Astruc D. (Ed.) Modern Arene Chemistry: Concepts, Synthesis, and Applications

Wiley-VCH Verlag GmbH & KGaA, 2002. — 617 p. — ISBN: 3-527-30489-4.From the very outset, arene chemistry has been one of the most varied and intensively studied areas of research, and has witnessed a rapid growth over the past few years in particular. This book, edited by the renowned chemist Didier Astruc, illustrates the incredible diversity to be found in this fascinating field.List of Contributors
Arene Chemistry: From Historical Notes to the State of the Art
Didier Astruc
The History of Benzene
The History of Aromaticity
Some Key Trends Towards Modern Arene Chemistry
Aromatic Chemistry: From the 19th Century Industry to the State of the Art
Organization of the Book and ContentThe Synthesis of Tris-Annulated Benzenes by Aldol Trimerization of Cyclic Ketones
Margaret M. Boorum and Lawrence T. Scott
AbstractTruxene and Truxone: Venerable Prototypes
Other Examples
Limitations
Experimental Observations and a Working Hypothesis
Guidance from Calculations
ConclusionsOligounsaturated Five-Membered Carbocycles – Aromatic and Antiaromatic Compounds in the Same Family
Rainer Haag and Armin de Meijere
AbstractCyclopentadienyl Cations
Fulvene and Spiroannelated Cyclopentadiene Derivatives
Polyunsaturated Di-, Tri-, and Oligoquinanes
Pentalene, Pentalenediide, and Pentalene Metal Complexes
Acepentalene, Acepentalenediide, and Acepentalene Metal Complexes
Generation of C20-FullereneThe Suzuki Reaction with Arylboron Compounds in Arene Chemistry
Akira Suzuki
AbstractReactions with Aryl Halides and Triflates: Synthesis of Biaryls
Aromatic–Aromatic Coupling
Aromatic–Heteroaromatic and Heteroaromatic–Heteroaromatic Couplings
Coupling of Arylboron Compounds Bearing Sterically Bulky or Electron-Withdrawing Substituents
Modified Catalysts and Ligands
Solid-Phase Synthesis (Combinatorial Methodology)
Reactions with 1-Alkenyl Halides and Triflates
Reactions with Aryl Chlorides and Other Organic Electrophiles
Miscellaneous
Applications in Polymer ChemistryPalladium-Catalyzed Amination of Aryl Halides and Sulfonates
John F. Hartwig
AbstractSynthetic Considerations
Prior CaX Bond-Forming Coupling Chemistry Related to the Amination of Aryl Halides
Novel Organometallic Chemistry
Organization of the Review
Background
Early Palladium-Catalyzed Amination
Initial Synthetic Problems to be Solved
Palladium-Catalyzed Amination of Aryl Halides with Amine Substrates
Early Work
Initial Intermolecular Tin-Free Aminations of Aryl Halides
Initial Intramolecular Amination of Aryl Halides
Second Generation Catalysts: Aryl Bis-phosphines
Amination of Aryl Halides
Amination of Aryl Triflates
Amination of Heteroaromatic Halides
Aminations of Solid-Supported Aryl Halides
Amination of Polyhalogenated Aromatic Substrates
Third-Generation Catalysts with Alkylmonophosphines
High-Temperature Aminations Involving P(tBu)3 as Ligand
Use of Sterically Hindered Bis(phosphine) Ligands
P,N Ligands and Dialkylphosphinobiaryl Ligands
Phenyl Backbone-Derived P,O Ligands
Low-Temperature Reactions Employing P(tBu)3 as a Ligand
Heterocyclic Carbenes as Ligands
Phosphine Oxide Ligands
Heterogeneous Catalysts
Aromatic CaN Bond Formation with Non-Amine Substrates and Ammonia Surrogates
