Bruckner Reinhard. Organic mechanisms: reactions, stereochemistry and synthesys

3rd edition. Springer-Verlag Berlin Heidelberg 2010. - 855 p.
This book is a continuation of a highly significant educational endeavor started by Reinhard Bruckner and joined by Michael Harmata. It is directed at understanding the language of chemistry: more specifically, the structures of organic compounds; how structure influences function, reactivity and change; and how this knowledge can be used to design and synthesize new structures. The book provides a coerstone for understanding basic reactions in chemistry and by extension the chemical basis for structure, function and change in the whole of science.

Contents

Radical Substitution Reactions at the Saturated C Atom

Bonding and Preferred Geometries in Carbon Radicals, Carbenium Ions and Carbanions
Preferred Geometries
Bonding
Stability of Radicals
Reactive Radicals
Unreactive Radicals
Relative Rates of Analogous Radical Reactions
The Bell–Evans–Polanyi Principle
The Hammond Postulate
Radical Substitution Reactions: Chain Reactions
Radical Initiators
Radical Chemistry of Alkylmercury(II) Hydrides
Radical Halogenation of Hydrocarbons
Simple and Multiple Chlorinations
Regioselectivity of Radical Chlorinations
Regioselectivity of Radical Brominations Compared to Chlorinations
Rate Law for Radical Halogenations; Reactivity/Selectivity Principle and the Road to Perdition
Chemoselectivity of Radical Brominations
Radical Chain Chlorination Using Sulfuryl Chloride
Autoxidations
Synthetically Useful Radical Substitution Reactions
Simple Reductions
Formation of 5-Hexenyl Radicals: Competing Cyclopentane Formation
Diazene Fragmentations as Novel Alkane Syntheses

Nucleophilic Substitution Reactions at the Saturated C Atom

Nucleophiles and Electrophiles; Leaving Groups
Good and Poor Nucleophiles
Leaving Groups: Good, Bad and Ugly
S_N2 Reactions: Kinetic and Stereochemical Analysis—Substituent Effects on Reactivity
Energy Profile and Rate Law for S_N2 Reactions: Reaction Order
Stereochemistry of S_N2 Substitutions
A Refined Transition State Model for the S_N2 Reaction; Crossover Experiment and Endocyclic Restriction Test
Substituent Effects on S_N2 Reactivity
SN1 Reactions: Kinetic and Stereochemical Analysis; Substituent Effects on Reactivity
Energy Profile and Rate Law of S_N1 Reactions; Steady State Approximation
Stereochemistry of S_N1 Reactions; Ion Pairs
Solvent Effects on S_N1 Reactivity
Substituent Effects on S_N1 Reactivity
When Do S_N Reactions at Saturated C Atoms Take Place According to the S_N1 Mechanism and When Do They Take Place According to the S_N2 Mechanism?
Getting by with Help from Friends, or a Least Neighbors: Neighboring Group Participation
Conditions for and Features of S_N Reactions with Neighboring Group Participation
Increased Rate through Neighboring Group Participation
Stereoselectivity through Neighboring Group Participation
S_Ni Reactions
Preparatively Useful S_N2 Reactions: Alkylations

