Lecture Slides • Spring 2020

Main topics include:
• Syllabus & i>clicker registration
• nomenclature and properties of alcohols
• preparation/reaction of alcohols review
• synthetic strategies using above runs

The following slides were presented during class on the dates indicated. These slides are only made available after the indicated class date. Every effort is made to correct errors found on slides during lecture before posting.

Prelab slides can always be found at the end of the class lecture slides.

Main topics include:
• Reduction of alcohols, esters and carboxylic acids; NaBH4, LiAlH4
• Chemoselectivity of reduction• oxidation of alcohols: chromic acid, Swern, Dess-Martin, PCC, PDC
• mechanisms of oxidation
• phenols: naming, properties, acidity
• extraction of phenols
• Determine Keq from pKa values
Main topics include:
• O vs. C-acylation (synthesis of aspirin)
• Kolbe-Schmidt reaction
• O-alkylation of phenols
• Grignard addition to ketones and aldehydes
• basicity of Grignards
• silyl protecting groups
• addition of acetylides; propargyl -OH
Lecture 3
Main topics include:
• acidic cleavage of ethers and phenols
• benzyl ethers as protecting groups
• preparation of ethers: Williamson; bromonium intermediates; addition of alcohols to alkenes
• epoxidation of alkenes
• physical properties of ethers
Main topics include:
thiol alkylation
• ring-opening of epoxides
• epoxides in synthesis
• nomenclature of ketones and aldehydes
• carbonyl bond strength (
σ vs. π)
• C=O polarity influence on bp and sol
• prep/rxns of aldehydes/ketones review
• hyperconjugation and inductive effect on ground state (C=O) stability
Lecture 5
Main topics include:
• types of carbonyl addition: condensation
• formation of imines and enamines
• pH dependence on rate of formation
• Keq imine vs. enamine (BDE of C=N)
• stabilized imines
• semicarbazones from semicarbazide
• Schiff bases from pyridoxal phosphate
• reductive amination
• Wolf-Kishner reduction
Main topics include:
• acetal formation; examples conditions
• mechanism; hemiacetal intermediate
• Dean-Stark trap with azeotropic diet.
• acetals protecting groups for carbonyl and diols
• stable hemiacetals
• glucose mutarotation
Lecture 7
Main topics include:
• Wittig reaction; phosphorus ylides
• acidity
• substituent effect
• percent ionization non-buffered (ICE)
• percent ionization buffered
• naming carboxylic acids
• physical properties
Main topics include:
• synthesis of carboxylic acids, review
• Grignard vs. nitrile synthesis of
• esterification through SN2
• Fisher esterification
• lactonization; macrolides
• mevalonolactone
• decarboxylation: diacids and b-ketoacids
• biological decarboxylations
Main topics include:
• carboxylic acid derivatives; naming
• addition/elimination mechanism
• reactivity of acid derivatives
• reactivity rationale; inductive/resonance
• conversion of acids to derivatives
• thionyl chloride in synthesis
• amides by DCC and mixed anhydride
• alcohol amine chemoselectivity for acylation with acid chlorides and anhyd
Main topics include:
• enols and enolates; enolization
• relative acidity of carbonyls
• kinetic vs. thermodynamic enolates
• Aldol condensation
• mixed aldol condensations

224-Lecture 12
Main topics include:
• classification, nomenclature of amines
• basicity of alkyl amines and aryl amines
• substituting effects in aryl amines
• decreased basicity of aromatic amines
• amidine bases: imidazole and DBU
• amines at physiological pH
• amino acids; zwitterions at phys. pH
• solubility and extraction of amines
Main topics include:
• basicity of amines review
• basicity of histamine N-atoms
• development of cimetidine (Tagement)
• LAH reduction to amines
• amine alkylation; quaternary salts
• Gabriel amine synthesis
• Curtius rearrangement
• Hoffmann elimination/rule
• Hoffmann transition states
Main topics include:
• SE-Ar with anilines; EDGs
• formation of diazonium ions
• substitution of diazonium ions (Sandmeyer reaction); in synthesis
• carbohydrate classification
• Fischer projections: review
• D and L aldohexoses
• anomers of pyranoses and furanoses
Main topics include:
• mutarotation: calculation of ratio
• increased preference for alpha anomer: solvation and anomeric effects
• redox reactions of carbohydrates
• chain extension of carbos: cyanohydrins
• chain shortening: Wohl degradation
224-Lecture 18
Main topics include:
• disaccharides; 1,4 and 1,6 linages
• amino acids; structure
• determine major form at specific pH
• classification of side-chains
• side chain Van der Waals interactions
• synthesis of amino acids: HVZ, reductive amination, Strecker, acetamidomalonate
224-Lecture 19
Main topics include:
• Arene oxidation; NIH shift
• Schiff bases of pyridoxal phosphate: -CO2, racemization, transamination
• peptides & amino acid analysis
• Sanger's rgt: 1-fluoro-2,4-dinitrobenzene
• ninhydrin staining
• Edman degradation with PITC
• enzyme hydrolysis: trypsin, chymotrypsi
• amino acid protecting groups
Lecture 20
Main topics include:
• protein structure
• lipids: definition and types
• waxes, phospholipids, fats & oils,
• fatty acid biosynthesis
• soaps; saponification
• detergents
• biodiesel
**Biosynthesis notes on D2L
Lecture 21
Main topics include:
•protaglandins and classification
• PGH2 biosynthesis
• cyclooxygenase inhibitors (COX1, COX2)
• terpenes and terpenoids: classification
• mevalonate pathway; isopentenyl diphophate (IPP); limonene biosynthesis
• steroids; fused ring structure
• biosynthesis of lanosterol
Main topics include:
•Skillbuilder 4
224-Lecture 11
Main topics include:
• reactions of derivatives
• Grignard vs. cuprate addition to acid halides
• DCC preparation of amides• saponification and transesterification
• making soap and biodiesel
• Grignard addition to esters and nitriles
• biological reactions of thioesters
• acetyl CoA in glucosamine synthesis
224-Lecture 13
Main topics include:
• Claisen condensation
• Dieckman condensation
• cholesterol and fatty acid biosynthesis
• acylation of ketones
• enolate alkylation
• malonic ester synthesis, decarboxylation
• acetoacetic ester synthesis
Main topics include:
•ATP and phosphorylation
• structural basis for phosphorylation potential
• coupled reactions and Keq
• Glycolysis steps (aldolase and and dehydrogenase mechanisms)
• Link reaction: pyruvate to acetyl CoA
• thiamine pyrophosphate mechanism
• other fates of pyruvate
Main topics include:
• Link reaction: pyruvate to acetyl CoA
• thiamine pyrophosphate mechanism
• other fates of pyruvate
• umpolung reactions: dithianes
• benzoin condensation
224-Lecture 24.pdf
Main topics include:
• conjugate addition, cuprates vs. Grignard
• Michael addition, Robinson annulation
• Hell-Volhard-Zelinski monohalogenation
• haloform reaction
• enolization and enol content
• monohalogenation of carboxylic acids
Main topics include:
• citric acid cycle & stoichiometry
• stages of energy extraction
• review: type of decarboxylation
• mechanisms of citric acid cycle
• symmetric citrate reacts asymmetrically
• Kreb's cycle as a source of biomolecules
224-Lecture 25.pdf
Main topics include:
• polymers
224-Lecture 26.pdf