Academic Year 2018/2019
- Docente: Marco Bandini
- Credits: 6
- SSD: CHIM/06
- Language: Italian
- Teaching Mode: Traditional lectures
- Campus: Bologna
- Corso: Second cycle degree programme (LM) in Photochemistry and molecular materials (cod. 8026)
Learning outcomes
At the end of the course the students will learn the main guidelines in order to design and to synthesize conjugated organic compounds. In particular, deep knowledge in the fields of “Nobel Prize “ transformations such as metal catalyzed cross-coupling reactions and metathesis reactions (i.e. ene-ene, ene-yno, yno-yno) will be acquired along the course. During the practical lessons the student will face the multi-step synthesis of a conjugated organic compound based on aromatic systems and the corresponding analytical/spectroscopic characterization.
Course contents
Prerequisites:
To student that plans to attend the course, in order to get maximum
comprehension of the topics of the lessons must be confident with
the programmes of the basic organic chemistry with particular
concern to the synthesis and functionalization of the main organic
functional groups (from alkanes to carboxylic derivate). The text
book “Organic Chemistry” by J. Clayden, N. Greeves, S. Warren is
kindly suggested. Moreover, the student should already be practice
with common lab glass-ware, with the setting of an organic
reaction, monitoring of the process by means of TLC and classic
work-up. Finally, the student is supposed to known how to get
structural information on a title organic species via
NMR-spectroscopy 1H and 13C.
1. Organic materials for opto-electronic
1.1. Basis of main p-conjugated polymeric
1.2. The electroluminescence
1.3. Structure/propriety relationships of the conjugated organic
compounds;
1.3.1.
Steric effects
1.3.2 Electronic effects
1.4 Organic compounds with blue-emission
1.4.1 Poly-fluorene
2. Synthesis and functionalization of
heteroaromatic compounds
2.1. Pyridine: resonance formula and dipole moment
2.2. Quinoline: resonance formula and dipole moment
2.3. Azoles: resonance formula and dipole moment
2.4. Pyrrole:
resonance formula and dipole moment and electronic analogy with Cp
anion.
2.5 Furan and thiophene: resonance formula and dipole moment
2.6 Main electron-rinc heteroaromatic benzo-fused: resonance
formula and dipole moment
2.7 Reactivity of pyridine towards electrophilic reactions
2.8 Electrophilic substitution of quinoline to the C atom
2.9 Regiochemistry of the SEAr in biaryl compounds
2.10 Acidity of the NH groups in azoles and analogoues
2.11 Lithiation of aromatic 5 and 6-membered rings. Activation of
the C-H
2.12 Lithiation of aromatic 5 and 6-membered rings: halogen
exchange
2.13 Radical halogenation (NBS) of electron-rich aromatic
compounds
2.14 Synthesis of aryl-boronic, aryl-sylane and aryl stannane
compounds
3. Pd-catalyzed cross-coupling
reactions
3.1 The Suzuki-Miyaura reactions
3.1.1 Scope, limitations and mechanistic details
3.2 The Hiyama reaction
3.2.1 Scope, limitations and mechanistic details
3.3 The Stille reaction
3.3.1 Scope, limitations and mechanistic details
3.4 The Mirozoki-Heck reaction
3.4.1 Scope, limitations and mechanistic details
3.5 The Hiyama reaction
3.5.1 Scope, limitations and mechanistic details
3.6 The Buchwald-Hartwig reaction
3.6.1 Scope, limitations and mechanistic details
3.7 The Cassar-Sonogashira reactop
3.7.1 Scope, limitations and mechanistic details
4. The metathesis reaction
4.1 The metathesis ene-ene
4.1.1 Metallo-carbenes: synthesis and properties
4.1.2 The Chauvin' postulate
4.1.3 The Grubb's catalysts (I and II generation) and the
Grubbs-Hoveyda catalysts
4.1.4 Types of metathesis reactions
4.1.5 Dissociative mechanism: the ring-closing case
4.1.6 The cross-metathesis reaction
4.1.7 Thermodynamic aspects in the RCM
4.1.8 Application of the RCM to the synthesis of polyfunctionalized
compounds
4.2 The metathesis ene-yno
4.2.1 The reaction machinery
4.2.2 Application of the ene-yno to the synthesis of
polyfunctionalized compounds
4.3 The metathesis yne-yno
4.3.1 Reaction machinery
4.3.2 Application of the ene-yno to the synthesis of
stereochemically defined unsaturated macrocycles
4.3.3 Application of the ene-yno to the synthesis of
functionalized poly-acenes
5. Laboratory work
5.1 Sequential multi-step synthesis and characterization of a
functionalized spiro-fluorenyl
5.2 Sequential multi-step synthesis and characterization of a
phosphorescent cyclometallated Iridio(III) complex
Readings/Bibliography
Teaching methods
Theoretical lessons 24 hs (use of black-board, and projection of
slides via ppt presentations).
Practical lessons 32 hs.
Attendance: The course is characterized by a compulsory attendance to the practical experiences (75% of the lab lessons).
Assessment methods
The assessment of the learning outcomes of the student is performed at the end of the course by means of oral examination with duration of 45 min. The student will be allowed to face the examination only is: i) in possess of documented attendance of the practical lessons (75% of the total), ii) having completed the scientific report regarding the practical experiences carried out in the laboratory. The scientific report is generally edited one per group (two-three students/group) by the student after the course and must be delivered to the Professor at least 10 days in advance with respect to the date of examination. The final outcome of the reports is then discussed directly with the components the group.
The oral examination generally begins with the structural analysis of one title molecule recently appeared in the literature. The student will be asked to propose a possible synthetic sequence for its preparation. Main disconnections will be related to the reactivity discussed during the course.
The final mark of the exam will be expressed in 30th and the will derive for the assessment of the oral exam (max: 22/30), the written report (max 7/30) and personal assessment of the candidate during the working time in the laboratory classes. Laude could be assigned in case of exceptional preparation and with a final and total mark not less that 32.
Teaching tools
The didactic material will be provided by the Professor to the students in electronic format. Moreover, all the literature articles describing the exercises discussed during the class-room will be available. All in one, the students will be asked to prepare the examination by studying notes taken during the classes.
Office hours
See the website of Marco Bandini