CONTENTS
FMO THEORY .................................................................................................................................. 3
Hybridization ...................................................................................................................................... 5
Formation of Grignard and Organolithium Reagents ............................................................................. 6
Addition of Organolithiums to Carboxylic Acids ................................................................................ 8
Nucleophillic reactions to carboxylic acid derivatives ........................................................................... 9
Nitrile hydrolysis ............................................................................................................................. 9
transesterification (one ester to another) ........................................................................................ 10
saponification (hydrolysis of ester – basic conditions) ..................................................................... 11
amine hydrolysis (aminolysis) ........................................................................................................ 12
amide hydrolysis ........................................................................................................................... 12
esters reacting with amines ........................................................................................................... 14
Grignard rxns on carboxylic acid derivatives ................................................................................... 14
Grignard rxns on that give us ketones instead of alcohols ................................................................ 15
how to make carboxylic acid derivatives more stable .......................................................................... 15
Thionyl chloride ............................................................................................................................ 17
acid chloride................................................................................................................................. 19
Ketones to alkenes (Wittig reaction; PPh3) ...................................................................................... 20
Formation of Amides From Esters .................................................................................................. 21
Acidic cleavage of ethers (SN2) ...................................................................................................... 22
Imines .......................................................................................................................................... 24
Enamines ..................................................................................................................................... 26
Substitution reactions ................................................................................................................... 27
SN1 reactions ........................................................................................................................... 27
SN1 vs SN2 reactions................................................................................................................. 29
SN1 – SN2 – E1 – E2 ................................................................................................................... 34
substitutions .................................................................................................................................... 35
saponification ............................................................................................................................... 35
cyanohydrin formation .................................................................................................................. 36
nitrile hydrolysis to carboxylic acid ................................................................................................. 36
ketone to alkene (wittig) ................................................................................................................ 37
acid chloride to make amides ........................................................................................................ 38
making secondary alcohols good lg ................................................................................................ 38
PBr3 ......................................................................................................................................... 39
SOCl2 ....................................................................................................................................... 40
Tosylates And Mesylates ............................................................................................................... 40
1
, One Good Idea (Which Doesn’t Actually Work That Well) ............................................................. 41
Introducing “Tosylates” and “Mesylates” .................................................................................... 42
alcohol to ketone .......................................................................................................................... 45
aldehyde/ketone to alcohol ........................................................................................................... 46
hydration of alkenes ...................................................................................................................... 47
imine – PADPED ........................................................................................................................... 49
reductive amination (amine – new amine) ....................................................................................... 50
Palladium on Carbon (Pd/C) .............................................................................................................. 51
Hydrohalogenation of Alkenes and Markovnikov’s Rule ...................................................................... 57
1. Reaction of Alkenes With Hydrohalic Acids (HCl, HBr, HI) .................................................. 57
2. Markovnikov’s Rule: Regioselectivity of HX Addition to Alkenes .......................................... 58
3. Stereoselectivity (Or Lack Thereof) In Addition of HX To Alkenes ......................................... 58
4. Hydrohalogenation of Alkenes: The Mechanism................................................................. 58
OsO4 (Osmium Tetroxide) for Dihydroxylation of Alkenes.................................................................... 61
stereospecific reaction .............................................................................................................. 62
The Mechanism for Dihydroxylation of Alkenes With OsO4 ........................................................... 62
Treatment of alkenes with cold, alkaline KMnO4 will also result in vicinal diols. ............................ 64
Catalytic OsO4 Using Stoichiometric Oxidant ............................................................................. 65
Hydroboration of Alkenes.................................................................................................................. 68
Alkene Reactions: Ozonolysis ........................................................................................................... 70
elimination ....................................................................................................................................... 74
alcohol to alkene .......................................................................................................................... 74
Electrophilic aromatic substitution .................................................................................................... 75
Halogenation of Benzene ............................................................................................................... 75
Nitration and Sulfonation .............................................................................................................. 78
Nitration of Benzene .................................................................................................................. 78
Addition of SO3H (Sulfonation) ................................................................................................... 79
Carbon-Carbon Bond Forming Reactions ........................................................................................... 80
EAS Reactions (3) – Friedel-Crafts Acylation and Friedel-Crafts Alkylation ........................................ 80
alkylytion to activate the alkyl halide ........................................................................................... 82
Carbocation Rearrangements Can Occur In The Friedel-Crafts Alkylation Reaction ....................... 84
acylation ................................................................................................................................... 85
2
,FMO THEORY
3
