| Topic |
Sub-topic |
| LESSON 1. Reactions of nucleophilic substitution on sp3 carbons. |
Bimolecular and unimolecular nucleophilic substitution reactions (SN2 and SN1): kinetic, mechanisms and stereochemistry. Competition between SN2 and SN1. Transformation of functional groups through SN2 and SN1 reactions: synthesis of Williamson, preparation of thiols and thioethers, preparation of amines, reactions of alcohols and ethers, opening of epoxides, conversion of carboxylic acids into methyl esters by reaction with diazomethane. |
| LESSON 2. Reactions of elimination. |
Bimolecular elimination (E2). Unimolecular elimination (E1). E1cb elimination. Intramolecular elimination (Ei). Mechanisms. Competition between substitution and elimination. Application of elimination reactions in organic synthesis: Hofmann elimination, Cope elimination, dehydration of alcohols, pinacol rearrangement. |
| LESSON 3. Reactions of nucleophilic addition to the carbonyl group. |
Structure and general reactivity of carbonyl group (aldehydes and ketones). General mechanism of nucleophilic addition. Non reversible nucleophilic additions: addition of organometallic compounds (alkyne anions, organolithium and Grignard reagents); addition of stabilised carbanions; addition of hydride. Reversible nucleophilic additions: addition of oxygenated and sulphur compounds (water, alcohols and thiols); addition of nitrogenous compounds (amines and other nitrogenous compounds); addition of cyanide of hydrogen. |
| LESSON 4. Reactions of nucleophilic substitution on the carbonyl group. |
Structure and general reactivity of carboxylic acids and derivatives. Relative reactivity of acid derivatives: basicity and electrophilic character. Non reversible addition-elimination reactions: the leaving group.
Reversible reactions of addition-elimination: basic and acid catalysis. Reactions with water and alcohols; reactions with ammonia and amines. Structure and reactivity of nitriles. Reactions of nitriles. |
| LESSON 5. Reactivity in alpha position of the carbonyl group. |
Enols and enolates: general reactivity. Reactions
of enolate anions of ketones and esters: alkylation of ketones, alkylation of esters. Halogenation of ketones. Reactions of enolate anions with carbonyl compounds: aldol reaction, Claisen condensation, Dieckmann condensation, reaction of Reformatsky. |
| LESSON 6. Reactions of oxidation-reduction. |
Reactions of oxidation of alcohols. Reactions of oxidation of carbonyl compounds. Oxidative cleavage of alkenes and alkynes. Reduction of aldehydes and ketones. Reduction of carboxylic acids, esters and nitriles. |
| LESSON 7. Conjugated additions to bifunctional compounds. |
Reactions of alpha-dicarbonyl compounds: transposition of benzilic acid, enolization. Reactions of beta-dicarbonyl compounds: enolization, alkylation, decarboxylation, malonic synthesis, acetyl acetic synthesis, Knoevenagel reaction, alkylation of dianions. Reactions of alpha,beta-unsaturated carbonyl compounds: reactions with electrophiles, reaction with nucleophiles, addition of organometallic compounds, addition of carbanions (Michael addition), Robinson annulation. |
| LABORATORY |
In these sessions experiments related with the theoretical content of the subject will be carried out. |
