TYPES OF CARBONYL COMPOUNDS - …

1 TYPES OF CARBONYL COMPOUNDS General Name Name formula suffix O -al Aldehyde C HR O Ketone C -one R' R O -oic C acidCarboxylic Hacid R O OAcid X=halogen -oylC halidehalide XR Acid OO -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 hydrophobichydrophilicgreasePhospholipid s - Fatty acid estersof glycerolglycerola triolPhosphatidylcholineLIPID BILAYERMICELLED etergents and "fatty acids" - amphiphilic moleculesCO2 OOOOOPOOONH3 OHOHOHH2OH2OH2OH2OH2OH2 OCO2 Homega-3-fattyacidAmides in Peptides and ProteinsH2 NOOHH2 NOOHH2 NOOHH2 NOOHH2 NOOHONH2 OOHglycinealaninephenylalanineasparagine glutamic acidFive of the 20 amino acid building blocks that go into all proteinsAll -amino acidsNHHNNHHNOOOOCO2 HProteins are polyamidesEach protein is defined by a specific primary sequence of amino acidsaaN 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 HOb-lactam g-lactam d-lactam O OO NH NH NH gb O aa bd

2 OH H2 NOH H2NH2N OH b O ga O b-amino acid g-amino acid d-amino acid bSUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES 1. Oxidation of alcohols N H 3 R1O OH CrOCl-Na2Cr2O7 will over-oxidize to carboxylic acid R1 H R1 R2 OH O O 1. R2 MgBr 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 AlCl4. Ozonolysis 1. O3 2. Zn/H3O+ OO H Overview of Reactions 4/27-5/9 - Reactions with carbonyls 1. Nucleophilic Addition: Reactions with Aldehydes and Ketones (Chapter 19) A. O -ONuH3O+HONu R R' Nu Example: Grignard Reaction Section 3O CH MgBr + HO Example: Cyanohydrin Formation Section O HO CN HH HCN Overview of Reactions 4/27-5/9 - Reactions with carbonyls 1.

3 Nucleophilic AdditionA. Hydration and Acetal Formation OH O H2 OHO OH O HO H3O+ Section Section O OOR H H+ HElectrophilic at C OHOH R No longer electrophilic at C RH 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 gH Br OO H O O H+ H O H O O H O O O H o H2O/H+ OH OH Br OH OH BrMg Mgelectrophile 1. 2. pH7 1. Nucleophilic of Reactions 4/27-5/9 - Reactions with carbonylsWittig Reactiontriphenyl phosphinePCH3-BrPCH3 BuLiPCH2 OPh3 PCH2 OPh = PhenylPh3 POSection of Reactions 4/27-5/9 - Reactions with carbonyls 1. Nucleophilic AdditionH2O Nu Nu -O Nu H3O+ R R' R R' Nu Overview of Reactions 4/27-5/9 - Reactions with AdditionB. continuedExample: Imine FormationHOH3O+H2 NNH2 OHNHH2 OHNHH2 OHNHHNHS ometimes called a Schiff base in biochemistrySection - Synthesis of Carboxylic Acids 1.

4 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 OO LiAlH4 OH LiAlH4 Ester hydride reduction OR H H Chapter + nucleophilic substitution nucleophilic addition MeMgBr O MeMgBr OH Ester grignard reactionO Me Section 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 Example:Ester Section O 2 O O 32O OH SOClCl OH CH CH OH OEt HCl O NR2O 2 Cl NHRE xample:AmideSection Overview of Reactions 4/27-5/9 - Reactions with carbonyls 3.

5 Alpha Substitution: Enolate/Enol Chemistry H O () O O O E E+ = must have " " H pKa 10-20electrophile enolate OH OH enol 2 BrOH O Br Alpha Halogenation Section Alpha AlkylationO OLi O Section LDA (base) CH3I Li N LDA =H aOverview of Reactions 4/27-5/9 - Reactions with carbonyls 4. Condensation Reactions: Enolate/Enol Chemistry O OO OH OR' base R R' R'' R'' R R H Aldol Reaction Section O O OHO 3 2H C H2 H3CO CHbase CHHH H3C H Claisen Condensation Section OO 3 O 2 O C H2 H3C H3C O + -Key in fatty acid biosynthesis CHEtO base CHEtO OEt OEt OEtOverview of Reactions 4/27-5/9 - Reactions with carbonyls 4. Condensation Reactions: Enolate/Enol Chemistry continued Michael Reaction Section OO OO 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