66173 - Organic Chemistry with Laboratory M

Learning outcomes

The student will learn how to devise a retrosynthetic approach to the sysnthesis, use transformations of functional groups, catalytic coupling reactions for the formation of both new C-C or Carbon-heteroatom bonds and how to tackle the challenge of the preparation of enantiomerically pure compounds. He/she will also know non- conventional methodologies for the synthesis of organic compounds such as the use of microwaves; of flow-reactors and of solid-supported synthetic methodologies. He/she will learn the modes to catalyze organic reactions like organo-catalysis, metallo-catalysis, mixed-catalysis, enzymatic catalysis and phase-transfer catalysis. He/she will also learn how to develop multi-step synthetic sequences of industrially relevant organic molecules, also enantiomerically pure and how to purify organic molecules with the more recent and advanced separation techniques.

Course contents

INSTITUTIONAL PART

Background knowledge: the background knowledge in organic chemistry expected from a student entering this course is that of a student who has completed an Eurobachelor(R) certified degree in Chemistry and visible here with the exceptions of cycloadditions and rearrangements

1. Backgrounds on stereochemistry, reaction mechanisms and catalysis
   1. Stereochemistry background
   2. Equilibria and rates of organic reactions
   3. Experimental techniques for determining the mechanism of a reaction
   4. Acid/base catalysis of organic reactions
2. Stereoselective synthesis
   1. Energy considerations in reactions generating stereoisomers
   2. Resolution of racemates
   3. The «chiral pool»
   4. Asymmetric synthesis
3. Pericyclic reactions
   1. The Diels-Alder reaction
   2. Photochemical and thermal [2 + 2] cycloadditions
   3. 1,3-Dipolar cycloadditions
   4. Sigmatropic rearrangements
4. Transition metal mediated organic reactions
   
   1. Elementary steps of organometallic reactions
   2. The Heck reaction
   3. Cross-coupling reactions of organometallics: the Stille, Suzuki, Kumada, Negishi and Sonogashira reactions
   4. Allylic electrophiles are activated by palladium(0)
   5. Palladium catalysed amination of aromatic rings
   6. Activation of alkenes by palladium(II)
   7. Alkene metathesis
5. Rearrangements
   
   1. Neighbouring group participation
   2. Payne, Meerwein and pinacolic rearrangements
   3. Migration to heteroatoms: Baeyer-Villiger and di Beckmann rearrangements
   4. Migration to carbenes and nitrenes

 

LABORATORY

The course will focus on the application of the principal techniques used for the structural identification and analysis of organic molecules The course will apply basic knowledge on spectroscopic methods such as Nuclear Magnetic resonance and Mass Spectroscopy to the solution of the structures of organic molecules.. The main part of the course will be carried out with exercitations on experimental data, and by exercitations on the spectrometers.

1. NMR Spectroscopy
1. Nuclear spin and resonance
2. NMR spectromers and FT technique.
3. Spin relaxation theory
4. Acquisition parameters, spectral width and RF pulses
5. 1H spectra: chimica shift, cpupling constants and integration
6. 13C spectra and DEPT techniques for the signal assignment
7. NOE spectra
8. exercitations
   
   
2. Mass Spectroscopy
1. Ionization techniques: electron impact, electron spray, MALDI
2. Ion analyzers: magnetic secton, quadrupolem ionic trap, TOF and FT-ICR
3. Fragmentation mechanism
4. Fragmentation analysis for the structural assignment of simple molecules
5. Practical exercitations on experimental mass spectra
   
   
3. Analysis of optically active compounds
1. Enantioselective HPLC
2. Enantiomeric purity by NMR spectroscpy
3. Enantiomeric purity by optical methods: polarimetry, circular dichroism
4. Use of X-ray diffraction for the absolute configuration.
   
   
4. Laboratory activities
1. Two multi-step syntheses related to the theoretical contents will be held by students in the chemical laboratory

Readings/Bibliography

Lectures' handouts available via web at Insegnamenti OnLine

Clayden, Greeves, Warren & Wothers "Organic Chemistry - 2nd Ed." - OUP 2012

Laboratory

1. D.H.Williams, I.Fleming; 'Spectroscopic Methods in Organic Chemistry' 5° ed. Inglese; McGraw-Hill Book Company. ISBN 0-07-709147-7
2. R.M.Silverstein, F.X.Webster, D.J.Kiemle, "Spectrometric identification of Organic Compounds", 7° ed,; Wiley International Edition. ISBN 0-471-42913-9

Teaching methods

PowerPoint presentations - Group exercises through the pedagogical platform "Insegnamenti OnLine"

Assessment methods

The assessment is done through three tests

1. a practical test based on the lab experiences
2. a written test which is held during one of the six exam sessions defined by the teachers during the academic year
3. an written test on the institutional part

The practical test allows to obtain a score between 0 and 3, and consists of: i) the identification of the structure of an unknown molecule synthesized in the laboratory on the basis of NMR and mass spectroscopic data, to be made during laboratory experiments (from 0 to 1 point); ii) reports on experiments performed in the laboratory, whose evaluation will determine the understanding of conducted experiments, the ability to write a short scientific report, and processing, interpretation and presentation of data collected during the experiences (0 to 2 points).

Only students who attended the experimental activities of the laboratories will be admitted to the final wirtten tests. The delivery of the laboratory reports shall be made in any case before the spring examination session.

The written test will be held during exam sessions and it consists of an exercise in structural assignment with a score between 0 and 8 points. The time available for the test is 90 minutes. The exercise of structural assignment involves the use of experimental data of NMR / mass spectroscopy data for the determination of the structure of an unknown organic compound.

The written test on the istitutional part assigns a score between 0 and 20 points. This test aims to assess the level of learning of the concepts given in class and the student's ability to apply them to the understanding and resolution of real problems taken from the scientific literature.

The final grade is obtained by adding the scores obtained in the practice test rating (0-3 points), that obtained in the final written test exam (0-8 points) and that of the oral test (0-20 points).

Overall scores above 30 points are equivalent to 30 cum laude. Scores obtained in the final oral and written tests have a 12-month validity. After that, written tests must be retaken.

Teaching tools

PDF presentations available via web, through the pedagogical platform Insegnamenti OnLine - the University delivery system of teaching materials

On-line exercises

On-line self-assessment test

LABORATORY
The teacher will use Powerpoint Presentations (available to the students at the beginning of the lessons) for the theoretic part, and printed spectra for the exercitations. The course will proceed with theoretical concepts, followed by examples and exercise

Students with specific learning disabilities (SLD) or other disabilities, can contact the University Service for Students with Disabilities (http://www.studentidisabili.unibo.it/) or the contact person of the Department (giorgio.bencivenni2@unibo.it) or the teachers of the course.

Office hours

See the website of Paolo Righi

See the website of Andrea Mazzanti

See the website of Luca Bernardi