ORGANIC CHEMISTRY II

Teachers: 
Credits: 
8
Site: 
PARMA
Year of erogation: 
2021/2022
Unit Coordinator: 
Disciplinary Sector: 
Organic Chemistry
Semester: 
First semester
Year of study: 
2
Language of instruction: 

ITALIAN
(Some Slides are in English)

Learning outcomes of the course unit

At the end of the course the student is expected to be able to:
1. KNOWLEDGE AND UNDERSTANDING.
1a. To recognize the main functional groups within complex molecules.
1b. To recognize nomenclature, structure and reactivity of the main classes of organic compounds, be they linear, cyclic, heterocyclic, or fused bicycles.
1c. To explain and appropriately exemplify the principles that guide the main organic reactions and allow the rational interpretation of reaction mechanisms.
2. APPLIED KNOWLEDGE AND UNDERSTANDING.
2a. To implement the theoretical knowledge acquired to solve simple problems.
2b. To predict the outcome of chemical transformations.
2c. To critically address the design of a credible synthetic plan to access simple molecules.
3. COMMUNICATION AND LEARNING SKILLS.
3a. To communicate in a clear way and with appropriate technical language conclusions and knowledge to specialist and non-specialist interlocutors, in accordance with the training objectives described above.
4. MAKING JUDGEMENTS.
4a. To evaluate in a critical way a synthetic strategy aimed at obtaining a polyfunctionalized molecule of small dimensions.
5. ABILITY TO LEARN.
5a. To communicate the results of empirical research through the drafting of a critical research report.

Prerequisites

The Course of Organic Chemistry II provides the good acquisition of all the topics covered during Organic Chemistry I and in particular:
1. Molecular electronic configuration: atomic orbitals, molecular orbitals and hybrid orbitals.
2. Structure and hybridization of carbon chains.
3. Conformational and configurational analysis of carbon chains.
4. Acid-base equilibria.
5. Nucleophiles and electrophiles.
6. Main classes of chemical reactions: addition, substitution, redox.
7. Structure and nomenclature of the main classes of functional groups treated during Organic Chemistry I.
8. Inductive effects and resonance effects.
NB: Passing the final examination of Organic Chemistry I is mandatory in order to attend the examination but NOT the lessons of Organic Chemistry II. That said, in order to better understand and follow the lessons of the course, it is important that the concepts listed above have been studied and understood by the student, even if the Organic Chemistry I exam has not yet been passed and/or taken.

Course contents summary

The course, divided into several phases, will deal with the chemistry of the main classes of organic compounds not covered in the Organic Chemistry I course, which can be traced back to three main areas:
1. REACTIVITY OF CARBANIONS;
2. REACTIVITY OF CARBOCATIONS;
3. PERICYCLIC REACTIONS.
Emphasis will be given to the problems related to the formation of new carbon-carbon bonds, formation and manipulation of functional groups, protections and deprotections in complex systems. Total synthesis methodologies, retro-synthetic analysis of simple targets and possible disconnections will be treated in parallel with the above-mentioned topics.

Course contents

1. CARBANION REACTIVITY (2.75 CFU)
1a. Carbanions: structure, synthesis and reactivity
1b. Enols and enolates; keto-enolic tautomer; acidity and basicity of enolizable compounds.
1c. Enolization catalyzed by acids and bases; metal enolates; ammonium enolates; silicon stabilized enolates; kinetic enolates vs. thermodynamic enolates; control of the Z/E geometry of an enolate; non-carbonylic enolates; ilids.
1d. Halogenation and nitrosation of enolates
1e. Alkylation of enolates and enamines: malonic synthesis and inter- and intramolecular Michael reaction.
1f. The aldol reaction: the "classical" acidic and base-catalyzed aldol reaction; the cross aldol reaction; Mukaiyama variant; intramolecular aldol reaction; Henry's reaction; Knovenagel's reaction.
1g. Mannich reaction: imine and imminium ions; direct and indirect Mannich reaction; Pictet-Spengler reaction.
1h. Claisen and Dieckmann Reactions; acetoacetic synthesis.
1i. Domino reactions: Bayliss-Hillman reaction; Robinson annulation.

2. PRINCIPLE OF VINYLOGY (0.25 CFU)
2a. Definitions
2b. Vinylogous Aldol, Mannich, ad Michael reactions.

3. OLEFINATION REACTIONS (0.25 CFU)
3a. Stabilized and non-stabilized phosphorus ylides.
3b. Wittig reaction; Horner-Hemmons and its variants; Still-Gennari reaction.
3c. Sulfur ylides and Julia olefination.

4. CARBOCATION REACTIVITY (0.5 CFU)
4a. Carbocations: basic structure, synthesis and reactivity.
4b. Pinacolic and semi-pinacolic rearrangement; ring expansion and contraction; Wagner-Meerwein rearrangement; Grob fragmentation.
4c. Prins reaction.

5. AROMATIC COMPOUNDS (2 CFU)
5a. Aromaticity and nomenclature of aromatic compounds
5b. Reactivity of Benzene and its derivatives
5c. Electrophilic Aromatic Substitution (EAS)
5d. Diazonium salts
5e. Synthesis of mono- and multi-substituted benzene derivatives
5f. Nucleophilic Aromatic Substitution; Benzyne.

6. INTRODUCTION TO PALLADIUM CHEMISTRY (1 CFU)
6a. Transition metals
6b. Introduztion to the reactivity of Palladium complexes
6c. Palladium-catalyzed cross couplings: Heck, Suzuki, Stille, Sonogashira.

7. PERICYCLIC REACTIONS (1.0 CFU)
7a. Classification of pericyclic reactions.
7b. Woodward-Hoffmann Rules
7c. Diels-Alder Reaction
7d. Sigmatropic transpositions.

8. PRINCIPLES OF CHEMICAL SYNTHESIS (0.25 CFU)
8a. Introduction to chemical synthesis: divergent vs convergent synthesis
8b. Protecting groups
8c. Applications to the total synthesis of drugs

Recommended readings

Suggested textbook:
1. For general issues: W. H. BROWN, B. l. IVERSON, E. V. ANSLYN, C. S. FOOTE, "Chimica Organica", Sesta Edizione, EdiSES 2019.
2. For advanced issues: J. CLAYDEN, N. GREEVES, S. WARREN, "Organic Chemistry", Second edition, Oxford 2012.
Reference books (available at the library and at the professor office):
3. Kurti Laslo, Czako Barbara "STRATEGIC APPLICATIONS OF NAMED REACTIONS IN ORGANIC SYNTHESYS", Academic Press, 2005.

Free Apps:
1. “CHEMISTRY BY DESIGN” also available at: https://chemistrybydesign.oia.arizona.edu
2. “REACTION FLASH”, Elsevier

Free App for 3D animations of molecules and mechanisms of action:
ChemTube 3D
https://www.chemtube3d.com/

Teaching methods

The lessons will be held "in presence" and in accordance with the didactic regulations of the CTF Course, attendance to the course is mandatory. In case of emergency period restrictions that prevent access to the University premises, the lessons will be provided by "distance learning" in synchronous (direct) mode, through the use of the Teams and Elly platforms.
During the lessons, moments of frontal teaching will alternate with interactive moments with the students. To promote active participation several activities will be proposed through the use of some digital resources such as Elly Discussion Forums or practice tests through the Office 365 Forms application.
The didactic activities will be conducted by privileging modalities of active learning alternated to heuristic Socratic lessons. During the heuristic-socratic lessons will be privileged the dialogical confrontation with the classroom, on the theoretical aspects of the topics of the course, in order to bring out any pre-knowledge on the topics in question by the trainees. In the second part of the lesson will be activated cycles of experiential learning in which students will be required to apply the theoretical concepts learned to the resolution of appropriate written exercises. In addition, "case studies" taken from the scientific literature (empirical research projects) will be analyzed and the students will have to critically analyze them according to the methodological criteria illustrated in the lessons and in the bibliographic and didactic material.
The slides used to support the lessons will be uploaded weekly on the Elly platform. In order to download the slides it is necessary to register for the online course. The slides are considered an integral part of the teaching material. Non-attending students are reminded to check the available didactic material and the indications provided by the teacher through the Elly platform.
The recordings of the lessons and the links to the Forms exercises will be available to the students on the Elly platform: the presence of this material does not exempt the student from the mandatory "in presence" attendance of the course.

Assessment methods and criteria

The final examination consists of a colloquium and a written assay on a reported total synthesis to be discussed at the end of the colloquium. The colloquium deals with the execution of exercises on asymmetric synthesis and reactivity of organic compounds. This test is aimed at verifying whether the student has developed the skill and ability of 1) recognizing the relationship between structure and properties of organic compounds, 2) predicting the behavior of a given organic chemistry transformation among those comprised in the program, 3) selecting and deploying information from the theory study in order to furnish solutions to a given practical organic synthesis problem, and finally 4) acquiring learning skills and communication skills by employing appropriate language to both specialized and non-specialized audience.
The written assay will focus on a critical comment on the published synthesis of a target, as well as on the mechanisms and transition states of key reactions exploited during the synthesis. Each student has to submit its own written assignment within two weeks of the date of the colloquium. All information related to the execution of the assay will be discussed during the course lessons and will be uploaded on the Elly platform.
The colloquium is evaluated on a 0-30 scale and will affect the 80% of the final grade.
The written assay is evaluated on a 0-30 scale and will affect the 10% of the final grade.
The critical discussion on the written assay is evaluated on a 0-30 scale and will affect the 10% of the final grade.
The final grade, defined not analytically but subjectively by the teacher, will be communicated immediately at the end of the oral test.
Please note that online registration is REQUIRED.
If, due to the continuation of the COVID-19 emergency, it is necessary to integrate with the remote mode, the carrying out of the profit examinations will proceed as usual: an oral interview conducted in two parts:
1. Oral exam regarding the topics of the course;
2. Oral presentation of the written report
Each student enrolled in the call will receive (about 5 days before the date of the call) an email with the following informations:
1. Date and time of convocation
2. Teams links to access the exam session (only for remote mode)
3. Links to upload the identity document (only for remote mode)
4. Operating instructions about the examination.