Electrophilic Additions to the C=C Double Bond

The Concept of cis- and trans-Addition
Vocabulary of Stereochemistry and Stereoselective Synthesis I
Isomerism, Diastereomers/Enantiomers, Chirality
Chemoselectivity, Diastereoselectivity/Enantioselectivity, Stereospecificity/Stereoconvergence
Electrophilic Additions that Take Place Diastereoselectively as cis-Additions
A Cycloaddition Forming Three-Membered Rings
Additions to C=C Double Bonds That Are Related to Cycloadditions and Also Form Three Membered Rings
cis-Hydration of Alkenes via the Hydroboration/Oxidation/Hydrolysis Reaction Sequence
Heterogeneous Hydrogenation
Enantioselective cis-Additions to C=C Double Bonds
Vocabulary of Stereochemistry and Stereoselective Synthesis II: Topicity, Asymmetric Synthesis
Asymmetric Hydroboration of Achiral Alkenes
Thought Experiment I on the Hydroboration of Chiral Alkenes with Chiral Boranes: Mutual Kinetic Resolution
Thought Experiments II and III on the Hydroboration of Chiral Alkenes with Chiral Boranes: Reagent Control of Diastereoselectivity, Matched/Mismatched Pairs, Double Stereodifferentiation
Thought Experiment IV on the Hydroboration of Chiral Olefins with Chiral Dialkylboranes: Kinetic Resolution
Catalytic Asymmetric Synthesis: Sharpless Oxidations of Allylic alcohols
Additions that Take Place Diastereoselectively as trans-Additions (Additions via Onium Intermediates)
Addition of Halogens
The Formation of Halohydrins; Halolactonization and Haloetherification
Solvomercuration of Alkenes: Hydration of C=C Double Bonds through Subsequent Reduction
Additions that Take Place or Can Take Place without Stereocontrol Depending on the Mechanism
Additions via Carbenium Ion Intermediates
Additions viaCarbanionIntermediates

?-Eliminations

Concepts of Elimination Reactions
The Concepts of ?,?- and 1,n-Elimination
The Terms syn- and anti-Elimination
When Are syn- and anti-Selective Eliminations Stereoselective?
Formation of Regioisomeric Alkenes by b-Elimination: Saytzeff and Hofmann Product(s)
The Synthetic Value of Het¹/Het² in Comparison to H/Het-Eliminations
?-Eliminations of H/Het via Cyclic Transition States
?-Eliminations of H/Het via Acyclic Transition States: The Mechanistic Alteatives
E2 Eliminations of H/Het and the E2/S_N2 Competition
Substrate Effects on the E2/S_N2 Competition
Base Effects on the E2/S_N2 Competition
A Stereoelectronic Effect on the E2/S_N2 Competition
The Regioselectivity of E2 Eliminations
The Stereoselectivity of E2 Eliminations
One-Pot Conversion of an Alcohol to an Alkene
E1 Elimination of H/Het from Rtert—X and the E1/S_N1 Competition
Energy Profiles and Rate Laws for E1 Eliminations
The Regioselectivity of E1 Eliminations
E1 Eliminations in Protecting Group Chemistry
E1_cb Eliminations
Unimolecular E1_cb Eliminations: Energy Profile and Rate Law
Nonunimolecular E1_cb Eliminations: Energy Profile and Rate Law
Alkene-Forming Step of the Julia-Lythgoe Olefination
E1_cb Eliminations in Protecting Group Chemistry
?-Eliminations of Het¹/Het²
Fragmentation of ?-Heterosubstituted Organometallic Compounds
Peterson Olefination
Oxaphosphetane Fragmentation, Last Step of Wittig and Hoer–Wadsworth–Emmons Reactions

Substitution Reactions on Aromatic Compounds

Electrophilic Aromatic Substitutions via Sigma Complexes (Ar-SE Reactions)
Mechanism: Substitution of H⁺ vs ipso-Substitution
Thermodynamic Aspects of Ar-SE Reactions
Kinetic Aspects of Ar-SE Reactions: Reactivity and Regioselectivity in Reactions of Electrophiles with Substituted Benzenes
Ar-SE Reactions via Sigma Complexes: Individual Reactions
Ar—Hal Bond Formation by Ar-SE Reaction
Ar—SO₃H Bond Formation by Ar-SE Reaction
Ar—NO₂ Bond Formation by Ar-SE Reaction
Ar—N=N Bond Formation by Ar-SE Reaction
Ar—Alkyl Bond Formations by Ar-SE Reaction
Ar—C(OH) Bond Formation by Ar-SE Reactions and Associated Secondary Reactions
Ar—C(=O) Bond Formation by Ar-SE Reaction
Ar—C(=O)H Bond Formation through Ar-SE Reaction
Electrophilic Substitution Reactions on Metalated Aromatic Compounds
Electrophilic Substitution Reactions of ortho-Lithiated Benzene and Naphthalene Derivatives
Electrophilic Substitution Reactions in Aryl Grignard and Aryllithium Compounds That Are Accessible from Aryl Halides
Electrophilic Substitutions of Arylboronic Acids and Arylboronic Esters
Nucleophilic Substitution Reactions of Aryldiazonium Salts
Nucleophilic Substitution Reactions via Meisenheimer Complexes
Mechanism
Examples of Reactions of Preparative Interest
Nucleophilic Aromatic Substitution via Arynes, cine Substitution

