Chemical Sciences

Enolate Anions and Enamines (8 hours). Aldol condensation. Mechanism. Cross aldolic reaction and intramolecular aldolic reaction. Oriented aldolic reaction: kinetic and thermodynamic control in the formation of enolates. Claisen and Dieckmann condensations. Cross Claisen condensations. Enamines. Alkylation and acylation of enamines. Acetoacetic synthesis and malonic synthesis. Michael addition (conjugate addition). Robinson's annulation. Heterocyclic compounds (5 hours). Pentatomic rings: Furan, thiophene and pyrrole. Paal-Knorr synthesis. Aromatic electrophilic substitutions. Benzoderivatives. Synthesis of indole according to Fisher. Pyridine. Hantsch synthesis. Aromatic nucleophilic substitutions. Chichibabin reaction. Pyridine N-oxides. Tautomeric equilibria in hydroxypyridines. Quinoline. Skraup synthesis. Pyrimidine. Purine. Carbohydrates (10 hours). Classification. Fischer and Haworth projections. D,L Configuration. Monosaccharides, cyclic structure, mutarotation. Monosaccharide Reactions: glycosides formation; enolization; tautomerization and isomerization; eters, acetals and esters preparation. Alditols. Reducing sugars. Oxidation reactions. Reaction with periodic acid. Osazones. Kiliani-Fischer synthesis. Ruff and Wohl degradation. The Fischer proof of the structure of (+)-glucose. Disaccharides. Polisaccharides. Amino acids, peptides and proteins (7 hours). Nomenclature, structure and classification. Acid-base properties. Isoelectric point. Amino acids synthesis, Resolution and Asymmetric synthesis. Peptides e proteins. Amino acids analysis of peptides. Peptide sequence and synthesis. Proteins structure. Lipids (4 hours). Lipids, Waxes, fats and oils. Soaps. Phospholipids. Prostaglandins and different eicosanoids. Terpenoids. Steroids. Nucleic Acids (2 hours). Nucleotides and nucleic acids. Pairing DNA bases. Pericyclic Reactions (4 hours). Molecular orbital theory and pericyclic reactions of pi systems. Electrocyclic reactions. Symmetry properties of orbitals and stereochemistry of electrocyclic reactions. Cycloaddition reactions. Diels Alder reaction: stereochemistry, regioselectivity, substituent effect. Sigmatropic rearrangement. Reductions (6 hours). Hydrogenation by homogeneous and heterogeneous catalysts. Reduction by III and IV group metal hydrides. Reduction by hydrogen atom donors. Reduction by solvated electrons: carbonyl compounds reduction, Birch reduction, Titanium-mediated reductions, Pinacol coupling. Reductive deoxygenation of carbonyl compounds. Oxidations (6 hours). Oxidation of alcohols by transition metal oxidants and by other oxidation reagents. Addition of oxygen at carbon-carbon double bonds, synthesis of glycols and epoxides. Reaction of Alkenes with Singlet Oxygen, Oxidative Cleavage of Carbon-Carbon Double Bonds, Ozonolysis, Oxidative Cleavage of Glycols. Oxidation of Ketones and Aldehydes. Oxidative Decarboxylation.

The student should have a good knowledge of the fundamental topics taught in the first course of Organic Chemistry and in the course of General Chemistry of the Bachelor in Chemistry (three years program). Essential Requirement. The student should have an appropriate knowledge of the English language since one of the adopted textbook (F. A. Carey, R. J. Sundberg “Advanced Organic Chemistry”, Part B; V Edition, Springer, 2007) is written in English. Important Requirement. The student should use electronic devices such as PC, tablet or smartphone in order to have access to the course teaching material available in the course website (https://elearning.uniroma1.it/course/view.php?id=14443). Useful Requirement.

B. Botta “Chimica Organica” II Edizione, edi-ermes, Milano, 2019 F. A. Carey, R. J. Sundberg “Advanced Organic Chemistry”, Part A-B; V Edition, Springer, 2007

2 h Frontal Lessons with a 15 min break.