, 4
FMO THEORY .................................................................................................................................. 3
Hybridization ...................................................................................................................................... 5
Formation of Grignard and Organolithium Reagents ............................................................................. 6
Addition of Organolithiums to Carboxylic Acids ................................................................................ 8
Nucleophillic reactions to carboxylic acid derivatives ........................................................................... 9
Nitrile hydrolysis ............................................................................................................................. 9
transesterification (one ester to another) ........................................................................................ 10
saponification (hydrolysis of ester – basic conditions) ..................................................................... 11
amine hydrolysis (aminolysis) ........................................................................................................ 12
amide hydrolysis ........................................................................................................................... 12
esters reacting with amines ........................................................................................................... 14
Grignard rxns on carboxylic acid derivatives ................................................................................... 14
Grignard rxns on that give us ketones instead of alcohols ................................................................ 15
how to make carboxylic acid derivatives more stable .......................................................................... 15
Thionyl chloride ............................................................................................................................ 17
acid chloride................................................................................................................................. 19
Ketones to alkenes (Wittig reaction; PPh3) ...................................................................................... 20
Formation of Amides From Esters .................................................................................................. 21
Acidic cleavage of ethers (SN2) ...................................................................................................... 22
Imines .......................................................................................................................................... 24
Enamines ..................................................................................................................................... 26
Substitution reactions ................................................................................................................... 27
SN1 reactions ........................................................................................................................... 27
SN1 vs SN2 reactions................................................................................................................. 29
SN1 – SN2 – E1 – E2 ................................................................................................................... 34
substitutions .................................................................................................................................... 35
saponification ............................................................................................................................... 35
cyanohydrin formation .................................................................................................................. 36
nitrile hydrolysis to carboxylic acid ................................................................................................. 36
ketone to alkene (wittig) ................................................................................................................ 37
acid chloride to make amides ........................................................................................................ 38
making secondary alcohols good lg ................................................................................................ 38
PBr3 ......................................................................................................................................... 39
SOCl2 ....................................................................................................................................... 40
Tosylates And Mesylates ............................................................................................................... 40
1
, One Good Idea (Which Doesn’t Actually Work That Well) ............................................................. 41
Introducing “Tosylates” and “Mesylates” .................................................................................... 42
alcohol to ketone .......................................................................................................................... 45
aldehyde/ketone to alcohol ........................................................................................................... 46
hydration of alkenes ...................................................................................................................... 47
imine – PADPED ........................................................................................................................... 49
reductive amination (amine – new amine) ....................................................................................... 50
Palladium on Carbon (Pd/C) .............................................................................................................. 51
Hydrohalogenation of Alkenes and Markovnikov’s Rule ...................................................................... 57
1. Reaction of Alkenes With Hydrohalic Acids (HCl, HBr, HI) .................................................. 57
2. Markovnikov’s Rule: Regioselectivity of HX Addition to Alkenes .......................................... 58
3. Stereoselectivity (Or Lack Thereof) In Addition of HX To Alkenes ......................................... 58
4. Hydrohalogenation of Alkenes: The Mechanism................................................................. 58
OsO4 (Osmium Tetroxide) for Dihydroxylation of Alkenes.................................................................... 61
stereospecific reaction .............................................................................................................. 62
The Mechanism for Dihydroxylation of Alkenes With OsO4 ........................................................... 62
Treatment of alkenes with cold, alkaline KMnO4 will also result in vicinal diols. ............................ 64
Catalytic OsO4 Using Stoichiometric Oxidant ............................................................................. 65
Hydroboration of Alkenes.................................................................................................................. 68
Alkene Reactions: Ozonolysis ........................................................................................................... 70
elimination ....................................................................................................................................... 74
alcohol to alkene .......................................................................................................................... 74
Electrophilic aromatic substitution .................................................................................................... 75
Halogenation of Benzene ............................................................................................................... 75
Nitration and Sulfonation .............................................................................................................. 78
Nitration of Benzene .................................................................................................................. 78
Addition of SO3H (Sulfonation) ................................................................................................... 79
Carbon-Carbon Bond Forming Reactions ........................................................................................... 80
EAS Reactions (3) – Friedel-Crafts Acylation and Friedel-Crafts Alkylation ........................................ 80
alkylytion to activate the alkyl halide ........................................................................................... 82
Carbocation Rearrangements Can Occur In The Friedel-Crafts Alkylation Reaction ....................... 84
acylation ................................................................................................................................... 85
2
,FMO THEORY
3
, 4
