Catalysis UCSB - Chapter 23 PDF

Chapter 23: Catalysis
Zhang
Chem 109C
21--1
21
Zhang
Chem 109C
Catalyst and Catalysis: Introduction
Catalyst is a compound that by its addition to a reaction increases

the rate of the reaction without itself being consumed or
changed at the end of the reaction (cycle).
The reaction is then called being catalyzed
catalyzed.
The phenomenon of catalyst in accelerating reaction is called
catalysis.
Me
Me
HN
Ph3PAuNTf 2 (5 mol %)
MsOH (1.2 equiv), 4 MS
Me
Me
CH2Cl2
Me
Me
quantitative (NMR)/ 61% (isolated)
H+
Ph3PAu+
Me
HN
Me
Me
Me
Me
HN
Au
PPh3
H+
Me
Me
Ph3PAu+
Au
PPh3
HN
Me
Me
MsO
23--2
23
Catalyst and Catalysis: Introduction
Zhang
Chem 109C
Catalyst increases the reaction rate by providing a pathway with

lower free energy of activation (reaction kinetics)
23--3
23
Catalysis in Organic Reactions
Zhang
Chem 109C
In organic reactions, several ways to accelerate reactions by

catalysts:
Increase electrophilicity
Increase nucleophilicity
Increase leaving ability as a nucleofuge (decrease electrophilicity)
Increase the stability of a transition state
Four types of catalysis:
acid catalysis
base catalysis
nucleophilic catalysis
metal-ion catalysis
23--4
23
Acid Catalysis: Ester Hydrolysis
Zhang
Chem 109C
23--5
23
Acid Catalysis
Zhang
Chem 109C
Specific-acid catalysis and general acid catalysis

Specific-acid catalysis: proton is fully transferred before the slow step of
the reaction (typically strong acidic conditions, two-stages)
General acid catalysis: proton transfer to the reactant during the slow
step of the reaction (typically under weak acidic conditions, one stage)
23--6
23
Acid Catalysis
Zhang
Chem 109C
General-acid catalysis vs
vs. specific-acid catalysis
23--7
23
Base Catalysis
Zhang
Chem 109C
General-base catalysis vs
vs. specific-base catalysis
23--8
23
Nucleophilic Catalysis
Zhang
Chem 109C
The catalyst is nucleophile and forms a covalent bond with

reactants/intermediates
Also called covalent catalysis
23--9
23
Metal--Ion Catalysis
Metal
Zhang
Chem 109C
Lewis acid catalysis (metal ions are Lewis acids)
23--10
23
Metal
Zhang
Chem 109C
Examples:
23--11
23
Metal
Zhang
Chem 109C
23--12
23
Intramolecular Reactions
Zhang
Chem 109C
1000
times
faster
Effective molarity (EM) is the concentration of the reactant that would

be required in an intermolecular reaction for it to achieve the same
rate as intramolecular reaction
23--13
23
Intramolecular Reactions
Zhang
Chem 109C
R = Me, EM = 2.3 x 104 M

R = iPr
iPr,, EM = 1.3 x 106 M
EM = 2.2 x 105 M
EM = 1 x 107 M
23--14
23
Zhang
Chem 109C
Intramolecular Catalysis
A catalyst is embedded or covalently bonded to substrates
Also called anchimeric effect/assistance
Due to intramolecularity,
y, the catalysis
y should be more efficient.
70000 times
Faster in the
Trans isomer
23--15
23
Intramolecular Catalysis: Example
Zhang
Chem 109C
23--16
23
Intramolecular Catalysis: Example
Zhang
Chem 109C
23--17
23
Catalysis in Biological Reactions
Zhang
Chem 109C
Most biological catalysts are enzymes (belongs to globular proteins)

Substrates and active sites (where the reaction occurs)
Substrates bound to the active site

Specificity (molecular recognition)
Lock-and-key model
Induced-fit model
Hexokinase
Red: before binding
Blue: after binding
23--18
23
Enzyme Catalysis
Zhang
Chem 109C
How do enzymes do catalysis?

Reacting groups are brought together in a proper orientation
Some of the amino acid side chains as well as bounded metal ions as
catalyst
Stabilizing the transition states and intermediates via van der Waals
interactions, electrostatic interactions, and H-bonding.
Naming of enzymes
End typically with ase
ase , indicating breaking the bond
Peptidase: breaking the peptide bond
Esterase: breaking the ester bond
Synthase
Synthesizing instead of breaking it down.
23--19
23
Carboxypeptidase A
Zhang
Chem 109C
Metalloenzyme
y
(enzymes containing
tightly bound metal
ions)
Hydrolyze C-terminal
except lysine and
arginine.
23--20
23
Serine Proteases
Zhang
Chem 109C
Trypsin, chymotrypsin and elastase are members of endopeptidases

known as serine proteases
23--21
23
Serine Proteases
Zhang
Chem 109C
Proposed
mechanism for
chymotrypsincatalyzed
hydrolysis
23--22
23
Lysozyme
Zhang
Chem 109C
Catalyze the hydrolysis of the bacterial cell wall NAM-NAG bond

(NAM: N-Acetylmuramic acid)
23--23
23
Protein pH
pH--Rate Profile
Zhang
Chem 109C
lysozyme
The pHs at which the enzyme are 50% active corresponds to the
pKa of enzyme
enzymes
s catalytic groups (as long as those values are at
lease 2 units apart.
Why pKa of Asp52 is 3.8 but pKa of Glu35 is 6.7 instead of 4.25 in
its free form?
23--24
23
Glucose--6-Phosphate Isomerase
Glucose
Zhang
Chem 109C
23--25
23
Aldolase
Zhang
Chem 109C
23--26
23

Catalysis UCSB - Chapter 23 PDF

Uploaded by

Copyright:

Available Formats

Catalysis UCSB - Chapter 23 PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Catalysis UCSB - Chapter 23 PDF

Uploaded by

Copyright:

Available Formats

Chapter 23: Catalysis

Catalyst and Catalysis: Introduction

Catalyst is a compound that by its addition to a reaction increases

quantitative (NMR)/ 61% (isolated)

Catalyst and Catalysis: Introduction

Catalyst increases the reaction rate by providing a pathway with

Catalysis in Organic Reactions

In organic reactions, several ways to accelerate reactions by

Four types of catalysis:

Acid Catalysis: Ester Hydrolysis

Specific-acid catalysis and general acid catalysis

The catalyst is nucleophile and forms a covalent bond with

Lewis acid catalysis (metal ions are Lewis acids)

Effective molarity (EM) is the concentration of the reactant that would

R = Me, EM = 2.3 x 104 M

Intramolecular Catalysis: Example

Intramolecular Catalysis: Example

Catalysis in Biological Reactions

Most biological catalysts are enzymes (belongs to globular proteins)

Substrates bound to the active site

How do enzymes do catalysis?

Trypsin, chymotrypsin and elastase are members of endopeptidases

Catalyze the hydrolysis of the bacterial cell wall NAM-NAG bond

You might also like