SubjectsSubjects(version: 901)
Course, academic year 2022/2023
  
Organic Synthesis III - MC270P104
Title: Organic Synthesis III
Guaranteed by: Department of Organic Chemistry (31-270)
Faculty: Faculty of Science
Actual: from 2021
Semester: winter
E-Credits: 3
Examination process: winter s.:
Hours per week, examination: winter s.:2/1 C+Ex [hours/week]
Capacity: unlimited
Min. number of students: unlimited
Virtual mobility / capacity: no
State of the course: taught
Language: English
Note: enabled for web enrollment
Guarantor: prof. RNDr. Martin Kotora, CSc.
Teacher(s): prof. RNDr. Martin Kotora, CSc.
RNDr. David Nečas, Ph.D.
Opinion survey results   Examination dates   Schedule   
Annotation
Last update: prof. RNDr. Martin Kotora, CSc. (31.05.2021)
Clasification of organometalic compounds, their preparation and properties. Basic formalism of organometalic reactions, reaction mechaninisms. Reactions catalyzed or mediated by transition metal complexes: cross-coupling reactions, cycloaddition reactions, conjugated additions, activation of C-H and C-C bonds, functionalization of C-C double and triple bonds.
Literature
Last update: prof. RNDr. Martin Kotora, CSc. (31.05.2021)

1. Transition Metals in the Synthesis of Complex Organic Molecules, 2nd Edition (Hegedus, L. S.)

2. Review articles in journals such as Chemical Reviews, Chemical Society Reviews, Angewandte Chemie, European Journal of Organic Chemistry, atd.

Requirements to the exam
Last update: prof. RNDr. Martin Kotora, CSc. (31.05.2021)

The course begins in the first week of the winter semester.

Requirements for examination:
1. To attend all lectures.

2. To submit homeworks on time.

3. To submit a seminar work prior to the examination.

Syllabus
Last update: prof. RNDr. Martin Kotora, CSc. (31.05.2021)

Notice: Individual subchapters might be subject to change.

1.Introduction
1.1. Basic Principles
1.2. Pathways for the Formation of Organo-Transition Metal Species
1.3. Transmetallation and Ligand Transfer

2. Electronic and Steric Ligand Effects in Transition Metal-Catalyzed Reactions (Mainly Phosphorus Ligands)
2.1. Introduction and Definitions (Steric and Electronic Effects)
2.2. Ligand Effect on Oxidative Addition/Reductive Elimination (General Guidelines)
2.3. Some Typical Examples of Ligand Effects
2.4. Influence of Electronic Tuning on Enantioselectivity
2.5. Bite Angle
2.6. Some Typical Examples of Influence of Bite Angle

3. Cross-Coupling Reactions
3.1. Introduction
3.2. Negishi Coupling
3.3. Kumada-Tamao Coupling
3.4. Sonogashira Coupling
3.5. Stille Coupling
3.6. Suzuki Coupling
3.7. Reactivity of Trans and Cis Vinyl Halides.
3.8. Glaser and Chodkiewicz-Cadiot Coupling
3.9. Other Cross-Coupling Reactions (coupling between sp3 and sp3 carbons)
3.10. Nozaki-Hiyama-Kishi coupling

4. [2+2+2]-Cycloaddition Reactions
4.1. Introduction
4.2. Intermolecular Cyclotrimerization
4.3. Co-cyclotrimerization of Diynes and Alkynes
4.4. Intramolecular Cyclotrimerization of Triynes
4.5. Cyclotrimerization of Two Alkynes and a Nitrile
4.6. Cyclotrimerization of Diynes and a Nitrile
4.7. Cyclotrimerization of Alkynes with Other Unsaturated Compounds

5. Other Cycloadditions
5.1. Introduction
5.2. [2+1] Cycloadditions
5.3. [2+2] Cycloadditions
5.4. [3+2] Cycloadditions
5.5. [3+3] Cycloadditions
5.6. [4+1] Cycloadditions
5.7. [4+2] Cycloadditions
5.8. [4+3] Cycloadditions
5.9. [4+4] Cycloadditions
5.10. [5+n] Cycloadditions (n = 1, 2)
5.11. [6+2] Cycloadditions
5.12. [2+2+1] Cycloadditions
5.13. Other [2+2+2] Cycloadditions
5.14. [4+2+2] Cycloadditions
5.15. [2+2+2+2] Cycloadditions
5.16. [4+4+1] Cycloadditions

6. C-H Bond Activation
6.1. Introduction
6.2. Dehydrogenation
6.3. Formation of Carbon-Carbon Bonds via CO and Isonitrile Insertion
6.4. Formation of Carbon-Carbon Bonds via Alkene and Alkyne Insertion into Unsupported C-H bonds
6.4.1. Hydroarylation, etc.
6.4.2. Hydroacylation
6.5. Formation of Carbon-Carbon Bonds via Alkene and Alkyne Insertion into Potentially Chelating Systems
6.6. Cascade Alkene Insertion into Unsupported C-H bonds and Potentially Chelating System
6.7. Activation of Acidic C-H bonds in Alkynes
6.8. Activation of Acidic C-H bonds in Carbonyl and Related Compounds

7. Carbon-Carbon Bond Activation
7.1. Introduction
7.2. Alkene-Alkene Ring Closing Metathesis
7.3. Enyne Metathesis
7.4. Flexibility of Alkene-Alkene and Alkene-Alkyne Metathesis in Organic Synthesis
7.5. Diyne Metathesis
7.6. Small Ring Cleavage
7.6.1. Cleavage of Simple Cyclopropanes
7.6.2. Cleavage of Alkylidenecyclopropanes
7.6.3. Cleavage of Vinylcyclopropanes
7.6.4. Cleavage of Cyclobutanes
7.6.5. Cleavage of Cyclobutanones
7.6.6. Cleavage of Cyclobutenones and Cyclobutenediones
7.7. Other Transition Metal Catalyzed Carbon-Carbon Bond Cleavage Reactions
7.8. Transition-Metal Catalyzed Rearrangements
7.9. Carbon-Carbon Bond Cleavage in Organometallic Compounds of Early Transition Metals Metallacycles

8. Conjugate additions
8.1. Introduction
8.2. Terminology and Classifications
8.3. Additions of Stabilized Carbanions and Other Nucleophiles
8.4. Additions of Non-stabilized Carbanions (Organocopper, -nickel, etc)
8.5. Conjugate Additions Catalyzed by Transition Metals

9. Transition Metal Catalyzed Cyclizations
9.1. Introduction
9.2. Cyclization via Metallacycle intermediate
9.3. Cyclization via Hydrometallation
9.4. Cyclization via Activation of C-H bonds
9.5. Cyclizations via Oxidative additions
9.6. Radical Cyclization (Halotropic Cyclizations)
9.7. Lewis acid Catalyzed Cyclizations

10. Double and triple bond functionalization
10.1. Introduction
10.2. Heck Reaction
10.3. Other Double Bond Functionalization
10.4. Triple Bond Functionalization

11. Application of Catalysis in Organic Synthesis

Entry requirements
Last update: prof. RNDr. Martin Kotora, CSc. (31.05.2021)

Applicants should have a solid knowledge of basic and intermediate organic and inorganic chemistry.

 
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