Nucleophilic Substitution Reactions at the Carboxyl Carbon

C=O-Containing Substrates and Their Reactions with Nucleophiles
Mechanisms, Rate Laws, and Rate of Nucleophilic Substitution Reactions at the Carboxyl Carbon
Mechanism and Rate Laws of S_N Reactions at the Carboxyl Carbon
S_N Reactions at the Carboxyl Carbon: The Influence of Resonance Stabilization of the Reacting C=O Double Bond on the Reactivity of the Acylating Agent
S_N Reactions at the Carboxyl Carbon: The Influence of the Stabilization of the Tetrahedral Intermediate on the Reactivity
Activation of Carboxylic Acids and of Carboxylic Acid Derivatives
Activation of Carboxylic Acids and Carboxylic Acid Derivatives in Equilibrium Reactions
Conversion of Carboxylic Acids into Isolable Acylating Agents
Complete in SituActivation of Carboxylic Acids
Selected S_N Reactions of Heteroatom Nucleophiles at the Carboxyl Carbon
Hydrolysis and Alcoholysis of Esters
Lactone Formation from Hydroxycarboxylic Acids
Forming Peptide Bonds
SN Reactions of Heteroatom Nucleophiles with Carbonic Acid Derivatives
S_N Reactions of Hydride Donors, Organometallics, and Heteroatom-Stabilized Carbanions on the Carboxyl Carbon
When Do Pure Acylations Succeed with Carboxylic Acid (Derivative)s, and When Are Alcohols Produced?
Acylation of Hydride Donors: Reduction of Carboxylic Acid Derivatives to Aldehydes
Acylation of Organometallic Compounds and Heteroatom-Stabilized Carbanions With Carboxylic Acid (Derivative)s: Synthesis of Ketones
Acylation of Organometallic Compounds and Heteroatom-Stabilized Carbanions with Carbonic Acid Derivatives: Synthesis of Carboxylic Acid Derivatives

Carboxylic Compounds, Nitriles, and Their Interconversion

Preparation of Nitriles from Carboxylic Acid (Derivative)s
Transformation of Nitriles and Heteroatom Nucleophiles to Carboxylic Acid (Derivative)s

Carbonic Acid Derivatives and Heterocumulenes and Their Interconversion

Preparation of Heterocumulenes from Carbonic Acid (Derivatives)
Transformation of Heterocumulenes and Heteroatom Nucleophiles into Carbonic Acid Derivatives
Interconversions of Carbonic Acid Derivatives via Heterocumulenes as Intermediates

Additions of Heteroatom Nucleophiles to Carbonyl Compounds and Subsequent Reactions–Condensations of Heteroatom Nucleophiles with Carbonyl Compounds

Additions of Heteroatom Nucleophiles or Hydrocyanic Acid to Carbonyl Compounds
On the Equilibrium Position of Addition Reactions of Heteroatom Nucleophiles to Carbonyl Compounds
Hemiacetal Formation
Formation of Cyanohydrins and ?-Aminonitriles
Oligomerization of Aldehydes—Polymerization of Formaldehyde
Addition of Heteroatom Nucleophiles to Carbonyl Compounds in Combination with Subsequent S_N1 Reactions of the Primary Product: Acetalizations
Mechanism
Formation of O,O-Acetals
Formation of S,S-Acetals
Formation of N,N-Acetals
Addition of Nitrogen Nucleophiles to Carbonyl Compounds in Combination with Subsequent E1 Eliminations of the Primary Product: Condensation Reactions

