This document discusses metathesis reactions and their applications in organic synthesis. It begins with definitions and examples of different types of metathesis reactions including alkene, alkyne, and enyne metathesis. It then covers the key catalysts used, such as Grubbs and Schrock catalysts, as well as the 2005 Nobel Prize awarded for the development of metathesis reactions. The document concludes by outlining several important applications of metathesis in synthesizing biologically active compounds and natural products.
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. These types of metathesis are called ring closing metathesis, cross metathesis or ring opening polymerization, respectively.
Created by Elizabeth Billings
Edited by Margaret Hilton
Honors Organic Chemistry
Chem 2321 (Sigman), 2013, University of Utah
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. These types of metathesis are called ring closing metathesis, cross metathesis or ring opening polymerization, respectively.
Created by Elizabeth Billings
Edited by Margaret Hilton
Honors Organic Chemistry
Chem 2321 (Sigman), 2013, University of Utah
THE PERICYCLIC REACTION THE MOST COMMON TOPIC INCLUDE THE SYLLABUS OF MANY SCIENCE STUDY INCLUDING BSC, MSC , PHARMA STUDY, AND MORE HENCE WE ARE COVERED ALL THE DATA OF IT HOPE THIS WILL MAKE READER EASY.
Organometallic Reactions and CatalysisRajat Ghalta
Organometallic compounds undergo a rich variety of reactions (oxidative addition, reductive elimination, cyclometalization, migratory insertion, carbonylation, hydrometallation hydrate elimination, etc ) that can sometimes be combined into useful homogeneous catalytic cycles. In this presentation, I have discussed organometallic reactions of particular importance for synthetic and catalytic processes like the oxo process (hydroformylation), heck coupling reaction, Wilkinson’s Catalyst
(Hydrogenation) etc.
The video lecture for this presentation is available at the following link on YouTube
https://youtu.be/3sxal579RNM
The presenation will be useful for Ug/PG (Chemistry) students
A carbene is any neutral carbon species which contains a non-bonding valance pair of electrons.
Contributed by Alison Brown & Nathan Buehler, Undergraduates, University of Utah
These are chemical shift reagents and solvent induced shifts have their application in resolving the NMR Spectra of complex structures by inducing shift with respect to reference compound. Thus useful in interpretation of structures of complex organic compounds.
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THE PERICYCLIC REACTION THE MOST COMMON TOPIC INCLUDE THE SYLLABUS OF MANY SCIENCE STUDY INCLUDING BSC, MSC , PHARMA STUDY, AND MORE HENCE WE ARE COVERED ALL THE DATA OF IT HOPE THIS WILL MAKE READER EASY.
Organometallic Reactions and CatalysisRajat Ghalta
Organometallic compounds undergo a rich variety of reactions (oxidative addition, reductive elimination, cyclometalization, migratory insertion, carbonylation, hydrometallation hydrate elimination, etc ) that can sometimes be combined into useful homogeneous catalytic cycles. In this presentation, I have discussed organometallic reactions of particular importance for synthetic and catalytic processes like the oxo process (hydroformylation), heck coupling reaction, Wilkinson’s Catalyst
(Hydrogenation) etc.
The video lecture for this presentation is available at the following link on YouTube
https://youtu.be/3sxal579RNM
The presenation will be useful for Ug/PG (Chemistry) students
A carbene is any neutral carbon species which contains a non-bonding valance pair of electrons.
Contributed by Alison Brown & Nathan Buehler, Undergraduates, University of Utah
These are chemical shift reagents and solvent induced shifts have their application in resolving the NMR Spectra of complex structures by inducing shift with respect to reference compound. Thus useful in interpretation of structures of complex organic compounds.
