TECNOLOGIE IN SINTESI ORGANICA
- Overview
- Assessment methods
- Learning objectives
- Contents
- Bibliography
- Teaching methods
- Contacts/Info
The student must show a good knowledge of the organic chemistry provided in the Organic Chemistry Courses I and II
The verification consists of a written test. The type of exercises can include: 1) the synthesis guided through the reagents used, 2) the planning of the synthesis of a target from an assigned precursor, 3) the reactivity of a molecule in the presence of a set of reagents
At the end of the course the student must demonstrate
a) be able to write in detail the mechanism of the main oxidation, reduction and interconversion reactions between the main functional groups
b) know how to plan a multi-stage synthesis of targets starting from precursors assigned with particular attention to chemo- and stereoselectivity
Course program.Definition and examples of selectivity (regio- chemo- stereo-). Stereospecificity.
Oxidation reactions. Oxidations mediated by DMSO (Albright, Pfitzner Moffatt, Barton, Parikh Doering, Swern). Corey Kim method. Dess Martin periodinane. Ley Griffith method (TPAP). N-oxammonium salts (TEMPO). Oppenauer reaction. Oxidation with hypochlorites. Oxidation with MnO2, DDQ, Pyridinium chorochromate (PCC), pyridinium dichromate (PDC), Sarrett, Pinnick. Oxidations with KMnO4, Ag oxide, bromine.
Baeyer Villiger reaction. Corey Ganem method. Alpha-hydroxylation of carbonyls: Vedejs, Rubottom, Davis, oxidation of enolates. Oxidation of Malaprade. Lead (IV) acetate. Ozone. Lemieux Johnson, Lemieux Rudloff, ruthenium tetroxide and derivatives. Fetizon, oxidations with SeO2. Oxidations with 1 O2. Epoxidation of alcohols. Nucleophilic epoxidation. Enantioselective epoxidation (Jacobsen, Shi and Sharpless). Dihydroxylation of alkenes (osmilation, Upjohn process, KMnO4, Sharpless). Prévost and Woodward methods. Oxidation to alpha-diketones (Riley). Oxidation of nitrogen- compounds. Oxidation of sulfur compounds.
Reduction reactions. Classification of reducing agents: electrophilic and nucleophilic. LiAlH4, Redal®, Hydroallumination. Epoxide reduction (Fürst Plattner rule). DiBAH, LiAl(OtBu)3H, Diborane. NaBH4, LiBH4, Super-Hydride®, K- and L-selectride®, NaBH3CN. Chemoselectivity in reductions with hydrides. Weinreb amides. Ionic reduction (Kursanov). Reduction of aldehydes / ketones to methyl / methylenes : Wolff Kishner, Clemmensen, Mozingo, Via tosylhydrazones. Reduction of alcohols to alkanes from tosylates, alkyl halides. Barton McCombie. Catalytic hydrogenation (general). Reduction of alkenes, alkynes (to E- / Z-alkenes). Diimide. Formic acid. Hydride transfer (Hantzsch ester). Reductions via SET (Birch, enone reduction, McMurry). Use of Sm (II) iodide and Bu3SnH.
Synthesis and interconversion of the main functional groups. Mitsunobu. Synthesis of alcohols, phenols, aldehydes (aliphatic and aromatic) and ketones (aliphatic and aromatic). Synthesis of carboxylic acids (aliphatic and aromatic). Synthesis of esters (Tischenko). Synthesis of amides. Synthesis of amines (aliphatic and aromatic, Buchwald Hartwig). Synthesis of nitriles. Synthesis of alkyl halides (Appel) and ary halides. Metallorganic reagents (lithium-magnesium-copper). Coupling C-C catalyzed by Pd (Heck, Suzuki, Stille, Sonogashira). Synthesis of simple targets through the use of enolates.
Bibliography:
• J. Clayden, N. Greeves, S. Warren Organic Chemistry, 2nd Edition, Oxford University Press 2012 (ISBN 978-0-19-927029-3)
• J. Clayden, S. Warren Solution Manual for Organic Chemistry Accompany, 2nd Edition, Oxford University Press 2013 (ISBN 978-0-19-966334-7)
• M. Nantz, G. Zweifel Modern Organic Synthesis, Macmillan Higher Education, 2010
The copy of the exam themes (with related solutions) from previous years are distributed to interested students
The course consists exclusively of lectures during which some exercises related to the lesson are assigned.
The teacher receives the students in his studio ("Cube" - Via Valleggio 9, Floor 4) and is available to students by appointment via e-mail