Participation to the lessons is recommended but not mandatory

Written test lasting ca. 2 h Oral test lasting ca. 45 min

J. McMurry “Chimica Organica” VIII Edizione, Piccin, Padova, 2013

Lessons are held in a class with the aid of the blackboard and video projection system

Enolates and Enamine (6 ore). Aldol Condensation. Mechanisms. Cross Aldol Condensation. Kinetic and thermodynamic control. Claisen and Dieckmann Reactions. Enamines. Alkylation and acylation of enamines. Malonic and acetoacetic synthesis. Michael addition (conjugate addition). Robinson anullation. Heterocyclic compounds (4 ore). 5-membered rings: Furan, tiofene e pyrrole. Paal-Knorr synthesis. Benzoderivatives. Fisher indole synthesis. Pyridine. Hantsch synthesis. Chichibabin reaction. Pyridine N-oxides. Tautomerisms in hydroxypyridine. Quinoline. Skraup Synthesis. Pyrimidine. Purina. Carbohydrates (10 hours). Classification. Fischer and Haworth projections. D,L Configuration. Monosaccharides, cyclic structure, mutarotation. Monosaccharide Reactions: glycosides formation; enolization; tautomerization and isomerization; eters, acetals and esters preparation. Alditols. Reducing sugars. Oxidation reactions. Reaction with periodic acid. Osazones. Kiliani-Fischer synthesis. Ruff and Wohl degradation. The Fischer proof of the structure of (+)-glucose. Disaccharides. Polisaccharides. Amino acids, peptides and proteins (7 hours). Nomenclature, structure and classification. Acid-base properties. Isoelectric point. Amino acids synthesis, Resolution and Asymmetric synthesis. Peptides e proteins. Amino acids analysis of peptides. Peptide sequence and synthesis. Proteins structure. Lipids (3 hours). Lipids, Waxes, fats and oils. Soaps. Phospholipids. Prostaglandins and different eicosanoids. Terpenoids. Steroids. Nucleic Acids (2 hours). Nucleotides and nucleic acids. Pairing DNA bases. Pericyclic Reactions (8 hours). Molecular orbital theory and pericyclic reactions of pi systems. Electrocyclic reactions. Symmetry properties of orbitals and stereochemistry of electrocyclic reactions. Cycloaddition reactions. Diels Alder reaction: stereochemistry, regioselectivity, substituent effect. Sigmatropic rearrangement. Reductions (6 hours). Hydrogenation by homogeneous and heterogeneous catalysts. Reduction by III and IV group metal hydrides. Reduction by hydrogen atom donors. Reduction by solvated electrons: carbonyl compounds reduction, Birch reduction, Titanium-mediated reductions, Pinacol coupling. Reductive deoxygenation of carbonyl compounds. Oxidations (6 hours). Oxidation of alcohols by transition metal oxidants and by other oxidation reagents. Addition of oxygen at carbon-carbon double bonds, synthesis of glycols and epoxides. Reaction of Alkenes with Singlet Oxygen, Oxidative Cleavage of Carbon-Carbon Double Bonds, Ozonolysis, Oxidative Cleavage of Glycols. Oxidative Decarboxylation. Oxidation of Ketones and Aldehydes. Allylic Oxidation. Stereochemistry.

The student should have a good knowledge of the fundamental topics taught in the first course of Organic Chemistry and in the course of General Chemistry of the Bachelor in Chemistry (three years program). Essential Requirement. The student should have an appropriate knowledge of the English language since one of the adopted textbook (F. A. Carey, R. J. Sundberg “Advanced Organic Chemistry”, Part B; V Edition, Springer, 2007) is written in English. Important Requirement. The student should use electronic devices such as PC, tablet or smartphone in order to have access to the course teaching material available in the course website (https://www.chem.uniroma1.it/didattica/offerta-formativa/insegnamenti/chimica-organica-ii-con-laboratorio-al). Useful Requirement.

F. A. Carey, R. J. Sundberg “Advanced Organic Chemistry”, Part B; V Edition, Springer, 2007

2 h Frontal Lessons with a 15 min break.