Amides, Sulfonamides, and Carbamates
Allylamine as an Ammonia Surrogate
Imines
Protected Hydrazines
Azoles
Amination of Base-Sensitive Aryl Halides
Applications of the Amination Chemistry
Synthesis of Biologically Active Molecules
Arylation of Secondary Alkylamines
Arylation of Primary Alkylamines
Applications in Materials Science
Polymer Synthesis
Synthesis of Discrete Oligomers
Synthesis of Azacyclophanes
Synthesis of Small Molecules for Materials Applications
Palladium-Catalyzed Amination in Ligand Synthesis
Mechanism of Aryl Halide Amination and Etheration
Oxidative Addition of Aryl Halides to L2Pd Complexes (L = P(o-tolyl)₃, BINAP, DPPF) and its Mechanism
Formation of Amido Intermediates
Mechanism of Palladium Amide Formation from Amines
Reductive Eliminations of Amines from Pd(II) Amido Complexes
Competing b-Hydrogen Elimination from Amido Complexes
Selectivity: Reductive Elimination vs. b-Hydrogen Elimination
Overall Catalytic Cycle with Specific Intermediates
Mechanism for Amination Catalyzed by P(o-C₆H₄Me)₃ Palladium Complexes
Mechanism for Amination Catalyzed by Palladium Complexes with Chelating Ligands
Mechanism of Amination Catalyzed by Palladium Complexes with Sterically Hindered Alkyl MonophosphinesFrom Acetylenes to Aromatics: Novel Routes – Novel Products
Henning Hopf
AbstractThe Aromatization of Hexa-1,3-dien-5-yne to Benzene: Mechanism and Preparative Applications
The Construction of Extended Aromatic Systems from Ethynyl Benzene Derivatives
Bridged Aromatic Hydrocarbons Containing Triple Bonds (Cyclophynes)Functional Conjugated Materials for Optonics and Electronics by Tetraethynylethene Molecular Scaffolding
Mogens Brøndsted Nielsen and Francois Diederich
AbstractArylated Tetraethynylethenes
Nonlinear Optical Properties
Photochemically Controlled cis–trans Isomerization: Molecular Switches
Electrochemically Controlled cis–trans Isomerization
Tetraethynylethene Dimers
Two-Dimensional Scaffolding: Expanded Carbon Cores
Perethynylated Dehydroannulenes
Perethynylated Expanded Radialenes
Cyclic Platinum s-Acetylide Complex of Tetraethynylethene
Linearly p-Conjugated Oligomers and Polymers: Poly(triacetylene)s
Lateral Aryl Substitution
Aromatic Spacer Units
Donor–Donor and Acceptor–Acceptor End-Functionalization
Conclusions
AbbreviationsThe ADIMET Reaction: Synthesis and Properties of Poly(dialkylparaphenyleneethynylene)s
Uwe H. F. Bunz
AbstractScope and Coverage of this Review
Historical Perspective
Syntheses
PPEs by Acyclic Diyne Metathesis (ADIMET) Utilizing Schrock’s Tungsten
Carbyne Complex
Synthesis of Diarylalkynes Utilizing the Mori System
Cycles
Alkyne-Bridged Polymers by ADIMET
Reactivities of PPEs
Solid-State Structures and Liquid-Crystalline Properties of the PPEs
Organometallic Poly(aryleneethynylene)s
Poly(dialkylparaphenyleneethynylene)s
Spectroscopic Properties of Dialkyl-PPEs
UV/vis Spectroscopy of Dialkyl-PPEs
Fluorescence Spectroscopy: The Excited State Story
Self-Assembly of PPEs on Surfaces: From Jammed Gel Phases to Nanocables and Nanowires
PPE-Based Organic Light-Emitting Diodes (OLEDs)
Conclusions and OutlookThe Chromium-Templated Carbene Benzannulation Approach to Densely Functionalized Arenes (Dotz Reaction)
Karl Heinz Do¨tz and Joachim Stendel jr.
