Detergents and "fatty acids" - amphiphilic molecules CO2
hydrophobic
hydrophilic
CO2H
omega-3-fatty acid
H2O H2O
H2O
Phospholipids - Fatty acid esters of glycerol
grease OH
H2O H2O
OH
glycerol a triol
OH H2O
MICELLE O O
O
O
LIPID BILAYER
O O P O O
NH3
Phosphatidylcholine
O
Amides in Peptides and Proteins
OH
O
NH2
a OH
H2N
OH
H2N
O
O
glycine
alanine
OH
H2N
OH
H2N
O
O
O
phenylalanine
OH
H2N
glutamic acid
asparagine
Five of the 20 amino acid building blocks that go into all proteins All a-amino acids
Proteins are polyamides H N
N H
O
Each protein is defined by a specific primary sequence of amino acids
O
O
H N
N H
O
CO2H
b -Lactam Antibiotics H2N
H
H
Other Penicillins varied at this position
S
H H N
N
O
HO2C
H
O
g-lactam
NH
Penicillin G
H
d-lactam� NH
NH
O
O
b
N
HO2C
b-lactam
H2N
S
O
6-Aminopenicillamic acid
a
H
O
OH O
b-amino acid
a
H2N
H2N
g
g
O
b a
OH
g-amino acid
d
b
OH O
d-amino acid
SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES� 1. Oxidation of alcohols � ClN H CrO3 R1�
O
R2 R1
H
R1
OH�
Na2Cr2O7 will over-oxidize to carboxylic acid
O
O
Na2Cr2O 7� H 2SO4�
OH
R1
R1
R2
R2
1. R2MgBr 2. pH7
H
R1
OH
2. From alkynes O�
O
2+
R1
H
Hg , H2 O H2 SO 4
R1
Me�
R1
H
1. RBH2 2. H2 O2, NaOH
R1
H
SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES� 3. Friedel-Crafts Acylation O Cl
O R
R
AlCl3
4. Ozonolysis 1. O3 2. Zn/H3O+
H
O
O
Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 1. Nucleophilic Addition: Reactions with Aldehydes and Ketones (Chapter 19) O
A.� R
-O
Nu
H3O+
HO
R'� Nu
Example: Grignard Reaction�
O
Section 19.8
HO
CH3MgBr +
Example: Cyanohydrin Formation O
Section 19.7
HO
CN
HCN H
H
Nu�
Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 1. Nucleophilic Addition A. Hydration and Acetal Formation O
H2O
HO
OH
OH
O
O
HO
H3O+ Section 19.11
Section 19.6
O R
H
O
O
R�
H
+
OH OH
Electrophilic at C
H
No longer electrophilic at C�
OH R
HO
OH OH
H
HO
OH OH
R
H
HO
R
O
O
O
H
R
H
H2O
O
R
H
Protected (masked) aldehyde
O
Acetals as Protecting Groups for Aldehydes�
X
H Br O
OH OH
H
H
BrMg O
+
H Br
M go
O
Mgo
O
H BrMg
electrophile
O
O O
1.
H
2. pH7 H OH
O
H
H2O/H+
OH
O
O
Overview of Reactions 4/27-5/9 - Reactions with carbonyls 1. Nucleophilic Addition A.
CH3-Br
BuLi P
P
CH3
P
CH2
O
triphenyl phosphine
Ph3P Wittig Reaction
Section 19.12
Ph3PO
CH2
O
Ph = Phenyl
Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 1. Nucleophilic Addition O
B. R
-O
Nu
H3O+
H2O
Nu
Nu R
R' Nu
R'
Overview of Reactions 4/27-5/9 - Reactions with carbonyls 1. Nucleophilic Addition B. continued Example: Imine Formation H
O
O NH2
H2O
H3O+
H
NH
H H2N
H
H N
H2O NH
Sometimes called a Schiff base in biochemistry
H
NH
Section 19.9
SUMMARY - Synthesis of Carboxylic Acids� 1.
Oxidative cleavage of alkene R'
HO
KMnO4
HO O
R
2.
R
O R'
Oxidation of 1 alcohols and aldehydes O� R
H OH
R
H R
3.
O�
Jones Oxidation�
OH�
H
Carboxylation of Grignard Reagents O� RMgBr�
CO2� R
OH�
Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 2. Nucleophilic Acyl Substitution: Reactions with Carboxylic Acid derivatives (Chapter 21) O R
-O
O
Nu Y
Y
-
R
Nu
Y Nu Y = Leaving Group
O
LiAlH4 OR
O
RO-Li+
LiAlH4 H
O OR
Ester hydride reduction Chapter 17.5
H
nucleophilic substitution
MeMgBr
OH
nucleophilic addition
O
RO-Li+�
nucleophilic substitution
MeMgBr Me
OH Me Me
nucleophilic addition�
Ester grignard reaction Section 21.6
Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 2. Nucleophilic Acyl Substitution Carboxylic Acid Derivatives
Example:Acyl Halide Section 21.4 O
OH
O
Example:Ester Section 21.6 O
Cl
OH
SOCl2
O
OEt
CH3CH2OH HCl
O
Cl
O
NHR2
NR2
Example:Amide Section 21.7
Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 3. Alpha Substitution: Enolate/Enol Chemistry O
O
O
H must have "a " H (pKa 10-20)
E+ = electrophile
enolate
O E
OH
OH
enol
OH
Br2
O Br
O
H
LDA (base)
Alpha Halogenation Section 22.3
OLi
Alpha Alkylation Section 22.8
O CH3I LDA =
Li N
Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 4. Condensation Reactions: Enolate/Enol Chemistry O
O
O
base�
R'�
R
R
OH
R' R''
O
R''
R
H
Aldol Reaction O
Section 23.2-23.7
OH
O
base
O H�
CH3
H
H3C Claisen Condensation
O EtO
H
C H2
H�
Section 23.8-23.9
O
O
base CH3
H3C
CH2
O
EtO
+
O
CH2
H3C
O
H3C OEt
C H2
OEt -
OEt
Key in fatty acid biosynthesis
Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 4. Condensation Reactions: Enolate/Enol Chemistry continued� Section 23.11�
