Julio Alvarez-Builla, Juan Jose Vaquero,

Transcription

1 Edited by Julio Alvarez-Builla, Juan Jose Vaquero, and Jose Barluenga Modern Heterocyclic Chemistry Volume 1 WILEY- VCH WILEY-VCH Verlag GmbH & Co. KG aa

2 List of Contributors XV Volume 1 1 Heterocyclic Compounds: An Introduction 1 Julio Alvdrez-Builla andjosi Barluenga 1.1 Heterocyclic Compounds: An Introduction Structure and Reactivity of Aromatic Five-Membered Systems Structure and Reactivity of Aromatic Six-Membered Systems Basic Literature on Heterocyclic Compounds 8 References 9 2 Three-Membered Heterocycles. Structure and Reactivity 11 S. Shaun Murphree 2.1 Aziridines Properties of Aziridines Synthesis of Aziridines Aziridinarion ofalkenes Aziridinarion ofimines Ring Closure of Amines Ring Contraction of Other Heterocycles Reactivity of Aziridines Nucleophilic Ring Opening N-Elaboration Reactions Azirdinyl Anion Chemistry Ring Expansions H-Azirines Properties of Azirines Synthesis of Azirines Neber Route From Vinyl Azides 45

3 From Other Heterocycles Reactivity of Azirines Addition of Nucleophiles Cycloadditions Rearrangements into other Heterocycles Oxiranes Properties of Oxiranes Synthesis of Oxiranes Using Dioxiranes Using other Oxidants without Metal Catalysts Metal-Catalyzed Epoxidation of Alkenes Epoxidation of Electron-Deficient Alkenes Epoxidation of Carbonyl Compounds Ring-Closing Reactions Reactivity of Oxiranes Nucleophilic Ring Opening Rearrangements Radical Chemistry Reduction and Deoxygenation Oxiranyl Anions Thiiranes Properties Synthesis of Thiiranes 109 of Thiiranes From Epoxides From Alkenes From Haloketones Reactivity of Thiiranes Nucleophilic Ring Opening Desulfurization Diaziridines Properties of Diaziridines Synthesis of Diaziridines Oxidative Methods using Hypohalites Via Hydroxylamine Other Methods 222 Derivatives Reactivity of Diaziridines Diaziridines Diaziridinones and Diaziridinimines H-Diazirines Properties of Diazirines Synthesis of Diazirines Reactivity of Diazirines Oxaziridines Properties of Oxaziridines Synthesis of Oxaziridines 129

4 VII Reactivity of Oxaziridines Nitrogen Transfer Reactions Oxygen Transfer Reactions Rearrangements Dioxiranes Properties of Dioxiranes Synthesis Reactivity of Dioxiranes 136 of Dioxiranes Epoxidation of Alkenes Hydroxylation of Alkanes Oxidation of Sulfur 138 References Four-Membered Heterocycles: Structure and Reactivity 163 C6rard Rousseau and Sylvie Robin 3.1 Azetidines Introduction Physicochemical Synthesis Cyclization Data 165 Reactions Ring Transformations Cycloadditions Reactivity and Useful Reactions Reactions at the Nitrogen Atom Oxidizing Reactions Reactions with Nucleophiles and Bases Reactions of C-Metallated Azetidines Ring Expansions Cleavage ofthe Azetidine Ring Enzymatic Resolutions of Azetidines Oxetanes Introduction Physicochemical NMR Data 189 Data Infrared Spectroscopy Natural or Bioactive Compounds Synthesis of Oxetanes and Oxetan-2-ones [2+2] Paterno-Biichi Cyclizations Catalyzed [2+2] Cyclizations Ring Contraction of Butanolides Oxirane Ring Opening by Carbanionic Attacks Williamson Reactions Isomerization of Oxiranyl Hydroxyls Oxirane Ring Expansions Electrophilic Cyclizations 196

5 VIII Contents [2+2] Cycloaddition of Ketene and Carbonyl Compounds Acyl Halide-Aldehyde Cyclocondensations C-H Insertions Carbonylative Ring Expansion Reactions P-Hydroxy Acid Cyclizations Reactivity p-lactones Oxetanes Thietanes Introduction Physicochemical Data Natural and Bioactive Compounds Synthesis of Thietanes Synthesis by Formation of a S-C Bond Synthesis by Formation of a C-C Bond Synthesis by Formation of Two S-C Bonds Synthesis from Other Sulfur Heterocycles Synthesis by [2+2] Cycloaddition Synthesis by Miscellaneous Methods Reactivity and Useful Reactions Reactions with Electrophilic Reagents Reactions with Oxidizing Agents Reactions with Nucleophilic Reagents Reactions with Bases Reactions with Metal Complexes and Salts Electrocyclic Reactions Cleavage and Other Reactions Other Four-Membered Heterocycles Selenetanes Introduction Synthesis of Selenetanes Reactivity Telluretanes Phosphetanes Arsetanes Siletanes Introduction Preparation of Siletanes Reactivity Germetanes Introduction Preparations Reactivity Bismetanes and Stibetanes 254 References 254