Addition of Hydride Donors and of Organometallic Compounds to Carbonyl Compounds

Suitable Hydride Donors and Organometallic Compounds; the Structure of Organolithium Compounds and Grignard Reagents
Chemoselectivity of the Addition of Hydride Donors to Carbonyl Compounds
Diastereoselectivity of the Addition of Hydride Donors to Carbonyl Compounds
Diastereoselectivity of the Addition of Hydride Donors to Cyclic Ketones
Diastereoselectivity of the Addition of Hydride Donors to ?-Chiral Acyclic Carbonyl Compounds
Diastereoselectivity of the Addition of Hydride Donors to ?-Chiral Acyclic Carbonyl Compounds
Enantioselective Addition of Hydride Donors to Carbonyl Compounds Addition of Organometallic Compounds to Carbonyl Compounds
Simple Addition Reactions of Organometallic Compounds
Enantioselective Addition of Organozinc Compounds to Carbonyl Compounds: Chiral Amplification
Diastereoselective Addition of Organometallic Compounds to Carbonyl Compounds
1,4-Additions of Organometallic Compounds to ?,?-Unsaturated Ketones; Structure of Copper-Containing Organometallic Compounds

Conversion of Phosphorus- or Sulfur-Stabilized C Nucleophiles with Carbonyl Compounds: Addition-Induced Condensations

Condensation of Phosphonium Ylides with Carbonyl Compounds: Wittig Reaction
Bonding in Phosphonium Ylides
Nomenclature and Preparation of Phosphonium Ylides
Mechanism of the Wittig Reaction
Wittig–Hoer Reaction
Hoer–Wadsworth–Emmons Reaction
Hoer–Wadsworth–Emmons Reactions Between Achiral Substrates
Hoer–Wadsworth–Emmons Reactions between Chiral Substrates: A Potpourri of Stereochemical Specialties
(Marc) Julia–Lythgoe- and (Sylvestre) Julia–Kocienski Olefination

The Chemistry of Enols and Enamines

Keto-Enol Tautomerism; Enol Content of Carbonyl and Carboxyl Compounds
?-Functionalization of Carbonyl and Carboxyl Compounds via Tautomeric Enols
?-Functionalization of Ketones via Their Enamines
?-Functionalization of Enol Ethers and Silyl Enol Ethers

Chemistry of the Alkaline Earth Metal Enolates

Basic Considerations
Notation and Structure of Enolates
Preparation of Enolates by Deprotonation
Other Methods for the Generation of Enolates
Survey of Reactions between Electrophiles and Enolates and the Issue of Ambidoselectivity
Alkylation of Quantitatively Prepared Enolates and Aza-enolates; Chain-Elongating Syntheses of Carbonyl Compounds and Carboxylic Acid Derivatives
Chain-Elongating Syntheses of Carbonyl Compounds
Chain-Elongating Syntheses of Carboxylic Acid Derivatives
Hydroxyalkylation of Enolates with Carbonyl Compounds (Aldol Addition): Synthesis of ?-Hydroxyketones and b-Hydroxyesters
Driving Force of Aldol Additions and Survey of Reaction Products
Stereocontrol
Condensation of Enolates with Carbonyl Compounds: Synthesis of Michael Acceptors
Aldol Condensations
Knoevenagel Reaction
Acylation of Enolates
Acylation of Ester Enolates
Acylation of Ketone Enolates
Acylation of the Enolates of Active-Methylene Compounds
Michael Additions of Enolates
Simple Michael Additions
Tandem Reactions Consisting of Michael Addition and Consecutive Reactions

