Chemistry 447                                                Advanced Organic Chemistry                                   Spring 2005

Course Outline
  1. Bonding and Structure (Review) (Chapter 1.1-1.2, 3.8)
    1. Valence Bond Theory and Resonance Theory
    2. Hybrid Orbitals and Molecular Geometry, s vs p bonds
    3. Angle Strain and Chemical Reactivity
  2. Conformational Analysis and Molecular Mechanics (Chapter 3.1-3.4)
    1. Steric Strain and Molecular Mechanics
    2. Conformations of Acyclic Molecules
    3. Conformations of Cyclohexane and Substituted Cyclohexanes
    4. Other Ring Sizes
    5. Alkenes and Dienes - "Double Bond Strain"
    6. Prediction of Most Stable Hydrocarbon Isomers - "Stabilomers"
      1. Group Increments
      2. Molecular Mechanics Calculations
      3. General Principles
  3. Molecular Orbital Theory of Molecular Structure (Chapter 1.3-1.7)
    1. Methods and Approximations
      1. LCAO approximation
      2. semi-empirical vs ab initio calculations
    2. Qualitative Application of MO Theory
    3. Huckel MO Theory for p -Systems
      1. conjugated linear polyenes
      2. conjugated cyclic polyenes (annulenes)
    4. Perturbation MO Theory and Chemical Reactivity
    5. Hyperconjugation
  4. Aromaticity (Chapter 9)
    1. Basic Concept - Aromaticity, Antiaromaticity, and Nonaromaticity
      1. Criteria for Aromaticity - Theoretical vs Experimental
    2. The Annulenes
    3. Aromatic Ions
    4. Homoaromaticity
    5. Fused Ring Systems
    6. Heterocyclic Aromatics
  5. Concerted Pericyclic Reactions and Orbital Symmetry (Chapter 11 and parts of Chapter 4)
    1. Examples of Concerted Pericyclic Reactions
      1. Types of Experimental Evidence for Concertedness (Chapter 4, especially 4.2 and 4.12)
    2. Electrocyclic Ring Closure/Opening (Chapter 11.1)
      1. Examples
      2. Stereochemistry - disrotatory vs conrotatory
      3. Theory
        1. Orbital Symmetry Correlation Diagrams
        2. Frontier Molecular Orbital Theory
        3. Aromatic/Antiaromatic Transition States
        4. The Woodward-Hoffmann Rules
    3. Sigmatropic Rearrangements (Chapter 11.2)
      1. Stereochemistry and Terminology
      2. Theoretical Treatments
    4. Cycloadditions (Chapter11.3)
      1. Stereochemistry and Terminology
      2. Theoretical Treatments
    5. The Unified Woodward-Hoffmann Rules
    6. Concerted Reactions of Excited States - "Photochemically-Allowed Processes" (Chapter 13.2)
  6. Substituent Effects and Linear Free Energy Relationships (Chapter 4.3)