Structure, Hybridization, Resonance, Aromaticity o # of bonds-1=sp (e.g.
3 bonds = sp2) o Aromaticity= 4n+2 electrons o Strained ring causes greater heat of combustion Acids and Bases o Lewis acid= accepts electron pair o Higher percentage of s character means more acidic hydrogen Stereoisomerism o Constitutional Isomers Isomers that have different atom connectivity o Stereoisomers Same connectivity but different arrangement in space Enantiomers Stereoisomers that are nonsuperimosable mirror reflections Diastereomers Stereoisomers that are not mirror reflections of each other o Stereocenter= sp3 carbon bonded to four different substituents o Assigning R/S configuration If lowest group is pointing away, determine normally If lowest group is not pointing away, exchange with group pointing away and determine reverse Nucleophilic Substitutions and Eliminations o o Alkyl o Strong Base o Weak Base o Poor Halide Nucleophile o 1 o Sn2 o Sn2 o No rxn. o 2 o Mostly E2 o Sn2 o Sn1/E1 in polar, protic solvents o 3 o E2 o Sn1/E1 in o Sn1/E1 in polar, protic solvent polar, protic solvents o Relative strength of nucleophiles Negatively charged nucleophiles react faster in substitution reactions that neutral nucleophiles Nucleophilic strength is in the same order as base strength when the nucleophilic atoms are in the same period of the periodic table Nucleophilic strength increases with increasing atom size when the nucleophilic atoms are in the same column of the periodic table o Leaving group ability Increases with decreasing base strength o Base strength and structure
Stronger base when not stabilized by resonance o Allylic and benzylic halides undergo Sn2 faster than simple alkyl halides o Requirements for E2 elimination in cyclohexene ring Beta hydrogen must be trans and diaxial Electrophilic additions o Oxymercuration-demercuration (alkene->alcohol) Markovnivokv product Hg(OAc)2, H2O followed by NaBH4 o Hydroboration-oxidation (alkene->alcohol) Anti-M product, syn-addition THF, BH3 followed by H2O2, -OH o Bromination Anti-addition o Epoxidation Formed with peroxyacids (-CO3H) Maintain starting stereochemistry o Diels-Alder Reaction Reaction with conjugated diene and alkene (with heat) Preferred transition state: endo (trans to the one carbon atom bridge) Nucleophilic addition at Carbonyl groups o Nucleophilic attack at carbonyl carbon Consequence of electrophilic character of carbonyl carbon atom o 1,2 addition Grignard, HCN, LiCH3 o 1,4 addition Gilman (CuLi) OH NH3 Nucleophilic substitution at Carbonyl groups o Carboxylic acid derivative reactivity Acyl chloride>acid anhydride>ester>amide Enols and Enolate Ion Reactions o Resonance stabilization of enolate ions Remove proton from carbon atom and determine number of resonance structures More resonance= more acidic o Kinetic product 1,2-dimethoxyethane [(CH3)2CH2]NLi,-78C Electrophilic and Nucleophilic Aromatic Substitution Free Radical Substitutions and Additions o Addition of high heat is usually indicative of free radical reactions
Generation of allylic radical is favored over generation of any alkyl radical Easier to remove tertiary allylic than primary allylic o Reactivity- selectivity principle Highly reactive species are nonselective and relatively non- reactive species are very selective o Pyrolysis (hemolytic cleavage at extremely high temperatures) Favors more stable radical formation Oxidations and Reductions o Periodic acid (HIO4) Cleaves the carbon-carbon bond of alpha hydroxyl aldehydes, ketones, alpha dicarbonyl compounds and 1,2-diols Spectroscopy o IR o O-H and N-H o 3400 o C-H (sp3) o 3000-2850 2 o C-H (sp ) o 3100-3000 o C-H (sp) o 3300 o C(triple)C and C(triple)N o 2100 o C=O o 1700 o C=C, aromatic C-C o 1600 o Aromatic C-C o 1500 o HNMR o Sp3 C atom o 1 o C atom attached to pi system o 2 o C atom attached to O atom o 3-4 2 o Sp C atom o 5-6 o Aromatic C atom o 7-8 o Aldehyde C atom o 10 o Carboxylic acid O atom o 11-12 Synthesis and Qualitative Analysis o