Reaction Mechanisms
657

Section: B079
3 Credit Hours
TR 4:00 - 5:15 pm
Room: LD 018

Textbook

Writing Reaction Mechanisms in Organic Chemistry, 2^nd edition, by Audrey Miller and Philippa Solomon, © 2000 (ISBN 0-12-496712-4). The optional (although highly recommended) text is Electron Flow in Organic Chemistry by Paul H. Scudder © 1992 (ISBN 0-471-61381-9). The Solomon text is very practical, with many practice problems and advice for solving them. The Scudder text provides an in-depth look at the system of electron flow pathways that is recommended by the IUPAC (which we will discuss in class). In addition to these textbooks, several others are good additions to your library, such as March’s Advanced Organic Chemistry by Smith and March, the two-volume Advanced Organic Chemistry by Carey and Sundberg, or the classic physical organic textbook Mechanism and Theory in Organic Chemistry by Lowry and Richardson. You will be receiving handouts concerning various topics in physical organic throughout the semester. These, along with the lecture notes, will complement the textbook.

Course Requirements

The prerequisite is C342; however, this should be considered a minimum. Ideally, you should have completed two semesters of physical chemistry as well. Although not required, some organic chemistry beyond the standard 2-semester undergraduate sequence would help. This may be either advanced coursework or research experience. While the knowledge you get from undergraduate organic is enough, if you haven’t looked at organic for a few years you will probably need some review.

Evaluation

Grades will be based on in-class examinations. There will be a total of four examinations of which your best three will each count for one third of your grade. Note that the fourth exam takes the place of the regularly scheduled final exam. There will also be several ungraded problem sets given throughout the course. These problem sets will include “textbook” style problems, as well as some requiring analysis of reactions that have appeared in the recent literature. These sets, as well as numerous other problems, will be discussed in class.

Exam dates

Exams will be given on the dates listed below. Note that since you may drop an exam, makeups will not be given except under extreme circumstances.

• Exam 1: Thursday, September 18
• Exam 2: Thursday, October 16
• Exam 3: Thursday, November 13
• Exam 4: Tuesday, December 9 during the normal class time.

(Note that this is not the regularly scheduled final exam day)

***Last day to withdraw is Tuesday, Nov. 11.

Tentative Course Outline

• Structure and Reactivity
• Application of Resonance Theory to Mechanisms
• Aromatic Systems
• General Mechanistic Principles and Reaction Classes
• Acids and Bases
• Stereochemical Effects on Mechanisms
• Linear Free Energy Relationships (Hammett Plots)
• Physical Methods
  • Kinetics and thermodynamics
  • Spectroscopy
  • Isotopic substitution
• Anions and Related Systems
  • Nucleophilic substitutions
  • Neighboring group effects
  • Carbanion rearrangements
• Cations and Related systems
  • Electrophilic reactions
  • Migrations to electrophilic centers
  • Carbenes and carbenoids
  • Nitrenes
• Free Radical Reactions and Rearrangements
• Physical Methods for Radicals and Transient Intermediates
  • Electrochemistry
  • Resonance methods (NMR, ESR, CIDNP)
• Concerted Mechanisms
  • Pericyclic reactions
  • Cycloadditions and cycloreversions
  • Sigmatropic rearrangements
• Other Mechanistic Studies
  • Photochemistry
  • Organometallic systems
  • Biochemical systems