Total synthesis of Sterpurenone New, Total Synthesis of (훽)-Cyperolone, Protecting Group-Free Total Synthesis of (−)-Lannotinidine B, Enantiospecific Total Synthesis of the (−)-Presilphiperfolan-8-ol, Enantioselective Total Synthesis of (−)-Pavidolide B, total synthesis of Eupalinilide E
Water as a solvent in microwave assisted organic synthesisPrashantChavan93
Prashant Chavan
Reserach Scholar
M.S.(Pharm) in Medicinal Chemistry
National Institute of Pharmaceutical Education and Research Mohali, Punjab (India) 160062
mcm20_prashant@niper.ac.in
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Source: Tetrahedron Lett. 2011 December 21; 52(51): 6855–6858.
GRIGNARD REAGENT RMgX.A Grignard reagent is an organomagnesium compound which can be described by the chemical formula 'R-Mg-X' where R refers to an alkyl or aryl group and X refers to a halogen. They are generally produced by reacting an aryl halide or an alkyl halide with magnesium.A Grignard reagent or Grignard compound is a chemical compound with the general formula R−Mg−X, where X is a halogen and R is an organic group, ..
Richard's aventures in two entangled wonderlandsRichard Gill
Since the loophole-free Bell experiments of 2020 and the Nobel prizes in physics of 2022, critics of Bell's work have retreated to the fortress of super-determinism. Now, super-determinism is a derogatory word - it just means "determinism". Palmer, Hance and Hossenfelder argue that quantum mechanics and determinism are not incompatible, using a sophisticated mathematical construction based on a subtle thinning of allowed states and measurements in quantum mechanics, such that what is left appears to make Bell's argument fail, without altering the empirical predictions of quantum mechanics. I think however that it is a smoke screen, and the slogan "lost in math" comes to my mind. I will discuss some other recent disproofs of Bell's theorem using the language of causality based on causal graphs. Causal thinking is also central to law and justice. I will mention surprising connections to my work on serial killer nurse cases, in particular the Dutch case of Lucia de Berk and the current UK case of Lucy Letby.
This pdf is about the Schizophrenia.
For more details visit on YouTube; @SELF-EXPLANATORY;
https://www.youtube.com/channel/UCAiarMZDNhe1A3Rnpr_WkzA/videos
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Slide 1: Title Slide
Extrachromosomal Inheritance
Slide 2: Introduction to Extrachromosomal Inheritance
Definition: Extrachromosomal inheritance refers to the transmission of genetic material that is not found within the nucleus.
Key Components: Involves genes located in mitochondria, chloroplasts, and plasmids.
Slide 3: Mitochondrial Inheritance
Mitochondria: Organelles responsible for energy production.
Mitochondrial DNA (mtDNA): Circular DNA molecule found in mitochondria.
Inheritance Pattern: Maternally inherited, meaning it is passed from mothers to all their offspring.
Diseases: Examples include Leber’s hereditary optic neuropathy (LHON) and mitochondrial myopathy.
Slide 4: Chloroplast Inheritance
Chloroplasts: Organelles responsible for photosynthesis in plants.
Chloroplast DNA (cpDNA): Circular DNA molecule found in chloroplasts.
Inheritance Pattern: Often maternally inherited in most plants, but can vary in some species.
Examples: Variegation in plants, where leaf color patterns are determined by chloroplast DNA.
Slide 5: Plasmid Inheritance
Plasmids: Small, circular DNA molecules found in bacteria and some eukaryotes.
Features: Can carry antibiotic resistance genes and can be transferred between cells through processes like conjugation.
Significance: Important in biotechnology for gene cloning and genetic engineering.
Slide 6: Mechanisms of Extrachromosomal Inheritance
Non-Mendelian Patterns: Do not follow Mendel’s laws of inheritance.
Cytoplasmic Segregation: During cell division, organelles like mitochondria and chloroplasts are randomly distributed to daughter cells.
Heteroplasmy: Presence of more than one type of organellar genome within a cell, leading to variation in expression.
Slide 7: Examples of Extrachromosomal Inheritance
Four O’clock Plant (Mirabilis jalapa): Shows variegated leaves due to different cpDNA in leaf cells.
Petite Mutants in Yeast: Result from mutations in mitochondrial DNA affecting respiration.
