Logical Approach to Mechanism Writing

Solving mechanism problems is not a matter of remembering particular mechansms and particular compounds. A logical series of steps can be followed:

  1. Analyze the transformation: define the correlations between reactants and products.

  2. Identify stereoelements and possible stereochemical outcomes; that is, determine if your mechanism must explain a stereochemical event, and if so, what it is.

  3. If necessary after the analysis of (B), draw clear stereoprojections of reactants and products.

  4. Identify the fundamental mechanistic class or classes of the reaction. Only ten classes exist.

  5. For pericyclic processes, identify and draw the frontier orbitals or the fully interacting basis sets. Proceed to determine the feasibility of the process.

  6. For all other reactions, write the mechanism as a series of elementary processes.

    1. Elementary processes are reaction steps that proceed through single transition states; for heterolytic reactions they are always Bronsted or Lewis acid-base reactions.

    2. To keep track of bond making and breaking, use curly arrows or fishhooks.

      • Curly arrows are for heterolytic processes and the arrowheads have two barbs.

      • Fishhooks are for homolytic processes; the fishhook has but a single barb.
Some pitfalls:

This is where experience comes in.


This page last modified 10:56 AM on Monday August 15th, 2011.
Webmaster, Department of Chemistry, University of Maine, Orono, ME 04469