2 subsequent lessons for 3 times a week

Written test (2h duration) followed by an oral test (20 minutes duration)

- F. A. Carey, R. J. Sundberg “Advanced Organic Chemistry”, Part B; V Edition, Springer, 2007 - B. Botta “Chimica Organica” II Edizione, edi-ermes, Milano, 2019

Lectures in classroom (45 minutes duration) with the possiblity to be followed from home (blended mode)

Enolates and enamines. Reactivity od aldehydes and ketones on alpha position. Keto-enolic rearrangement. Reactivity of enols. Alpha -halogenation of ketones and carboxylic acids. Hell Volhardt Zelinsky reaction. Formation of enolates. Choice of a base of proper pKa. General enolate reactivity. Alkyation and condensation reactions. Aldol reaction, acid-and base catalysis. Mechanisms. Crossed aldol reaction. Intramolecular aldol reaction. Ester condensation. Claisen and Dieckmann condensations. Cross Claisen condensation. Knoevenagel reaction. Mannich reaction. Pseudo aldol reaction. Henry reaction. Enolates from beta-dicarbonyl compounds. Acetoacetic Ester synthesis. Enamines. Formation. Enamine alkylation and acylation. Stork reaction. Reactivity of alpha-beta-unsaturated systems. Nucleophylic 1,2- and 1,4-additions. Michael addition. Addition of organometallic reagents to conjugated systems. Robinson Annulation. Heterocyclic compounds. Electron-rich five-membered aromatic heterocycles. Furan, thiophene and pyrrole. Aromaticity and structure, resonance energy values. Paal-Knorr synthesis. General reactivity. Acid and base behaviour. Aromatic electrophylic substitutions. Benzoderivatoves of furan, thiophene and pyrrole. General reactivity, acid-base behaviour. Aromatic electrophylic substitutions. Fischer synthesis of indole. Electron poor aromatic heterocycles. Pyridine. acid-base behaviour. General reactivity. Aromatic electrophylic substitutions. Synthesis of pyridine N-oxides. Reactivity of N-oxides toward aromatic electrophylic substitutions. Aromatic nucleophylic substitution reactions of pyridine. Chichibabin reaction. Synthesis of pyridine by Hantzsch. Benzoderivatives of pyridine. Quinoline and Isoquinoline. General reactivity. Quinoline synhesis by Skraup. Polynitrogen heterocycles. Imidazol. Purine and pyrimidine. Lipids. Saturated and unsaturated fatty acids. Physico-chemical properties. Structure and melting points. Fatty acid esters. Waxes. Triglyceride esters, fats and oils. Saponification of triglycerides. Detergents. Structure of tensioactive agents. Micelles. Structure of phospholipides. Fluid mosaic model of cell membranes. Liposoluble vitamns. Vitamins A, D and K. Prostaglandines and eicosanoids. Terpenoid compounds. Steroids. Cholesterol, cortisone and bile acids. Nucleic acids. Structure of nucleosides and nucleotides. Purine and pyrimidine bases. Structure of nucleic acids, double helix model by Watson and Crick. Base pairing in DNA. Carbohydrates. Classification of carbohydrates. Aldoses and ketoses. Fischer projection of monosaccarides. D,L Monosaccaride stereochemistry. Linear structures of five-membered and six-membered aldose mnosaccarides derived from eritrose and treose. Ketohexoses. Fructose. Formation of cyclic hemiacetals. Cyclic structure of monosaccarides. Furanose and pyranose cyclic structures. From Fischer linear structures to Haworth and chair projections. Anomeric carbon. Mutarotation. Reactions of monosaccarides. Glucoside formation, aglycones. Stereochemical control in glucoside formation. Enolisation, tautomerism, enediole formation. Isomerisation of fructose. Protection of hydroxyl groups. Synthesis of ethers, acetals and esters. Monosaccaride reduction. Alditole formation. Reducing sugars. Oxidation of monosaccarides with bromine water, Tollens reagent and Fehling reagent. Aldonic acids. Oxidation of monosaccarides with nitric acid. Aldaric acids. Enzymatic oxidation. Glucuronic acid. Oxidation with periodic acid. Monosaccaride structure cleavage. Osazones. Kiliani- Fischer elongation synthesis. Wohl degradation. Ruff degradation. Fischer strcture demonstration for D-glucose. Disaccarides. Glycosidic