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Chapter 24 Ch
Catalysis
Irene Lee Case Western Reserve University Cleveland, OH 2004, Prentice Hall
Catalyst
A catalyst is a substance that increases the rate of a reaction without itself being consumed or changed
A catalyst increases the rate of the reaction by lowering the G of the reaction
A catalyst can provide a more favorable pathway for an organic reaction by: increasing the susceptibility of an electrophile to nucleophilic attack increasing the reactivity of a nucleophile increasing the leaving ability of a group by converting it to a weaker base
Nucleophilic Catalysis
Both the formation of the acyl imidazole and its subsequent hydrolysis are both faster than ester hydrolysis
An Acid-Catalyzed Reaction
The acid increases the rates of both slow steps of the reaction
In specific-acid catalysis, the proton is fully transferred before the slow step of the reaction p
In general-acid catalysis, the proton is transferred during the slow step of the reaction
Base Catalysis
A base catalyst increases th rate of the reaction by b t l ti the t f th ti b removing a proton from the reaction
specific-base catalyzed dehydration
In specific-base catalysis, the proton is completely removed before the slow step of the reaction
general-base catalysis
In general-base catalysis, the proton is removed during the slow step of the reaction
Metal-Ion Catalysis
A. A The metal ion increases the susceptibility of electron attack B. B The metal ion makes the leaving group a weaker base C. The metal ion increases the nucleophilicity of water
Metal-Ion-Catalyzed Decarboxylation
The metal-bound hydroxide is a better nucleophile than metal bound water The metal ion also decreases the basicity of the leaving group
The relative rate of reactant D is higher than the relative rate of B because the groups in D are less apt to adopt an unfavorable conformation for the reaction
Putting a reacting group and a catalyst in the same molecule increases the rate of the reaction
The trans isomer reacts much faster than the cis isomer
The rate of phenyl acetate hydrolysis is enhanced by an intramolecular general base catalysis
In the presence of nitro groups, the ortho-carboxyl substituent acts as an intramolecular nucleophilic p catalyst
The reactants are called substrates The substrate specifically fits and binds to the active site
Hexokinase undergoes a conformational change upon binding to a substrate red: before substrate-binding green: after substrate-binding
Some of the amino acids in the enzyme serve as catalytic groups; many enzymes have metal ions as catalysts Groups on the enzyme can stabilize the transition state y of the reaction
The binding pocket at the active site of serine proteases dictates substrate specificity
The amino acids at the active site of lysozyme are y y involved in binding the substrate
The pH-rate profile of an enzyme is a function of the p pKa values of the catalytic groups in the enzyme y g p y
Glucose-6-phosphate Isomerase