02B.

Principles of
Catalysis
CHEM 2313
SPRING 2018
 Specific versus General Catalysis
Specific catalyzed reactions involve a specific acid (H3O+) or base (OH–) associated
with the solvent. Proton transfer to/from the substrate occurs in a discrete step.

OH2
H
O [pt] OH

H 3C OCH3 H 3C OCH3

General catalyzed reactions involve contributions from all weak acids or bases
present. Proton transfer occurs together with another process in a “composite” step.

B
H Keep in mind that acids
O [pt] + [AdN] HO OH2 universally activate electrophiles
and bases activate nucleophiles.
H 3C OCH3 Engage acid catalysts with the
H 3C OCH3
electrophile and base catalysts
H 2O with the nucleophile.
 General Base-catalyzed Ester Hydrolysis
Weak bases also catalyze ester hydrolysis. Notice that the base is regenerated
when the product forms!

Amine is acting as a general

base catalyst. Bond
formation and deprotonation
happen simultaneously.

The norm for biochemical reactions

 Nucleophilic Catalysis
Addition or substitution by a nucleophile can accelerate reaction of the attached
carbon as an electrophile. This is called nucleophilic catalysis.

Consider the [SN2] substitution of hydroxide for chloride.

 Nucleophilic Catalysis
Addition or substitution by a nucleophile can accelerate reaction of the attached
carbon as an electrophile. This is called nucleophilic catalysis.

Addition of iodide (I–) accelerates the reaction. I– is both a better nucleophile and nucleofuge than Cl–!

Although R–I is less stable than R–Cl thermodynamically, it forms R–OH more
rapidly (kinetics!) than R–Cl. Catalysis is a wholly kinetic phenomenon.