bond. Celobiose, maltose, lactose and sucrose. Polysaccarides. Starch, amylose, and amylopectin, hyaluronic acid. Aminoacids and peptides. Structure of proteogenic aminoacids. Examples of non proteogenic aminoacids. Acid-base properties of alpha-aminoacids. Zwitterion form of alpha-aminoacids. Behavior of alpha-aminoacids in solution in presence of an electrical field. Electrophoresis. Isoelectric point. Reaction with ninhydrin. Synthesis of aminoacids from alpha-halo acids. Synthesis from acylaminomalonates. Strecker synthesis.Stereochemical resolution of aminoacids racemic mixtures. Stereoselctive synthesis of aminoacids. Peptides and proteines. Features of peptide bond. Analysis of peptide aminoacid composition. Primary structure. Determination of aminoacid sequence by Edman degradation. Reaction with cyanogen bromide. Selective enzymatic cleavage of a peptide chain. Peptide synthesis. Formation of peptide bond. Protection reactions for amino and carboxy groups in aminoacids. Carbodiimide promoted condensation reaction. Solid-phase synthesis of peptides. Merrifiled and Wang resins. Protein structure. Secondary and tertiary structure. Alpha-helix and beta-sheet. Quaternary structure. Pericyclic reactions. Classification. Molecular orbitals and pericyclic reactions in conjugated systems. Electrocyclic reaction. Orbital symmetry and stereochemistry of electrocyclic reactions. Cycloaddition reactions. Diels-Alder cycloaddition. Stereochemistry, regioselectivity and substituent effect. Sigmatropic rearrangements. [3,3]-Sigmatropic rearrangements, Claisen rearrangement. [1,3]-dipolar reactions. Click reaction. Reductions. Hydrogen addition to carbon-carbon multiple bonds. Homogeneous and heterogeneous catalytic hydrogenation. Partial reduction of alkynes. Hydrogen transfer from diimide. Catalytic hydrogenation of carbonyls and other functional groups. Reductions of various functional groups with third group metal hydrides. Boron and aluminum hydrides. Fourth group hydrogen donors. Dissolving metal reductions. Reductions of carbonyls. Birch reduction. Reductive removal of functional groups. Titanium-promoted dehalogenations and deoxygenations. Reductive coupling of carbonyl compounds. Pinacole rearrangement. Deoxygenation of carbonyls. Reduction of carbonyls to methylene groups and to alkenes. Oxidations. Oxidation of alcohols to aldehydes, ketones and carboxylic acids. Oxidation with transition metals and other oxidants. Addition of oxygen to C-C double bonds. Formation of epoxides. Peracids. Peroxidic compounds. Sharpless epoxidation. Synthetic transformation of epoxides. Allylic oxidation. Reaction of alkenes with singlet oxygen. Oxidative cleavage of C-C double bond. Oxidative cleavage of glycols. Oxidation of aldehydes and ketone. Transition metal oxidants, other oxidants. Oxidative decarboxylation.

The student should have a good knowledge of the fundamental topics taught in the first course of Organic Chemistry and in the course of General Chemistry of the Bachelor in Chemistry (three years program). Essential Requirement. The student should have an appropriate knowledge of the English language since one of the adopted textbook (F. A. Carey, R. J. Sundberg “Advanced Organic Chemistry”, Part B; V Edition, Springer, 2007) is written in English. Important Requirement. The student should use electronic devices such as PC, tablet or smartphone in order to have access to the course teaching material available on the Google ClassRoom site of the Course. Useful Requirement.

Botta, B. "Chimica Organica", II edizione, Ed Edises. Brown, W.H. "Chimica Organica, V edizione, Ed. Edises F. A. Carey, R. J. Sundberg “Advanced Organic Chemistry”, Part A; V Edition, Springer, 2007 F. A. Carey, R. J. Sundberg “Advanced Organic Chemistry”, Part B; V Edition, Springer, 2007

2 h Frontal teaching with a 15 min break.

Attendance at class is optional

Prelimiary written test, based on the answer to five questions about the program topics. This will be followed by oral exam of 40 minutes duration.

2 h Frontal teaching with a 15 min break.