OVERVIEW

This optional module aims at give students a thorough knowledge of the main orgaometallic methodologies applied to organic synthesis, as well as biocatalysis in organic synthesis. The module is normally given in english.

AIMS AND CONTENT

LEARNING OUTCOMES

To furnish advances concepts in organic synthesis. In particular: synthesis with organometal reagents/catalysts (including boron and phosphorus compounds); biocatalytic synthesis

PREREQUISITES

A good general knowledge of organic chemistry.

TEACHING METHODS

Lessons in classroom (32 hours). The module gives 4 credits and the student is expected to spend 68 hours for studying the module subjects.

SYLLABUS/CONTENT

1) Chemistry of organoboron and organocopper compounds (6 h)

1.1. Organoboron compounds

1.1.1 Nomenclature

1.1.2 Preparation of organoboron compounds

1.1.2.1 Hydroboration

1.1.2.2 Asymmetric hydroboration

1.1.2.3 Transmetalation

1.1.3. Functionalisation of trialkylboranes: synthesis of alcohols, ketones, amines, halogenides

1.1.4 Haloboranes

1.1.5 Formation of new C-C bonds with organoboron compounds

1.1.4.1 Reaction of aldehydes with allyl or crotyl boranes or boronates

1.1.5 Boronic acids and esters

1.1.5.1 Properties

1.1.5.2 Preparation by transmetalation

1.1.5.3 Preparation by hydroboration of alkynes

1.1.5.4 Preparation by hydroboration of alkenes

1.1.5.5 Synthesis of alkenyl halides

1.1.5.6 Petasis reaction

1.1.5.7 Matteson reaction

11.5.8 Barluenga reaction

1.2 Organocopper compounds

1.2.1 Types of Cu (I) organometal compounds

1.2.2 Conjugated addition to enones

1.2.3 Cross-coupling reactions

2) Transition metal catalysed reactions (16 h)

2.1 Generalities

2.1.1 Calculation of electron number and oxidation number

2.1.2 Catalityc cycles

2.2 Pd(0) catalysed reactions

2.2.1 Types of catalysts

2.2.2 Reactions starting from an oxidative addition to halides, triflates

2.2.2.1 CO Insertion

2.2.2.2 Heck reaction

2.2.2.3 Suzuki reaction

2.2.2.4 Negishi reaction

2.2.2.5 Stille reaction

2.2.2.6 Sonogashira reaction

2.2.3 Reaction of p-allyl palladium complexes with nucleophiles

2.2.4 Metallo-ene reactions

2.2.5 Domino reactions catalysed by Pd(0)

2.2.6 Buchwald-Hartwig reactions

2.3 Pd(II) catalysed reactions

2.4 Gold catalysed reactions

2.2.1 Introduction

2.2.2 Types of catalysts

2.2.3 Reaction of triple bonds with O and N nucleophiles

2.2.4 Hydroarylation

2.2.5 Enyne cycloisomerization

2.2.6 Reaction of silyl enol ethers and propargyl esters

2.5 Olefin metathesis

2.5.1 Generalities

2.5.1.1 Historical notes

2.5.1.2 Mechanism

2.5.1.3 Types of metathesis

2.5.1.4 Schrock catalyst

2.5.1.5 Grubbs catalyst

2.5.1.6 Hoveyda catalyst

2.5.2 Ring Closing Metathesis

2.5.3 Cross Metathesis

2.5.4 Ring Closing Enyne Metathesis

2.5.5 Domino metathesis

3) Biocatalysis in organic synthesis (10 h)

3.1 Generalities

3.1.1 Why to use enzymes

3.1.2 Enzyme classification

3.2 Hydrolases and Dehydrogenases

3.2.1 Hydrolysis of esters and acylation of alcohols

3.2.2 Kinetic resolution and dynamic kinetic resolution for obtainment of enantiopure secondary alcohols

3.2.3 Ketone reduction for obtainment of enantiopure secondary alcohols

3.2.4 Synthesis of enantiopure amines: kinetic resolution or use of amino transferases

3.2.5 Enzymatic desymmetrization with hydrolases and MAO

3.2.6 Oxidative desymmetrization of arenes

3.3 Formation of Glycosidic bonds

3.4 Formation of C-C bonds

RECOMMENDED READING/BIBLIOGRAPHY

There is no book covering exactly the programme. Students may use the slides that are uploaded in advance on aulaweb.

TEACHERS AND EXAM BOARD

Exam Board

LUCA BANFI (President)

ANDREA BASSO

CHIARA LAMBRUSCHINI (Substitute)

LISA MONI (Substitute)

RENATA RIVA (Substitute)

LESSONS

LESSONS START

February 24, 2025

EXAMS

EXAM DESCRIPTION

The exam will be oral and will regard exclusively the subjects treated during the lessons (the slides are available on aulaweb). Students must register 48 hours in advance on

https://servizionline.unige.it/studenti/esami/prenotazione

Students who have valid certification of physical or learning disabilities on file with the University and who wish to discuss possible accommodations or other circumstances regarding lectures, coursework and exams, should speak both with the instructor and with Professor Sergio Di Domizio (sergio.didomizio@unige.it), the Department’s disability liaison.

ASSESSMENT METHODS

The oral exam is always carried out by two teachers with at least 5 years of experience and will last at least 30 minutes. In this way, the commission is definitely able to verify with high accuracy if the student has reached or not the learning outcomes.

During the oral exam the student must demonstrate to have reached the learning outcomes, both orally and (most importantly) writing formulas, chemical equations, mechanisms.

When the commission will judge that the learning oucomes have not been reached, the students willbe invited to repeat the exam in one of the subsequent dates.

Exam schedule

FURTHER INFORMATION

Students who have valid certification of physical or learning disabilities on file with the University and who wish to discuss possible accommodations or other circumstances regarding lectures, coursework and exams, should speak both with the instructor and with Professor Sergio Di Domizio (sergio.didomizio@unige.it), the Department’s disability liaison.