Reading assignments are noted at the end of each major section.
Miller refers to Writing Reaction Mechanisms in Organic Chemistry, by Audrey
Miller and Philippa H. Solomon; C&S refers to Advanced Organic Chemistry, Part A
by Francis A. Carey and Richard J. Sundberg.
I. Introduction: Properties of Organic Molecules
- A. What is a reaction mechanism?
- B. Conventions in organic chemistry.
- 1. Drawing structures: cyclohexane and the diamond lattice; bicyclic structures; Newman/Fischer projections;
depiction of stereochemistry.
- 2. Rules for drawing resonance structures. The
relationship between resonance structures and valence bond theory and MO theory.
- 3. Stereochemical principles. (C&S Ch. 2)
- a. Enantiomers
- b. Diastereomers
- c. Prochiral relationships
- 4. Conformational properties of organic molecules (C&S Ch. 2)
- Energetic impact of changing molecular geometry
- Preferred conformations of simple molecules
- Cyclohexane derivatives
- Impact of conformations on reactivity:
Baldwin's rules, ring strain, the anomeric effect
- 5. "Electron pushing:" electronegativity and electron flow in reaction
- C. Introduction to mechanistic principles: potential energy diagrams, the Hammond postulate; the Curtin-Hammett principle; microscopic
Miller, Ch. 1, Ch 2, Ch. 3.
C&S secs. 1.1, 1.2, 2.1-2.6, 3.1-3.3.
- A. Structure and general elements of stabilization, pi donation(3.4.1, 4.4.1, 4.2.5, 4.4.1)
- B. Generation: heterolysis of R-X; addition of electrophiles to multiple bonds. (4.1.1, 5.1-5.3)
- C. Factors which promote or inhibit formation of carbocations.
- D. Reactions of carbocations.
- Polar addition to alkenes; source of Markownikov' rule (5.1-5.3)
- Isotope effects
- Primary KIE's: basis from Transition State Theory (3.5)
- Secondary KIE's
- Solvent and other KIE's
- Substituent effects: Hammett relationship and LFER's (3.6)
- E. Reactions of carbocations with nucleophiles
- a. Competition of different nucleophiles
- b. Sn1 vs. Sn2 reactivity (4.1)
- F. Loss of H+ from carbocations: E1 elimination (5.10)
- a. Direction of elimination
- b. Comparison with E2, E1cb mechanisms
- G. Rearrangements and migratory aptitudes. (4.4.4)
Reading: Miller, Secs. 3.1, 3.2, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6;
C&S Ch. 4 and 5; also 3.4, 3.5, 3.6.
- A. C-H acidity as a function of structure.
- B. Other methods of generation
- C. Structure & effect on reactivity (particularly aggregation
effects and enolate/enamine
- D. Reactions
- 1. Sn2; discussion of nucleophilicity.
- 2. Addition to C=O
- 3. Reprotonation
- 4. Other electrophiles
Reading: C&S Ch. 6.
- A. Structure:
comparison of singlet vs. triplet.
- B. Generation
- 1. a-elimination
- 2. From diazo compounds
- 3. Carbenoids
- 4. Stable carbenes.
- C. Reactions
- 1. Cyclopropanation
- 2. C-H insertion
- 3. Rearrangements
Reading: March Ch. 5 (handout);
Miller, Secs. 4.8, 4.9.
V. Free Radicals
- A. Structure; stable radicals and radical anions
- B. Generation: homolysis & bond strengths; photolysis.
- C. Reactions
- 1. Atom abstraction
- 2. Addition to multiple bonds
- 3. Fragmentation
- D. Chain reactions
Reading: Miller, Ch. 5.
C&S Ch. 11
Homework: 20 points each, 120 points total
Midterm exams: 100 points each, 200 points total
Final exam: 200 points
Letter grade will be assigned based on points earned out of 520 points total.
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Comments to K. Gable