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TYPES OF CARBONYL COMPOUNDS�
General Name Name formula suffix O -al Aldehyde C
HR O�
Ketone C� -one R' R
O -oic C acid
Carboxylic Hacid� R O
OAcid X=halogen -oylC halidehalide XR
Acid O O� -oic anhydrideC
O Canhydride R R
Name General Name formula suffix
O -oateEster C O
R' R
O
CLactone (cyclic ester) O
O
R' -amideCAmide NR
R"
Lactam� O
C R' (cyclic amide) N
hydrophobic hydrophilic
grease
Phospholipids - Fatty acid estersof glycerol
glycerola triol
Phosphatidylcholine
LIPID BILAYER
MICELLE
Detergents and "fatty acids" - amphiphilic molecules
CO2
O
OO
OO
P O
O
O
NH3
OH
OH
OH
H2O
H2O
H2O
H2O
H2O
H2O
CO2H
omega-3-fattyacid
Amides in Peptides and Proteins
H2NO
OH H2NO
OHH2N
O
OH H2NO
OH H2NO
OH
O
NH2
O OH
glycine alanine phenylalanine asparagine glutamic acid
Five of the 20 amino acid building blocks that go into all proteinsAll -amino acids
NH
HN
NH
HN
O
O
O
O
CO2H
Proteins are polyamides
Each protein is defined by a specific primary sequence of amino acids
a
a
N
S
H 2C
O
H2N HH
N
S
H 2C
O
H N
HH
O
HO6-Aminopenicillamic acid
Penicillin G
Other Penicillins varied at this position
-Lactam Antibiotics
HO
b-lactam g-lactam d-lactam�
O O
O
NH NH NH
gb O aa
bd OH H2NOH H2NH2N
OH b O g a O
b-amino acid g-amino acid d-amino acid
b
SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES�
1. Oxidation of alcohols �
N H 3
R1
O
OH�
CrOCl- Na2Cr2O7 will over-oxidize to
carboxylic acid R1� H
R1
R2
OH
O O 1. R2MgBr R2Na2Cr2O7�
H2SO4� H 2. pH7 R1 OH R1R1 R2
2. From alkynes
O� O Hg2 +, H2O
R1 H 1. RBH2R1 H H2SO4 R1 Me� 2. H2O2, NaOH
R1 H
SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES�
3. Friedel-Crafts Acylation O
R
3
O
RCl AlCl
4. Ozonolysis
1. O3
2. Zn/H3O+ O O H
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�1. Nucleophilic Addition: Reactions with Aldehydes and Ketones (Chapter 19)
A.� O -O Nu H3O+ HO Nu�
R R'�
Nu
Example: Grignard Reaction� Section 19.8
3
O CH MgBr +
HO
Example: Cyanohydrin Formation Section 19.7
O HO CN
HH HCN
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�1. Nucleophilic AdditionA. Hydration and Acetal Formation
OH O H2O HO OH O HO
H3O+ Section 19.6 Section 19.11
O O OR H H+
HElectrophilic at C OH OH R�No longer electrophilic at C�
R H
R H R H
O OO
R H
O
R H
H2O
( )
OH OH OH OH OH HO
HO
HO
Protected maskedaldehyde
O O
Acetals as Protecting Groups for Aldehydes�
H X o
BrMg M g H
Br O O
H
O O
H+
H
O H
O O
H
O O
O
H
o
H2O/H+
OH OH
Br
OH OH
BrMg Mg
electrophile 1.
2. pH7
1. Nucleophilic AdditionA.
Overview of Reactions 4/27-5/9 - Reactions with carbonyls
Wittig Reaction
triphenyl phosphine
P
CH3-Br
P CH3
BuLi
P CH2
O
Ph3P CH2
OPh = PhenylPh3PO
Section 19.12
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�1. Nucleophilic Addition
H2O Nu Nu B. O -O Nu H3O+
R R' R R'
Nu
Overview of Reactions 4/27-5/9 - Reactions with carbonyls1. Nucleophilic AdditionB. continued
Example: Imine Formation
H
OH3O+
H2N
NH2
O H
NH
H2O H
NH
H2O H
NH
H
N
H
Sometimes called a Schiff base in biochemistry Section 19.9
SUMMARY - Synthesis of Carboxylic Acids�1. Oxidative cleavage of alkene
R' KMnO4 HO HO O O
R R R'
2. Oxidation of 1 alcohols and aldehydes O�
O�H Jones Oxidation�
OH�
R
OH RH
R H
3. Carboxylation of Grignard Reagents
O�CO2�
RMgBr�R OH�
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�2. Nucleophilic Acyl Substitution:Reactions with Carboxylic Acid derivatives (Chapter 21)
R Y
O
Y R
O
Y-
Nu
-O Nu
Nu
Y = Leaving Group
O O LiAlH4 OH
LiAlH4 Ester hydride reduction
OR H H Chapter 17.5RO-Li+
nucleophilic substitution nucleophilic addition
MeMgBr O MeMgBr OH Ester grignard reactionO Me Section 21.6Me Me
OR RO-Li+�
nucleophilic substitution nucleophilic addition�
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�2. Nucleophilic Acyl SubstitutionCarboxylic Acid Derivatives
Example:Acyl Halide Section 21.4 Example:Ester Section 21.6 O
2
O O
3 2
O OH
SOCl
Cl OH
CH CH OH
OEt
HCl
O NR2O
2
Cl
NHR Example:AmideSection 21.7
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�3. Alpha Substitution: Enolate/Enol Chemistry
H
O
( )
O O
O
E
E+ = must have " " H
pKa 10-20electrophile enolate
OH OH
enol
2BrOH O
Br Alpha Halogenation Section 22.3
Alpha AlkylationO OLi O Section 22.8
LDA (base) CH3I Li N
LDA =H
a
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�4. Condensation Reactions: Enolate/Enol Chemistry
O O O OH OR' base�
R R'� R'' R'' R R H
Aldol Reaction Section 23.2-23.7
O O OH O
3 2H C H2
H3CO
CH
base
CH HH�
H3C H�
Claisen Condensation Section 23.8-23.9
O O
3
O
2
O
C H2
H3C
H3C
O + -
Key in fatty acid biosynthesis
CHEtO
base
CHEtO OEt
OEt
OEt
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�4. Condensation Reactions: Enolate/Enol Chemistry continued�
Michael Reaction Section 23.11�
O O O O
H H H O
O O
H
O
O O
H
OH
H
H
EtO
NaOEt
Me EtO Me
Me
EtO Me
Me
EtO Me
HOEt
Me