Slide 8: Importance of Extrachromosomal Inheritance
Evolution: Provides insight into the evolution of eukaryotic cells.
Medicine: Understanding mitochondrial inheritance helps in diagnosing and treating mitochondrial diseases.
Agriculture: Chloroplast inheritance can be used in plant breeding and genetic modification.
Slide 9: Recent Research and Advances
Gene Editing: Techniques like CRISPR-Cas9 are being used to edit mitochondrial and chloroplast DNA.
Therapies: Development of mitochondrial replacement therapy (MRT) for preventing mitochondrial diseases.
Slide 10: Conclusion
Summary: Extrachromosomal inheritance involves the transmission of genetic material outside the nucleus and plays a crucial role in genetics, medicine, and biotechnology.
Future Directions: Continued research and technological advancements hold promise for new treatments and applications.
Slide 11: Questions and Discussion
Invite Audience: Open the floor for any questions or further discussion on the topic.
3. Metathesis
Metathesis = Meta(Change) + thesis(position)
It is the change of parts of two substances in a chemical reaction
AB + CD AC + BD
or
AD + BC
AgNO3 + HCl AgCl + HNO3
NaCN + NH4Cl NaCl + NH4CN
3
4. Metathesis in an organic reaction entails redistribution of
alkenes/ alkynes fragments by the scission of carbon - carbon
double/ triple bonds. Two and two bonds are broken and
two new and two new bonds are formed.
4
5. Olefin metathesis was first observed in the 1950s (Herbert S.
Eleuterio, at Du Pont's petrochemicals department) ,
The reaction was extended with cyclopentene
They tell "the polymer we got looked like somebody took a pair of
scissors, opened up cyclopentene, and neatly sewed it up again"
However real mechanism of these reaction remained the mystery till
1990.
Discovery of olefin Metathesis
polymer
5
6. Olefin metathesis is an equilibrium process and with many
alkenes, substrates yields a mixture of starting material and two
or more alkenes products.
However, with terminal alkenes, one metathesis product is
ethylene gas (CH2=CH2), which escapes from the reaction
mixture and drives the equilibrium to the right.
Thus, monosubstituted alkenes (RCH=CH2) and 2,2-
disubstituted alkenes (R2C=CH2) are excellent metathesis
substrates because high yields of a single alkene product.
Characteristics of Metathesis Reactions
6
8. Transalkylidination or Transalkylation ?
At first, it was questioned , whether, olefin metathesis is exchange of
alkyl or alkylidene groups.
Which one is correct? 8
14. 4. Acyclic Diene Metathesis polymerization
+
+
C8 C8
C14 C2
Carrying this reaction out over and over with the more reactive
terminal double bonds leads to acyclic diene metathesis (ADMET)
polymerization with longer chain diene substrates.
Ru
C
14
16. Commercially available, as is synthetic precursor.
Must be handled under argon or nitrogen using
dry conditions.
Relatively intolerant of proton on heteroatoms.
Tolerant of S, P and nitrile functional groups.
High reactive.
Electron deficient Mo(VI), 14 electron species.
N Ar ligand, OR ligand and initial alkylidine
need to be bulky.
Electron withdrawing alkoxides increase
electrophilicity of metal center, hence increases
reactivity.
Schrock’s catalyst
16
17. Reasonably stable toward water, oxygen and
minor impurities ------ ease of handling.
Lower activity vs. Mo and imido alkylidene
catalyst.
High functional group tolerance.
Halides: catalyst activity I < Br < Cl.
Ru catalyst containing N-heterocyclic
imidazol-2- ylidene , Carbene.
Activity is significantly higher then
parent Ru complex.
Grubbs Catalyst
17
18. 1. Dr. Yves Chauvin at the Institute Francisdupetrole, France
2. Prof. Robert H. Grubbs, California Institute of Technology USA
3. Prof. Richard R. Schrock, Massachusetts institute of Technology,
Cambridge USA
The Nobel Prize In Chemistry 2005
For The Development Of Metathesis
Method In Organic Synthesis
18
25. Enyne metathesis
25
The Enyne metathesis is a ruthenium-catalyzed bond reorganization
reaction between alkynes and alkenes to produce 1, 3-dienes.
Alkyledine migration from the alkene to alkyne carbon. The
driving force thermodynamically stable 1,3-diene.
Catalyst
When the reaction is intramolecular, called as Ring Closure
Enyne Metatesis RCEM
26. Mechanism Of Enyne Metathesis
This is the proposed "yne-then-ene" mechanism.The driving force for
the reaction is the formation of thermodynamically stable conjugated
butadiene 26
29. Application Of Metathesis In Synthesis Of
Biologically Active Compounds
Highly functionalised novel bicyclic β-lactams
synthesis
These bicyclic β-lactams systems have been prepared via the enyne
metathesis reaction using catalytic quantities of trans (Cy3P)2Cl2Ru=CHPh
(Cy = Cyclohexyl)
29
Chem. Comm.1997, 1375
30. Complex Heterocyclic lactam
Fused bicyclic lactams having quinolizidine alkaloid skeletons are
commonly observed structural unit of many important compound
which display a broad rang of biological activity.
30
J. Org. Chem. 2004, 69, 6305
31. Balanol
It shows remarkable anticancer activity.
Also used against HIV infection, Rheumatoid Arthritis,
cardiovascular disorder, CNS dysfunction.
31
33. Turrianes
Turrianes are efficient DNA –cleaving agents under oxidative condition
in presence of copper ion and butyl amine.
These are naturally occurring cyclophanes and consist of aromatic unit
specially benzene and an aliphatic chain that form chain bridge between
benzene ring.
33
34. Sphorolipid lactone
They are natural products
Sphorolipid derivatives have antibacterial
and antifungal activity.
Present study documents in –vitro
spermicidal and anti -HIV virucidal activities against human
semen are similar to commercial spermicidal Nonoxynol-9 (N-9).
34
36. Dehydrohomoancepsenolide
Butenolide is natural product incampas a broad spectrum of
antibacterial, antimalarial, antitumor and herbicidal activity.
Dehydrohomoancepsenolide is a natural product.
36
37. Org. Lett. 2000, 2,2463
Synthesis of Dehydrohomoancepsenolide
37
38. BILN- 2061
BILN- 2061 is a new chemical entity
which shows promising results against
the Hepatitis C virus by inhibiting
Seine Protease of HCV.
38
BILN- 2061 developed by Boehringer-Ingelheim.
BILN- 2061is in Phase II Clinical trial in US and Europe.
BILN 2061, 15-membered macro cyclic compound containing
a (Z)- olefin.
40. Synthesis of ORL Pheromones
The omnivorous leaf roler (OLR) is a pest of appels, pears, peaches,
and nectarines.
The OLR pheromone is an 82:18 ratio of E to Z-tetradecenyl acetate
isomers. The C M metathesis reaction, using the second generation
Grubbs`catalyst, produces the desired isomeric ratio.
40
43. CIVETONE
It is one of the important valuable fragrance containing
compounds used in perfume industry, chemically macrocyclic
ketone.
Stereoslective synthesis of Civetone
Chem. comm. 2005, 2307-2320 43
47. Dendrimer a family of nano-sized, 3D polymer , a class of
macromolecules having highly branched architecture The name comes
from the Greek word δένδρον (dendron), which translates to "tree
47
48. The examples mentioned above illustrate the broad applications of
metathesis reactions for the synthesis of several drugs and many
other valuable chemical compounds. Thus this reaction has great
significance for both academic research and industry for
development of commercially valuable compounds.
The beauty of metathesis method is that it take shorter synthetic rout
give higher yield, fewer by-products and it tolerates different
functional groups, present in starting material.
Thus metathesis chemistry has opened up novel opportunity to
explore the enormous diversity of organic molecules and contribute
to a green chemistry.
Conclusions
48
