MODERN ARENE CHEMISTRY
CONTENTS ARENE CHEMISTRY: FROM HISTORICAL NOTES TO THE STATE OF THE ART 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 CONTENT REFERENCES THE SYNTHESIS OF TRIS-ANNULATED BENZENES BY ALDOL TRIMERIZATION OF CYCLIC KETONES ABSTRACT INTRODUCTION TRUXENE AND TRUXONE: VENERABLE PROTOTYPES OTHER EXAMPLES LIMITATIONS EXPERIMENTAL OBSERVATIONS AND A WORKING HYPOTHESIS GUIDANCE FROM CALCULATIONS CONCLUSIONS OLIGOUNSATURATED FIVE-MEMBERED CARBOCYCLES – AROMATIC AND ANTIAROMATIC COMPOUNDS IN THE SAME FAMILY CYCLOPENTADIENYL 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-FULLERENE THE SUZUKI REACTION WITH ARYLBORON COMPOUNDS IN ARENE CHEMISTRY REACTIONS WITH ARYL HALIDES AND TRI?ATES: SYNTHESIS OF BIARYLS AROMATIC–AROMATIC COUPLING AROMATIC–HETEROAROMATIC AND HETEROAROMATIC–HETEROAROMATIC COUPLINGS COUPLING OF ARYLBORON COMPOUNDS BEARING STERICALLY BULKY OR ELECTRON- WITHDRAWING SUBSTITUENTS MODI?ED CATALYSTS AND LIGANDS SOLID-PHASE SYNTHESIS (COMBINATORIAL METHODOLOGY) REACTIONS WITH 1-ALKENYL HALIDES AND TRI?ATES REACTIONS WITH ARYL CHLORIDES AND OTHER ORGANIC ELECTROPHILES MISCELLANEOUS APPLICATIONS IN POLYMER CHEMISTRY PALLADIUM-CATALYZED AMINATION OF ARYL HALIDES AND SULFONATES SYNTHETIC 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 TRI?ATES 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 ¼ 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 SPECI?C 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 MONOPHOSPHINES SUMMARY FROM ACETYLENES TO AROMATICS: NOVEL ROUTES – NOVEL PRODUCTS THE 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 ARYLATED TETRAETHYNYLETHENES NONLINEAR OPTICAL PROPERTIES PHOTOCHEMICALLY CONTROLLED CIS–TRANS ISOMERIZATION: MOLECULAR SWITCHES ELECTROCHEMICALLY CONTROLLED CIS–TRANS ISOMERIZATION TETRAETHYNYLETHENE DIMERS TWO-DIMENSIONAL SCA?OLDING: 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 ABBREVIATIONS THE ADIMET REACTION: SYNTHESIS AND PROPERTIES OF POLY(DIALKYLPARAPHENYLENEETHYNYLENE)S SCOPE 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 OUTLOOK THE CHROMIUM-TEMPLATED CARBENE BENZANNULATION APPROACH TO DENSELY FUNCTIONALIZED ARENES (DO¨TZ REACTION) MECHANISM 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 SPECI?C 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 OUTLOOK OSMIUM- AND RHENIUM-MEDIATED DEAROMATIZATION REACTIONS WITH ARENES {OS(NH3Þ5}2Þ – 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 4H-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)} QUADRANT ANALYSIS CYCLOADDITIONS CONCLUDING REMARKS THE DIRECTED ORTHO METALATION REACTION – A POINT OF DEPARTURE FOR NEW SYNTHETIC AROMATIC CHEMISTRY AIMS 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) 10311 FURANS AND THIOPHENES 10312 INDOLES P-DE?CIENT HETEROAROMATIC DIRECTED ORTHO METALATION (HETDOM) 10321 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 COMMENTS ARENETRICARBONYLCHROMIUM COMPLEXES: IPSO, CINE, TELE NUCLEOPHILIC AROMATIC SUBSTITUTIONS E?ECTS ON ARENE REACTIVITY OF CR(CO)3 COORDINATION COVERAGE AND DE?NITIONS 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 ACTIVATION OF SIMPLE ARENES BY THE CPFEB GROUP AND APPLICATIONS TO THE SYNTHESIS OF DENDRITIC MOLECULAR BATTERIES GENERAL 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(H6-C6ME6)]Þ GROUPS: A MOLECULAR BATTERY IN ACTION CONCLUSION CHARGE-TRANSFER EFFECTS ON ARENE STRUCTURE AND REACTIVITY MULLIKEN’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 E?ECT OF CHARGE TRANSFER ON THE STRUCTURAL FEATURES OF COORDINATED ARENES 13331 EXPANSION OF THE ARENE RING 13332 P-BOND LOCALIZATION IN THE ARENE RING 13333 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 MODI?CATION OF THE DONOR/ACCEPTOR PROPERTIES OF COORDINATED ARENE LIGANDS CT COMPLEXES AS CRITICAL INTERMEDIATES IN DONOR/ACCEPTOR REACTIONS OF ARENES E?ECTS OF THE DONOR/ACCEPTOR INTERACTION ON THE ET DYNAMICS OF ARENE DONORS 13511 STERIC CONTROL OF THE INNER/OUTER-SPHERE ELECTRON TRANSFER 13512 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 SUMMARY OXIDATIVE ARYL-COUPLING REACTIONS IN SYNTHESIS MECHANISTIC 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 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 COUPLING OXIDATIVE CONVERSION OF ARENOLS INTO ORTHO-QUINOLS AND ORTHO-QUINONE MONOKETALS – A USEFUL TACTIC IN ORGANIC SYNTHESIS ´ ABSTRACT HOW TO PREPARE ORTHO-QUINOLS AND ORTHO-QUINONE MONOKETALS WHY BOTHER WITH ORTHO-QUINOLS AND ORTHO-QUINONE MONOKETALS? 15121 SYNTHETIC REACTIVITY OF ORTHO-QUINOLS AND ORTHO-QUINONE MONOKETALS 15122 BIOSYNTHETIC IMPLICATIONS OF ORTHO-QUINOLS AND ORTHO-QUINONE MONOKETALS 15123 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 ADDITIONS MOLECULAR SWITCHES AND MACHINES USING ARENE BUILDING BLOCKS FROM 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