CHEM-474

Oxidation state of organic compounds. Oxidation of C=C. Mild oxidation of 1º-ols → CHO, 2º-ols → ketone. Harsh oxidation of alcohols, amines, nitriles. Reduction involving metal/metal complexes (Wilkinson’s vs Crabtree catalysts), hydride (NaBH4, LiAlH4, DIBAlH, Red-Al and their derivatives) reductions and reductions involving single electron transfer (SET).Classification of molecular rearrangments. Mechanism of intramolecular 1,2–shifts involving migration of a group from C to C, C to N, N to C. Mechanism and examples of Wagner–Meerwein, Pinacol–Pinacolone, Benzidine–Benzillic acid, rearrangments. Favorski, Wolf, Beckmann, Hofmann, Curtius, Lossen, rearrangments. Schmidt, Steven, Baeyer–Villiger, Dakin and Fries rearrangments. Hoffman, Mobius–Huckle theories of electrocyclic reactions. Introduction and classification, Fukii, theories of electrocyclic reactions, cycloaddition reactions involving 4n/4n+2 pi electrons, Diels-Alder, Alder-ene reactions, 1,3-dipolar additions, Sigmatropic reactions, Cope and Ireland-Claisen rearrangement, Structure, methods of generation, detection, reactions and synthetic applications of free radicals, carbenes, nitrenes. Role of free radicals in nature and environment.

OBJECTIVES

To develop basic concepts and logical understanding about mechanism of redox reactions, molecular rearrangements, and pericyclic reactions

READINGS

1. March, J., Advanced Organic Chemistry, Wiley, New York.

2. Clayden, Greeves, Warren and Wothers, Organic Chemistry, Oxford, London

COURSE CONTENTS

Week	Topics and Readings
1.	Oxidation state of organic compounds. Oxidation of C=C. Mild oxidation of 1º-ols → CHO, 2º-ols → ketone. Harsh oxidation of alcohols, amines, nitriles.
2.	Reduction involving metal/metal complexes (Wilkinson’s vs Crabtree catalysts), hydride (NaBH4, LiAlH4, DIBAlH, Red-Al and their derivatives) reductions and reductions involving single electron transfer (SET).
3.	Classification of molecular rearrangments. Mechanism of intramolecular 1,2–shifts involving migration of a group from C to C
4.	Classification of molecular rearrangments. Mechanism of intramolecular 1,2–shifts involving migration of a group from C to N, N to C
5.	Classification of molecular rearrangments. Mechanism of intramolecular 1,2–shifts involving migration of a group from C to O and O to C.
6.	Mechanism and examples of Wagner–Meerwein, Pinacol–Pinacolone, Benzidine–Benzillic acid, rearrangments.
7.	Favorski, Wolf, Beckmann, Hofmann, Curtius, Lossen, rearrangments.
8.	Schmidt, Steven, Baeyer–Villiger, Dakin and Fries rearrangments.
9.	Molecular rearrangements on aromatic systems
10.	Mid Term Exam
11.	Introduction and classification of pericyclic reactions
12.	Hoffman, Mobius–Huckle theories of electrocyclic reactions
13.	Fukii, theories of electrocyclic reactions
14.	Cycloaddition reactions involving 4n/4n+2 pi electrons
15.	Diels-Alder, Alder-ene reactions, 1,3-dipolar additions
16.	Sigmatropic reactions, Cope and Ireland-Claisen rearrangement
17.	Structure, methods of generation, detection, reactions and synthetic applications of free radicals. Role of free radicals in nature and environment.
18	Structure, methods of generation, detection, reactions and synthetic applications of nitrenes and carbenes