Advanced methods in organic synthesis

A.Y. 2020/2021
Overall hours
Learning objectives
The objective of the course is to make students develop a fundamental base of knowledge of the most innovative organic reactions in the realm of organic synthesis.
Expected learning outcomes
At the end of the course, the student should be able to select suitable reactions for a particular organic synthesis, based on the identification of the most effective possibilities among the available ones.
Course syllabus and organization

Single session

Lesson period
First semester
Lectures will be delivered in the streaming mode (synchronous teaching), following the official lecture timetable (start date: October 1, 2020), using the online communication platform Microsoft Teams, freely available to all the University of Milan (UNIMI) personnel and students within the Office 365 suite ( Lectures will be recorded and saved on the MS Stream website ( The links to access them will be published on the Ariel website of the course (, together with additional teaching material (e.g., lecture slides), and made available for the entire semester (October-February).
Examinations will take place in the usual form (see below) and, during the written tests "in itinere", the students will be monitored in the web conference mode using MS Teams. However, if allowed by the "social distancing" regulations, the written tests in itinere will take place in a suitable University room.
Course syllabus
- Reactions involving transition metals. Preparation and structure of organocopper reagents, reactions involving organocopper reagents and intermediates. Reactions involving organopalladium intermediates: palladium-catalyzed nucleophilic substitution and alkylation, the Heck reaction, palladium-catalyzed cross-coupling reactions, carbonylation reactions. Reactions involving other transition metals (organonickel compounds, reactions involving rhodium and cobalt). [2.0 credit]
- The olefin metathesis reaction: RCM (Ring Closing Metathesis), ROM (Ring Opening Metathesis), CM (Cross Metathesis), RCAM (Ring Closing Alkyne Metathesis), Enyne RCM, Enyne CM. Catalysts and reaction mechanism. Synthetic applications. [1.5 credit]
- Carbon-carbon bond-forming reactions of compounds of boron, silicon and tin. Organoboron compounds: synthesis of organoboranes; carbonylation and other one-carbon homologation reactions; homologation via alpha-halo enolates; stereoselective alkene synthesis; nucleophilic addition of allylic groups from boron compounds. Organosilicon compounds: synthesis of organosilanes; general features of Carbon-Carbon bond-forming reactions of organosilicon compounds; addition reactions to aldehydes and ketones; reactions with iminium ions; acylation reactions; conjugate addition reactions. Organotin compounds: synthesis of organostannanes; Carbon-Carbon bond-forming reactions of organotin compounds. [2.0 credit]
- Total syntheses: examples using the above described methods. [0.5 credit]
Prerequisites for admission
Good knowledge of organic synthesis; ideally the lectures should be followed after having acquired good knowledge about: (i) Alkylation of enolates and other carbon nucleophiles, (ii) Reaction of carbon nucleophiles with carbonyl compounds, (iii) Electrophilic additions to carbon-carbon multiple bonds, (iv) Organometallic compounds of the group I, II, and III metals.
Teaching methods
Traditional teaching. Exercises in the course timetable.
Teaching Resources
F. A. Carey, R. J. Sundberg, Advanced Organic Chemistry, Part B: Reactions and Synthesis, V Edition, 2007 Springer Science.
Assessment methods and Criteria
Written tests (2 tests "in itinere" and a written report on a literature paper) and final oral examination. Each written test is typically comprised of 10-15 open questions taken from the exercises of the recommended book (Carey & Sundberg, Part B). Usually, the allotted time for the written test is 3 hours. The mark is in thirtieths and corresponds to a detailed evaluation of the skills acquired by the student. The results of the written tests are communicated to the student via email and posted on the bulletin board anonymously (only badge number). The final oral exam (mark in thirtieths) is mainly focused on a discussion of the written tests.
CHIM/06 - ORGANIC CHEMISTRY - University credits: 6
Lessons: 48 hours