Construction and transformation of organic molecules

optional courses

Planning the structure of complex molecules: linear and convergent synthesis. The concept of synthons, building blocks. Rules of the synthetic strategy. Protective groups in organic synthesis - choice or necessity?

Selected problems in organic synthesis, stereochemistry - basic concepts and definitions:

chirality, enantiomers, diastereomers, selective and specific reactions, stereoselective and stereospecific reactions, asymmetric synthesis and asymmetric induction.

Significance of stereoisomers in nature. The stereochemistry of elimination, addition and cycloaddition reactions. Examples of regio- and stereoselective syntheses.

Classroom

The lecture is aimed at students who want to extend their knowledge of methods for construction and transformation of organic compounds with particular emphasis on issues related to the planning of the spatial structure of molecules.

Tools for construction and transformation of molecules:

The formation of carbon-hydrogen bonds: additions to the C = C bonds, addition to the C = O bonds, s stereochemically controlled homogeneous hydrogenation, enantioselective hydrosilylation.

Additions to the C = N bonds, hydrogenation and asymmetric hydrogen transfer of imines, imines hydrosilylation, 1,4-dihydropyridine as reducting agents for imines, oxime ethers, and related compounds.

The formation of carbon-oxygen bonds: the formal addition of an oxygen atom to alkene molecule, Katsuki-Sharpless epoxidation, Jacobsen epoxidation, Julia-Colonna epoxidation of activated alkenes, stereoselective dihydroxylation.

The formation of carbon-nitrogen bonds: stereoselective and tosyloaziridination and aziridination of alkenes.

Additions to olefinic bond: Stereocontrolled addition of HY-type reagents, nucleophilic addition of heteroatoms to olefins, α-functionalization of carbonyl compounds.

The formation of carbon-carbon bonds: alkylation of chiral enolates controlled by activating group, catalytic alkylation of enolates. Stereocontrolled aldol reactions, organokatalysis using amino acid derivatives, ureas, and thioureas. Nucleophilic addition to the carbonyl groups: by carbon sp3, sp2, and sp nucleophiles allyl; propargylation and alkenylation of carbonyl groups, additions of stabilized carbanions, stereoselective cyanosilylation.

Additions to the C = N bonds: Mannich and Strecker reactions, addition of carbon sp3, sp2, and sp nucleophiles.

Coupling reactions catalyzed with π-allyl complexes of transition metals.

Catalytic activation of C-H bonds.

Sigmatropic rearrangements: stereocontrolled Claisen rearrangement, Cope and ene reactions. Enantioselective Stetter reaction. Baylis-Hillman reaction and related processes.

Aromatic electrophilic and nucleophilic substitution. The replacement of hydrogen or other groups in aromatic systems.

The cyclization processes: cycloaddition reactions; Diels-Alder reactions, and hetero-Diels-Alder reactions and their stereochemical control. Enantioselective [3 + 2] cycloaddition, Simmons-Smith cyclopropanation. Complex pseudocyclization processes, multicomponent reactions.

Carbo- and heterocyclization processes: intramolecular Michael addition, Robinson annulation, hydroboration reaction, Pauson-Khand reaction.

Cyclization catalyzed by rhodium complexes. Enantioselective Heck reaction, the Nazarov reaction, Pictet-Spengler cyclization - stereochemical aspects. Enantioselective metathesis processes.

1. John McMurry, Chemia Organiczna, PWN Warszawa 2000, tom 1 i 2

2. Jacek Skarżewski, Wprowadzenie do Syntezy Organicznej, PWN Warszawa, Łódź 1999

3. Robert T. Morrison, Robert N. Boyd, Chemia Organiczna, PWN Warszawa 1997

4. Jacek Gawroński, Krystyna Gawrońska, Stereochemia w Syntezie Organicznej, PWN

Warszawa 1988

5. Przemysław Mastalerz, Chemia Organiczna, PWN Warszawa 1984

6. Robert M. Silverstein, Francis X. Webster, David J. Kiemle, Spektroskopowe metody

identyfikacji związków organicznych, PWN Warszawa 2007

7. Richard C. Larock, Comprehensive Organic Transformations, Wiley VCH, 1999

8. Michael B. Smith, Jerry March, March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, Wiley-Interscience, 2007

Deepening of the knowledge of modern methods of construction and transformation of organic molecules with particular emphasis on the stereochemical aspects is expected.

Written exam.

Not expected.