Rearrangements

Nomenclature of Sigmatropic Shifts
Molecular Origins for the Occurrence of [1,2]-Rearrangements
[1,2]-Rearrangements in Species with a Valence Electron Sextet
[1,2]-Rearrangements of Carbenium Ions
[1,2]-Rearrangements in Carbenes or Carbenoids
[1,2]-Rearrangements without the Occurrence of a Sextet Intermediate
Hydroperoxide Rearrangements
Baeyer–Villiger Rearrangements
Oxidation of Organoborane Compounds
Beckmann Rearrangement
Curtius Degradation
Claisen Rearrangement
Classical Claisen Rearrangement
Ireland-Claisen Rearrangements

Thermal Cycloadditions

Driving Force and Feasibility of One-Step [4+2]- and [2+2]-Cycloadditions
Transition State Structures of Selected One-Step [4+2]- and [2+2]-Cycloadditions
Stereostructure of the Transition States of One-Step [4+2]-Cycloadditions
Frontier Orbital Interactions in the Transition States of One-Step [4+2]-Cycloadditions
Frontier Orbital Interactions in the Transition States of the Unknown One-Step Cycloadditions of Alkenes or Alkynes to Alkenes
Frontier Orbital Interactions in the Transition State of One-Step [2+2]-Cycloadditions Involving Ketenes
Diels–Alder Reactions
Stereoselectivity of Diels–Alder Reactions
Substituent Effects on Reaction Rates of Diels–Alder Reactions
Regioselectivity of Diels–Alder Reactions
Simple Diastereoselectivity of Diels–Alder Reactions
[2+2]-Cycloadditions with Dichloroketene
1,3-Dipolar Cycloadditions
1,3-Dipoles
Frontier Orbital Interactions in the Transition States of One-Step 1,3-Dipolar Cycloadditions; Sustmann Classification
1,3-Dipolar Cycloadditions of Diazoalkanes
1,3-Dipolar Cycloadditions of Nitrile Oxides
1,3-Dipolar Cycloadditions and 1,3-Dipolar Cycloreversions as Steps in the Ozonolysis of Alkenes
A Tricky Reaction of Inorganic Azide

Transition Metal-Mediated Alkenylations, Arylations, and Alkynylations

Alkenylation and Arylation of Gilman Cuprates
Arylation and Alkynylation of Neutral Organocopper Compounds I
Alkenylation and Arylation of Grignard Compounds (Kumada Coupling)
Palladium-Catalyzed Alkenylations and Arylations of Organometallic Compounds
A Prelude: Preparation of Haloalkenes and Alkenylboronic Acid Derivatives, Important Building Blocks for Palladium- Mediated C,C Couplings; Carbocupration of Alkynes
Alkenylation and Arylation of Boron-Bound Groups (Suzuki Coupling)
Alkenylation and Arylation of Organozinc Compounds (Negishi Couplings) and of Functionalized Organozinc Compounds
Alkenylation and Arylation of Tin-bound Groups (Stille Reaction)
Arylations, Alkenylations and Alkynylations of Neutral Organocopper Compounds II
Heck Reactions

Oxidations and Reductions

Oxidation Numbers in Organic Chemical Compounds, and Organic Chemical Redox Reactions
Cross-References to Redox Reactions Already Discussed in Chapters 1–16
Oxidations
Oxidations in the Series Alcohol A Aldehyde A Carboxylic Acid
Oxidative Cleavages
Oxidations at Heteroatoms
Reductions
Reductions R_sp³—X ? R_sp³—H or R_sp³ —X ? R_sp³ —M
One-Electron Reductions of Carbonyl Compounds and Esters; Reductive Coupling
Reductions of Carboxylic Acid Derivatives to Alcohols or Amines
Reductions of Carboxylic Acid Derivatives to Aldehydes
Reductions of Carbonyl Compounds to Alcohols
Reductions of Carbonyl Compounds to Hydrocarbons
Hydrogenation of Alkenes
Reductions of Aromatic Compounds and Alkynes
The Reductive Step of the Julia–Lythgoe Olefination

Subject Index