Zaistev’s Rule versus Hoffman’s Rule

Zaitsev’s Rule: The major elimination product is the more highly substituted alkene (Hardinger
77).

Hofmann’s Rule: The major elimination product is the less highly substituted alkene (Hardinger
78).

So which one applies?

It is dependent on how much steric hindrance there is at the end of the base that directly
interacts with the beta hydrogen.

For example: the base tert-butoxide, (CH3)3CO- has a lot of steric hindrance.
As a result, the carbon with more steric hindrance won’t favorably occupy
the same region of space as tert-butoxide, and it’s harder for the negatively-
charged oxygen to reach that carbon’s beta hydrogens (Hardinger 78).

Therefore, it’s more energetically-favorable for the tert-butoxide to attack the

beta hydrogen on the less-substituted carbon.

In this case, Hofmann’s Rule would dominate because of the amount of steric hindrance of
the base, and the major product is the less highly substituted alkene.

If the base does not have significant steric hindrance, such as -OH, then Zaitsev’s Rule
dominates and the major product is the more highly substituted alkene. This is because the
oxygen of the base has only a hydrogen bonded to it, which doesn’t cause as much hindrance
as the base moves to attack the beta hydrogens. Therefore, the base is able to maneuver
around the nucleophile’s substituents more freely and carry out the reaction.

Note: E1 reactions always proceed according to Zaitsev’s Rule.

Note: Steric hindrance is only relevant at the business end of the base (Hardinger 78).

Hardinger, Steven. “Chemistry 14D Lecture Supplement” 4th Ed. Hayden McNeil. 2016. Print.