6 IX 4 Five-Membered Heterocycles: Pyrrole and Related Systems 269 Jan Bergman and TomaszJanosik 4.1 Introduction Nomenclature General Reactivity Relevant Physicochemical Data, Computational Chemistry, and NMR Data Fundamental Reactivity Patterns Relevant Natural and/or Useful Compounds Pyrrole Ring Synthesis Paal-Knorr Synthesis and Related Methods (4+1 Strategy) Other Cyclizations of Four-Carbon Precursors (5+0 and 4+1 Strategies) Knorr Synthesis and Related Routes (3+2 Strategy) Hantzsch Synthesis and Related Approaches (2+2+1 or 3+2 Strategy) Syntheses Involving Glycine Esters (3+2 Strategy) Van Leusen Method (3+2 Strategy) Barton-Zard Synthesis (3+2 Strategy) Trofimov Synthesis (3+2 Strategy) Cycloaddirion Reactions and Related Approaches (3+2 Strategy) Multi-Component Reactions (2+2+1 Strategy) Miscellaneous Transition Metal Catalyzed Methods (3+2 and 5+0 Strategies) Reactivity Reactions with Electrophilic Reagents General Aspects of Reactivity and Regioselectivity in Electrophilic Substitution Protonation Halogenation Nitration Reactions with Sulfur-Containing Electrophiles Acylation Reactions with Aldehydes, Ketones, Nitriles and Iminium Ions Conjugate Addition to a, 3-Unsaturated Carbonyl Compounds Reactions with Oxidants Reactions with Nucleophiles Reactions with Bases N-Metalkted Pyrroles C-Metallated Pyrroles Reactions with Radical Reagents Reactions with Reducing Agents 320

7 X Contents Cycloaddition Reactions Reactions with Carbenes and Carbenoids Photochemical Reactions Pyrryl-C-X Compounds: Synthesis and Reactions Transition Metal Catalyzed Coupling Reactions Pyrrole Derivatives Alkyl Derivatives Pyrrole Carboxylic Acids and Carboxylates Oxy Derivatives Aminopyrroles Dihydro- and Tetrahydro-Derivatives Addendum 349 References Five-Membered Heterocycles: Indole and Related Systems 377 Josi Barluenga and Carlos Vaidis 5.1 Introduction General Introduction System Isomers and Nomenclature General Properties Physicochemical Data General Reactivity Relevant Natural and/or Useful Compounds Indole Synthesis Introduction Synthesis of the Indole Ring from a Benzene Ring Indole Synthesis Involving a Sigmatropic Rearrangement Cyclization by Formation of the N-C2 Bond Ring Synthesis by Formation ofthe C3-C3a Bond Ring Synthesis by Formation ofthe C2-C3 Bond Cyclizations with Formation ofthe N-C7a Bond Synthesis of the Indole Ring by Annelation of Pyrroles Synthesis by Electrophilic Cyclization Palladium-Catalyzed Cyclizations Electrocyclizations [4 + 2] Cycloadditions Indoles from 3-Alkynylpyrrole-2-Carboxaldehydes Reactivity of Indole Reactions with Electrophiles Protonation Friedel-Crafts Alkylations ofindole Nitration Acylation Halogenation 452

8 XI Reactions with Bases N-Metallation of Indoles C-Metallation ofindoles Transition Metal Catalyzed Reactions General Considerations on Palladium-Catalyzed Cross-Coupling Reactions Reactions with Alkenes and Alkynes: Heck Reactions Sonogashira Reaction Cross-Coupling Reactions with Organometallic Reagents C-N Bond-Forming Reactions Transition Metal Catalyzed C-H Activation Radical Reactions Oxidation Reactions Reduction of the Heterocyclic Ring Catalytic Hydrogenation Metal-Promoted Reductions Metal Hydride Complexes Pericyclic Reactions Involving the Heterocyclic Ring Cycloaddition Reactions Electrocyclizations Sigmatropic Rearrangements Photochemical Reactions Reactions with Carbenes and Carbenoids Chemistry of Indole Derivatives Alkylindoles Oxiderivatives Oxindole N-Hydroxyindoles Aminoindoles Indole Carboxylic Acids Addendum Ring Synthesis Fischer Indole Synthesis Reactivity Reactions with Electrophiles Transition Metal Catalyzed Reactions 509 References Five-Membered Heterocycles: Furan 533 Henry N.C. Wong, Xue-Long Hou, Kap-Sun Yeung, and Hui Huang 6.1 Introduction Nomenclature General Reactivity Relevant Physicochemical Data Relevant Natural and Useful Compounds 540

9 XII Contents 6.2 Synthesis of Furans Introduction Monosubstituted Furans Disubstituted Furans Trisubstituted Furans Tetrasubstituted Furans Reactivity Reactions with Electrophilic Reagents Reactions with Nucleophilic Reagents Reactions with Oxidizing Reagents Reactions with Reducing Reagents Reactions with Acids or Bases Reactions of C-Metallated Furans Reactions with Radical Reagents Electrocyclic Reactions Photochemical Reactions Oxyfurans and Aminofurans Oxyfurans Aminofurans Addendum Additional Syntheses of Furans Additional Reactions of Furans 582 References Five-Membered Heterocycles: Benzofuran and Related Systems 593 Jie Wu 7.1 Introduction General Structure and Reactivity Relevant Physicochemical Data, Computational Chemistry and NMR Data Isolation of Naturally Occurring Benzofurans Synthesis of Benzofuran Transition Metal Catalyzed Benzofuran Synthesis Synthesis of 2,3-Disubstituted Benzo[b]furans Oxidative Cyclization Radical Cyclization Acid-and Base-Mediated Cyclization Olefin-Metathesis Approach Miscellaneous Progress in Solid-Phase Synthesis Uses of Benzofuran Uses of Benzofuran in Drug Discovery Uses of Benzofuran in Material Science 625 References 628