AbstractMechanism and Chemoselectivity of the Benzannulation
Mechanism
Chemoselectivity
Scope and Limitations
The Carbene Complex
Availability
The Carbene Ligand
The Chromium Template
The Alkyne
Regioselectivity
Diastereoselectivity
Thermal and Photochemical Benzannulation
Subsequent Transformations
Typical Experimental Procedure
Synthesis of Specific Arenes
Biaryls
Cyclophanes
Annulenes and Dendritic Molecules
Angular, Linear, and Other Fused Polycyclic Arenes
Fused Heterocycles
Synthesis of Biologically Active Compounds
Vitamins
Antibiotics
Steroids
Alkaloids
Summary and OutlookOsmium- and Rhenium-Mediated Dearomatization Reactions with Arenes
Mark T. Valahovic, Joseph M. Keane, and W. Dean Harman
Abstract{Os(NH₃)₅}²⁺ – The Pentaammineosmium(II) Fragment
Preparation of h2-Arene Complexes
Binding Selectivity
Hydrogenations
Benzene and Alkylated Benzenes
Benzene
Toluene
Xylenes
Naphthalene
Tandem Addition Reactions
Cyclizations
Anisole
Electrophilic Substitutions
Tandem Additions
Cyclization Reactions
Aniline
Electrophilic substitution
H-Anilinium Michael Additions
Electrophilic Addition Reactions
Michael–Michael–Michael Ring-Closure
Phenol
Electrophilic Substitution Reactions
Michael Addition Reactions
o-Quinone Methide Complexes
{TpRe(CO)(L)}Preparation of h2-Arene Complexes
Quadrant Analysis
Naphthalene
Cycloadditions
Concluding RemarksThe Directed ortho Metalation Reaction – A Point of Departure for New Synthetic Aromatic Chemistry
Christian G. Hartung and Victor Snieckus
AbstractAims of this Account
The DoM Reaction as a Methodological Tool
The N-Cumyl Carboxamide, Sulfonamide, and O-Carbamate DMGs
The Lithio Carboxylate and Carboxylate Ester DMGs
The Di-tert-Butyl Phosphine Oxide DMG
Heteroaromatic Directed ortho Metalation (HetDoM) in Methodological Practice
p-Excessive Heteroaromatic Directed ortho Metalation (HetDoM)
Furans and Thiophenes
Indoles
p-Deficient Heteroaromatic Directed ortho Metalation (HetDoM)
Pyridines
The DoM–Transition Metal Catalyzed Aryl–Aryl Cross-Coupling Symbiosis
The Suzuki–Miyaura–DoM Link
Aryl O-Carbamate and S-Thiocarbamate–Grignard Cross-Coupling Reactions
The DoM–Negishi Cross-Coupling Connection
DoM–Derived Cross-Coupling Reactions. Synthetic Comparison of Boron, Zinc, and Magnesium Coupling Partners
Beyond DoM: The Directed Remote Metalation (DreM) of Biaryl Amides and O-Carbamates – New Methodologies for Condensed Aromatics and Heteroaromatics
Heteroatom-Bridged Biaryl DreM. General Anionic Friedel–Crafts Complements for Several Classes of Heterocycles
Interfacing DoM with Emerging Synthetic Methods
Closing CommentsArenetricarbonylchromium Complexes: Ipso, Cine, Tele Nucleophilic Aromatic Substitutions
Francoise Rose-Munch and Eric Rose
AbstractEffects on Arene Reactivity of Cr(CO)₃ Coordination
Coverage and Definitions
Ipso Nucleophilic Aromatic Substitutions
Carbon–Oxygen, –Sulfur and –Selenium Bond Formation
Carbon–Nitrogen and Carbon–Phosphorus Bond Formation
Carbon–Carbon Bond Formation
Carbon–Hydrogen and Carbon–Metal Bond Formation
Cine and Tele Nucleophilic Aromatic Substitutions
Cleavage of CaF and CaCl Bonds
Cleavage of CaO Bonds
Cleavage of CaN Bonds
Concluding Remarks
AbbreviationsActivation of Simple Arenes by the CpFeB Group and Applications to the Synthesis of Dendritic Molecular Batteries
Didier Astruc, Sylvain Nlate, and Jaime Ruiz
AbstractGeneral Features of the CpFeþ Activation of Arenes
Complexation and Decomplexation
Solubility, Stability, and General Reactivity Trends
Single-Electron Reduction and Oxidation
Deprotonation
Reaction of the 19-Electron FeI Complex with O2: Extraordinary Reactivity of Naked Superoxide and its Inhibition
Nucleophilic Reactions
Heterolytic Cleavage of Aryl Ethers
CpFeþ-Induced Hexafunctionalization of Hexamethylbenzene for the Synthesis of Metallo-Stars
CpFeþ-Induced Octafunctionalization of Durene in the Synthesis of Metallodendrimer Precursors
CpFeþ-Induced Triallylation of Toluene and Reactivity of the Triallyl Tripod Towards Transition Metals
Nonaallylation of Mesitylene for the Synthesis of Dendritic Precursors of Large Metallodendrimers
CpFeþ-Induced Activation of Ethoxytoluene in the One-Pot Synthesis of a Phenol Dendron by Triple-Branching and Synthesis of Organometallic Dendrons
Convergent and Divergent Syntheses of Large Ferrocenyl Dendrimers with Good Redox Stabilities
Polyferrocenium Dendrimers: Molecular Batteries?
