefin metathesis is an ongoing challenge in organic synthesis. Schrock accidently created first stable metal carbene catalyst at mit. 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. Catalytic, transannular carbonyl olefin metathesis reactions paul s. Robust route for carbonylolefin metathesis april 27, 2016.
Big lewis questions in chemistry acidcatalyzed carbonylole. Remarkable innovations have been made in the preparation of new catalysts. This approach takes advantage of commercially available amino acids as chiral pool reagents and fecl3 as a lewis acid catalyst. Lewis acidcatalyzed carbonylolefin metathesis sciencedirect. The development of a catalytic carbonyl olefin metathesis strategy is reported, in the context of the ringopening metathesis of cyclopropenes with aldehydes using a simple hydrazine catalyst. Key words iodonium, carbonylolefin metathesis, metathesis, olefination, catalysis, functional group interconversion the carbonyl moiety is one of the most ubiquitous functional group in organic chemistry. From other alkenestransition metal catalyzed crosscoupling and olefin metathesis. Safe and generalizable catalyst for carbonylolefin. Ironiiicatalyzed carbonylolefin ringclosing metathesis represents a new approach toward the assembly of molecules traditionally generated by olefinolefin metathesis or olefination. Direct evidence for a coordinated carbene initiated process. Carbonylolefin metathesis for the synthesis of cyclic olefins. The olefin metathesis reaction the subject of 2005 nobel prize in chemistry can be thought of as a reaction in which all the carboncarbon double bonds in an olefin alkene are cut and then rearranged in a statistical fashion if one of the product alkenes is volatile such as ethylene or easily removed, then the reaction shown above can be driven completely to the right. Achievement of this goal would enable the development of a range of valuable processes, including ringopening and ringclosing carbonyl olefin metathesis, carbonyl olefination, and nonmetal based olefin metathesis. Specifically, in carbonylolefin metathesis reactions carbonyl and alkene substrates are interchanged directly to form new carbonyl and alkene products.
Organocatalytic carbonylolefin metathesis and olefin. Sep 28, 2018 the developed interrupted carbonyl olefin metathesis reaction complements the repertoire of wellestablished reactions between carbonyls and olefins and provides entry into the formation of complex, polycyclic tetrahydrofluorenes in a single synthetic step relying on tfoh as an inexpensive catalyst. Ironiiicatalyzed carbonyl olefin ringclosing metathesis represents a new approach toward the assembly of molecules traditionally generated by olefin olefin metathesis or olefination. Dec 22, 2019 compared with the ripeness of olefin metathesis, exploration of the construction of carboncarbon double bonds through the catalytic carbonylolefin metathesis reaction remains stagnant and has received scant attention. Olefin cross metathesis cm, on the other hand, represents an understudied area. Overall, these rigorous mechanistic studies catalogue the factors critical to concise reaction design, enhancing the use of carbonylolefin metathesis in the construction of medicinally important molecules.
Carbonyls and alkenes, two of the most common functional groups in organic chemistry, generally do not react with one another. Jun 01, 2016 the carbonyl olefin metathesis reaction was discovered around the same time as the olefin metathesis reaction, but has had limited applicability due to harsh reaction conditions and stringent. Herein, recent efforts to develop amild lewis acid catalyzed ringclosing carbonyl olefin metathesis rccom process are highlighted scheme 1c. Organocatalytic carbonylolefin metathesis journal of the. Catalysts for this reaction have evolved rapidly for the past few decades. Tandem olefin metathesis grubbs has reported a similar tandem olefin metathesis carbonyl olelination process for the preparation of cyclic olefins 31. Under these conditions, competing intermolecular olelination does not occur.
This strategy opens opportunities for new developments in the field of carbonyl olefin metathesis, which traditionally relied on stoichiometric amounts of transition. There are two general mechanistic schemes to perform this overall transformation. Considerable break through has been achieved exploring ironiii cata lysed carbonyl olefin metathesis reactions. A freshly open sample of anhydrous fecl3, used in a glovebox, did not. S5 in situ 1hnmr experiment for intramolecular carbonyl olefin metathesis. 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. Herein, we report detailed synthetic, spectroscopic, kinetic, and computational studies to determine the mechanistic features imparted by ironiii. Request pdf organocatalytic carbonylolefin metathesis the development of a catalytic carbonylolefin metathesis strategy is reported, in the context of the. Safe and generalizable catalyst for carbonylolefin metathesis reaction 1 june 2016, by heather zeiger scope of the ironiiicatalysed carbonylolefin. This approach is characterized by operational simplicity. The generality of this protocol for carbonyl olefin metathesis was later investigated for a series of acetophenones, bearing prenyl 26, geranyl 28, and homoprenyl 29 sidechains in the ortho position. This strategy relies on fecl3 as an inexpensive and environmentally benign catalyst and enables access to a variety of substituted tetrahydropyridines under mild reaction conditions. Herein, recent efforts to develop amild lewis acid catalyzed ringclosing carbonylolefin metathesis rccom process are highlighted scheme 1c. Robust route for carbonylolefin metathesis april 27.
The most commonly synthesized ring sizes are between 57 atoms. The carbonyl olefin metathesis reaction, like the well established olefin metathesis reaction, can be used to construct carboncarbon bonds. Organocatalytic carbonylolefin metathesis request pdf. Herein we describe the application of lewisacidcatalyzed carbonyl olefin metathesis toward the synthesis of substituted tetrahydropyridines from commercially available amino acids as chiral pool reagents. Mallick road, kolkata 700032, department of chemistry, balurghat college, balurghat, west bengal 733103. In addition to their prevalence in natural products, olefins can be reliably modified into a great diversity of functional groups with many readily available processes. This metallacycle then breaks up in the opposite fashion to afford a new alkylidene and new olefin. Dft study on the organocatalytic carbonylolefin metathesis. Gacl3catalyzed ringopening carbonylolefin metathesis. Carbonyl olefin metathesis is a type of metathesis reaction that entails, formally, the redistribution of fragments of an alkene and a carbonyl by the scission and regeneration of carboncarbon and carbonoxygen double bonds respectively. Organocatalytic carbonylolefin metathesis journal of. Our strategy is characterized by its operational simplicity, mild reaction conditions, and. Ironiiicatalysed carbonylolefin metathesis nasaads. Feiiicatalyzed carbonyl olefin metathesis of aliphatic ketone schindler, 2019.
Using dft to study the organocatalytic carbonylolefin metathesis. Using dft to study the organocatalytic carbonyl olefin metathesis. Apr 27, 2016 the olefin metathesis reaction of two unsaturated substrates is one of the most powerful carboncarbonbondforming reactions in organic chemistry. Mechanistic investigations of the ironiiicatalyzed. Olefin metathesis 3 2005 the nobel prize in chemistry yves chauvin prize share. Introduction during the last decade, a new synthetic route for the preparation of oligomeric products based on carbonyl olefin exchange reaction and reductive coupling of conjugated compounds has been. Herein, we report detailed synthetic, spectroscopic, kinetic, and computational studies to determine the mechanistic features imparted by ironiii, substrate, and temperature to the catalytic cycle.
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