Large Dendrimers Functionalized on their Branches by the Electron-Reservoir [FeCp(η⁶-C₆Me₆)]⁺ Groups: A Molecular Battery in ActionCharge-Transfer Effects on Arene Structure and Reactivity
Sergiy V. Rosokha and Jay K. Kochi
AbstractMulliken’s Quantitative Description of Intermolecular (Charge-Transfer) Complexes
Short Theoretical Background
Quantitative Evaluation of Arenes as Electron Donors
Spectral (UV/vis) Probe for the Formation of CT Complexes
IR Spectroscopic Studies of Charge-Transfer Complexation
Thermodynamics of Charge-Transfer Complexation
Structural Features of Arene Charge-Transfer Complexes
Bonding Distance of the Donor/Acceptor Dyad in Arene Complexes
Relationship Between Hapticity and Charge Transfer in Arene Complexes
Effect of Charge Transfer on the Structural Features of Coordinated Arenes
Expansion of the Arene Ring
p-Bond Localization in the Arene Ring
Loss of Planarity of the Arene Ring and the Transition from p- to s-Binding
Charge-Transfer Activation of Coordinated Arenes
Carbon–Hydrogen Bond Activation
Nucleophilic/Electrophilic Umpolung
Modification of the Donor/Acceptor Properties of Coordinated Arene Ligands
CT Complexes as Critical Intermediates in Donor/Acceptor Reactions of Arenes
Effects of the Donor/Acceptor Interaction on the ET Dynamics of Arene
Donors
Steric Control of the Inner/Outer-Sphere Electron Transfer
Thermal and Photochemical ET in Strongly Coupled CT Complexes
Electron-Transfer Paradigm for Arene Transformation via CT Complexes
Electron-Transfer Activation of Electrophilic Aromatic Substitution
Structural Pre-organization of the Reactants in CT Complexes
CT Complexes in Aromatic Nitration and Nitrosation
Concluding SummaryOxidative Aryl-Coupling Reactions in Synthesis
Guillaume Lessene and Ken S. Feldman
AbstractMechanistic Overview
Oxidative Coupling Reactions with Hypervalent Iodine Reagents
Other Reagents for the Oxidative Coupling Reaction
Iron(III)
Vanadium, Thallium, and Lead
Copper(II)
Electrochemical Methods
Other Metals
Contents xiii
Non-Metal Mediated Methods
Phase-Supported Oxidants
Reagents Supported on Inorganic Materials
Polymer-Supported Hypervalent Iodine Reagents
Control of Atropisomerism
Transfer of Chiral Information via the Molecular Backbone
Oxidative Coupling of Two Chiral Molecules
Stoichiometric Chiral Oxidation Reagents
Catalytic Enantioselective Oxidative CouplingOxidative Conversion of Arenols into ortho-Quinols and ortho-Quinone Monoketals – A Useful Tactic in Organic Synthesis
Stephane Quideau
AbstractHow to Prepare ortho-Quinols and ortho-Quinone Monoketals
Why Bother with ortho-Quinols and ortho-Quinone Monoketals?
Synthetic Reactivity of ortho-Quinols and ortho-Quinone Monoketals
Biosynthetic Implications of ortho-Quinols and ortho-Quinone Monoketals
Biomechanistic Implications of ortho-Quinols and ortho-Quinone Monoketals
Oxidative Dearomatization of ortho-Substituted Arenols
Anodic Oxidation
Metal-Based Oxidative Activation
Halogen-Based Reagents
Synthetic Applications of ortho-Quinols and ortho-Quinone Monoketals
Diels–Alder Cycloadditions
Photochemical Rearrangements
Nucleophilic Substitutions and AdditionsMolecular Switches and Machines Using Arene Building Blocks
Hsian-Rong Tseng and J. Fraser Stoddart
AbstractFrom Self-Assembling [2]Catenanes to Electronic Devices
A Hybrid [2]Catenane Switch
A Self-Complexing Molecular Switch
Pseudorotaxane-Based Supramolecular Machines
[2]Rotaxanes and Molecular Shuttles
The Evolution of Photochemically Driven Molecular Switches
Chemically Switchable Pseudorotaxanes
Molecule-Based XOR Logic Gate
Conclusions